Jalal Bacharouche

Mathieu Wagner

Carine Diebold

Jean-Nicolas Munsch

Patrice Brender

Sébastien Schlinger

Emilien Buet

Judith Böhmler

Guillaume Colombe

Arnaud Bach

Philippe Bernardo

Alexandre Geissler

Marie Palmieri

Mohammad Rajab

Houssam Hamie

Ahmad Fahs

Emilia Kulaga

Nicolas Ducruet

Helena Marques

Da Silva

Christine De Saint-Aubin

Alicia Henry

Campus... Dorris Moura

Abdallah Ghaddar

scientific and personal perspective. In particular, Enormous

Conclusion 59

Conclusion

Part 2: Drying-mediated assembly of gold NPs in mesoscale structures on model solid surfaces

Conclusion Conclusion

Part 3: Aging of the aggregation structures vs NPs mobility 177

Part 1: Presentation of the Nanomaterials _Introduction self-organize NPs into a well-defined structure on rigid substrates at the nanoscale.

Hence, highly-ordered particles distribution will lead to new collective physical properties. One of the most effective and simple method to achieve this challenge at the nanoscale, is to combine the adsorption of NPs and self-assembled monolayers (SAMs)

pre-coated surface.

SAMs are formed when molecules spontaneously adsorb as monomolecular layer on surfaces. The concept of this system corresponding to a two-dimensional molecular film that is self-organized at the liquid-gas interface, was introduced by Langmuir who received in 1932 the Nobel Prize in Chemistry for his work on monolayers and surface chemistry. Molecular self-assembled surfaces, especially surfaces made from octadecyltrichorosilane (C18H37SiCl3) were first introduced by Sagiv. 17 He used a technique which is an alternative to the method developed by Langmuir. The molecules in this case, spontaneously adsorb onto a solid surface to decrease its surface free energy. The chemisorption of the molecules "head groups" lead to the formation of wellorganized monolayers. Because of the strong molecules-surface interaction, these monolayers are more stable than the physisorbed ones obtained by Langmuir-Blodgett.

 19, 20 (e.g. Si: SiO2, Al: Al2O3, glass, etc.)

 In all cases, the interactions

"Anything which can be counted is finite and will come to an end" Ali Al-Mortadhâ (A) To those who had opened to me the door to live, to learn, to love and to be loved;

my father Hassan and my mother Zahra

My love for you is uncountable "Yestarday I was with you; today I have become the object of a lesson for you, and tomorrow I shall leave you..."

Ali Al-Mortadhâ (A) First of all, I would like to thank Dr. Hamidou Haidara who gave me the opportunity to join his group ("PMA" of the Institut de Science des Matériaux de Mulhouse) and who opened to me the prospects of research world. I am grateful for every discussion we had together, and for every lesson that lights me the way to knowledge. I express my gratitude to his rich humility, his humanity and his great attitude... I am indebted to my co-adviser Dr. Karine Mougin for his help at every step on the road of experimental work. I am thankful for his optimism, his patience and his trust in me. I would also like to thank her because she gave me the opportunity to work in the FANAS project (ESF) which showed me research life in different European countries and which allowed me to meet marked researchers. f.Influence of the topography of the substrate g.Influence of scan velocity

Conclusion

Conclusion

General conclusion 227

General Annexe: Combined electrostatic-covalent building of gold nanoparticles multilayers, and their size enhanced cohesive and SERS properties A1

General Introduction

The development and the structuring of materials at the nanoscale can address new physics but also can perform features that are operating on original principles. This originality is determined by the unique properties of nanomaterials. These properties are used in particular for new technological applications in many fields: medicine, energy, electronics, optics, catalysis... The critical parameter in most of these properties is the small size of the material itself or of the unit object composing the nanomaterial (typically from 1 nm to 100 nm) that causes an increase in the (surface / volume) ratio.

This work deals with the study of the drying-mediated assembly of colloidal gold nanoparticles (Au NPs) in mesoscale aggregation patterns and their manipulation by atomic force microscopy (AFM) on model surfaces. The objective of this work is twofold.

First, it is aimed at understanding and controlling the genesis of original drying structures and patterns NPs based complex fluids. And secondly, we seek to understand and relate the stability of the NP-based structures (cohesion and dislocation/ desaggregation) to the intrinsic mobility of the constitutive unit NPs on various substrates.

First, we will discuss the synthesis of two nanostructured materials. These materials are the basis of systems development at the mesoscopic scale, but also of the fundamental understanding of phenomena and physical parameters that are acting at the nanoscale.

These materials are the Au NPs and the self-assembled molecular surfaces (SAMs) on rigid substrates, which are the supports for the assembly and the structuring of NPs.

The morphology (size and shape) and the surface chemistry (functionality of grafted molecules) of NPs are adjusted during their chemical synthesis to control the physical and the chemical properties of the studied nano-objects. Similarly, the chemical nature and the surface topography of the substrates were modified and adjusted by grafting of homogeneous and heterogeneous self-assembled molecular films.

As a second step, we will discuss the assembly of NPs in mesoscale and complex aggregation patterns assisted by the wetting and the drying of complex fluids (suspensions of NPs, mixed NPs / biopolymers solutions) on model surfaces. Indeed, it is an important issue, both for understanding fundamental processes of self-organization, and for generating new and functional mesostructures (textured coatings for catalysis and adsorption, inkjet, conductive network of NPs, nanocomposites organic / inorganic).

These assembled structures of molecules and particles from the dewetting of multicomponent solutions are also recurrent in everyday life, as illustrated by the famous ring of drying suspensions drops, and described by Deegan "coffee-ring stains".

Moreover, the drying of certain complex fluids also leads to the emergence of aggregation structures, highly more complex than the annular aggregates that form at the periphery of drying colloidal drops [figure 1]. As described by Deegan, the richness and the aesthetics of these complex structures generated by these phenomena reflect not only the interfacial and bulk properties of the fluids (different sizes and characteristics length scales, phase changes during evaporation), but more importantly, the coupling between the fluid properties and those of the surface substrate (interactions, confining, hydrodynamic). The present work presents, in the case of two important materials, the suspensions of Au NPs and of polysaccharide (Sodium Alginate), the formation of these complex structures of aggregation (fractals, dendrites in particular [figure 1]). The mechanisms and the critical parameters that govern the formation of these complex patterns (size effect of NPs, drying temperature, surface chemistry of the substrate, and residual effect of ions pH in solutions ...) will be studied as well as their physical properties, and in particular, the optical and the thermomechanical properties. In addition, we will study the formation of (Alginate / Au NPs) assemblies in composites fibrillar structures and the different parameters that influence the formation of such complex structures and topology.

The combination between these processes of self-assembly of NPs assisted by wetting, and the use of templates in the system will be also discussed toward the formation of functional and regular structures of NPs, and (Alginate/NPs) composites at the mesoscale.

This study on the assembly of NPs assisted by the wetting and the drying of complex fluids will enable us to better describe, on a phenomenological standpoint, the mechanisms behind the morphogenesis of complex or functional structures, with the ultimate goal to control their formation and their collective properties (physicochemical, thermomechanical, optical ...).

In a third step, we will be interested in the study and the understanding of the aging of the so-formed structures. This aging causes the degeneration of these structures and results in their breakup, via the mobility of nanoparticle aggregates on the surface. The parameters that will be addressed in the aging study are the kinetics of degeneration, the NPs size and functionalization, the presence of alginate in the structure and the environmental conditions (the relative humidity). To better understand this issue of mobility of NPs, a detailed study based on the manipulation of nanoparticles by atomic force microscopy in tapping mode (AFM) [Figure 2] will be developped. The threshold dissipated energy to manipulate (move) the NPs can be quantified according to the intrinsic parameters of the particle (size, shape, and chemical nature), the chemical nature and topography of the substrate, and finally the operating and environment conditions. This work will enable us to understand the mechanisms and characterize the critical parameters at the origin of the wetting and drying mediated assembly of molecules and particles in complex structures, and to control some of their morphology, depending on the nature of the fluid and the substrate. Finally, this work proposes a mechanism of evaluation and of monitoring of the stability and the aging of these aggregation structures, in particular, those from the drying process of films and drops of solutions of nano-objects (colloidal suspensions: metal nanoparticles, blood: proteins, viruses ...).

Introduction

On December 29, 1959, the influential physicist Richard P. Feynman presented a talk to the American Physical Society entitled "There's Plenty of Room at the Bottom: An Invitation to Enter a New Field of Physics." 1 Among physicists, this is respectfully called "the classic talk". He asked "Why cannot we write the entire 24 volumes of the Encyclopedia Brittanica on the head of a pin?" and introduced the concept of nanotechnology.

Though Feynman's speech inspired many researchers, it wasn't until the mid-1980s that nanotechnology began to seep into the cultural mainstream conversation. In 1986, the researcher K. Eric Drexler wrote "Engines of Creation" which laid out extensive prospects of emerging nanotechnology research. 2 What is nanotechnology? "For many scientists it is nothing startlingly new; we have been working at the nanoscale for decades, through electron microscopy, scanning probe microscopies or simply growing and analysing thin films. For most other groups, however, nanotechnology means something far more ambitious, miniature submarines in the bloodstream, little cogs and gears made out of atoms, space elevators made of nanotubes, and the colonization of space"… 3 Nanotechnology is primarily concerned with making things smaller. Scientists have been studying and working with nanoparticles for centuries, but the effectiveness of their work has been hampered by their inability to see the structure of nanoparticles. In recent decades the development of microscopes capable of displaying particles as small as atoms has allowed scientists to see what they are working with. The ability to see nano-sized materials has opened up a world of possibilities in a variety of industries and scientific endeavors. Because nanotechnology is essentially a set of techniques that allow manipulation of properties at a very small scale, its applications is spread out in a large range of domains varying from medicine, 4 environment, 5 food, 6 electronics, 7 energy, 8 up to space and MEMs 9 [figure 1.1]. In this context of emerging nanoscience and nanotechnology, gold, which is the subject of one of the most ancient themes of investigation in science, now leads to an exponentially increasing number of publications in the field of nanoparticles (NPs), particularly of colloidal solutions. 10 Historically, the extraction of gold started in the 5 th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that "soluble" gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass and for coloring ceramics and these applications are still continuing now. Perhaps the most famous example is the Lycurgus Cup that was manufactured in the 5th to 4th century B.C. It is ruby red in transmitted light and green in reflected light, due to the presence of gold colloids. 7 B. Yu, M. Meyyappan, Solid-State Electronics, 2006, 50, 536. 8 V. Balzani, A. Credi, M. Venturi, Nanotoday, 2007, 2, 8. 9 S. Santoli, Acta Astronautica, 1999, 44, 117. London. 11 The reputation of soluble gold until the Middle Ages was to disclose fabulous curative powers for various diseases, such as heart and venereal problems, dysentery, epilepsy, and tumors, and for diagnosis of syphilis (detailed in the first book on colloidal gold written by the philosopher and medical doctor Francisci Antonii in 1618). 12 However, we had to wait until 1857 and Faraday to understand the composition and the synthesis of this solution. Indeed, he published a paper entitled 'Experimental relations of gold (and other metals) to light' 13 in Philosophical Transactions and reported during his Bakerian lecture at the Royal Society in London on 5 February 1857, the formation of deep red solutions of colloidal gold by reduction of an aqueous solution of chloroaurate (AuCl4 -) using phosphorus in CS2 (a two-phase system). He investigated the optical properties of thin films prepared from dried colloidal solutions and observed reversible color changes of the films upon mechanical compression (from bluish-purple to green upon pressurizing). The term "colloid" (from the French, colle) was coined shortly thereafter by Graham, in 1861. 14 Dealing with gold nanoparticles, the recent and major progresses have been performed

in the spherical NPs synthesis and functionalization. The control of the NPs structural parameters such as particle diameter, chemical surface functionality, leads to a better 11 H. Tait (ed.), Five thousand years of glass, London, The British Museum Press, 1991.

12 F. Antonii, Panacea Aurea-Auro Potabile; Bibliopolio Frobeniano: Hamburg, 1618. 13 M. Faraday, Philos. Trans., 1857, 147, 145.

control of their organization on rigid substrates. 10,15 However, additional parameters such as operating conditions (temperature, humidity rate), additives and asymmetrical nanoparticles (rods, wires, triangles and tubes structures) also contribute to create either well-ordered or more random arrangement of NPs. 16 The key issue of these nanoscience topics is the full control of all these physico-chemical parameters to easily between the substrate and the organic films are sufficiently strong (chemical or physical ones) that they insure SAMs stability.

Molecular self-assembly opens new perspectives as the possibility of direct grafting on rigid substrate, a high capacity molecular compaction, a highly ordered network, a thermal stability over a wide temperature range, and an adjusted surface reactivity according to the choice of terminal features of embedded molecules. They also offer a unique combination of physical properties that allows fundamental studies of interfacial chemistry, solvent-molecule interactions and self-organization. For instance, SAMs represent invaluable surface in bioanalytical, organometallic, physical organic, bioorganic and electrochemistry. 25 They can serve as models for studying membrane properties of cells and organelles and cell attachment on surfaces. 26 SAMs can also be used to modify the surface properties of electrodes, electronics connection and mechanical properties, in the field of electronics and electrochemistry especially NEMS and MEMS. 26 In this part, we will discuss the synthesis of two nanostructured materials. These materials are the Au colloidal NPs and the self-assembled molecular surfaces (SAMs) on rigid substrates, which are the supports for the assembly and the structuring of NPs.

First, we introduce the synthesis of spherical gold nanoparticles. The morphology (size and shape) and the surface chemistry (functionality of grafted molecules) of NPs are adjusted during their chemical synthesis to control their physical and chemical properties. These NPs where then characterized by using transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy (UV-VIS). Finally, we present the elaboration of homogeneous and patterned SAMs (micro-contact printing) and their characterization by wettability, ellipsometry and atomic force microscopy (AFM). 22

Why gold?

What are the characteristics that make gold an ideal material for nanotechnologies? In its natural form (in volume), gold is a yellow metal structure face-centered cubic, whose boiling point is at 1068 ° Celsius. Like other materials such as platinum (Pt) and Palladium (Pd), but cheaper to operate, gold (Au) is chemically inert. It is characterized by its resistance to oxidation; it is a metal which does not deteriorate over time (an advantage that does not exist with most of other metals).

Gold NPs are also able to express new physical, chemical and mechanical properties, and provide opportunities to develop new phenomena. Its macroscopic properties are not those used at the nanometer scale. At this scale (1 nm = 10 -9 m) gold has very interesting optical properties. For instance, spherical Au NPs suspensions change of color from red to purple depending on NPs size. Other colors like green and blue can also be obtained by varying NPs form factor, such as NPs more or less elongated (rods).

In addition, when a metal particle is subjected to an electromagnetic field whose 0.0001 0.001 0.01 0.1 1 10 100 1000 µm

Real solutions

Hardly visible

Nano-Colloidal solutions

Visible by TEM

Emulsions and suspensions

Visible by SEM wavelength  is much larger than the particle size :  >> particles, all the free electrons of the conduction band sustain the same field and oscillate collectively in phase. When the frequency of these oscillations corresponds to the frequency of the electromagnetic field, there is a resonance phenomenon, known as surface plasmon resonance (SPR).

This resonance occurs in the region of visible, hence the coloring of these NPs. For example, 10 nm diameter gold NPs have a plasmon resonance band at 520 nm and suspension is red colored (absorption in green).

Finally, the chemical reactivity of gold NPs and their properties of adsorption and oxydoreduction of molecules are related to their surface area due to the variation of configurations of atoms and the electron density at NPs surface. This chemical reaction provides specific catalytic properties of gold NPs. In particular, nanostructured films based Au NPs have appeared as promising functional structures for applications as catalysis. 1,2,3 Another interesting application is the Surface Enhanced Raman Spectroscopy (SERS). 4,5,6 Indeed, when a light wave is highly intense (laser), it causes a non-linear response of the material. Thus, the absorption of light energy by gold NPs dispersed in a dielectric environment (insulating material) generates both: linear optical effects and non-linear and thermal effects. The contribution of NPs versus non-linear effects is based on the strong local fields that exist around them. The plasmon resonance induced by the incident light wave leads to highly intense electric fields. This purpose reinforces the non-linear effects and appears to play an important role in the phenomenon of Raman Scattering and detection of traces of molecules [See general Annexe].

a. Methods of preparation

Since 1990, the preparation and stabilization of colloidal suspensions containing metal nanoparticles have been intensively studied. According to Aiken and Finke, 7 the synthesis of colloids can be achieved using one of the five main modes listed below: Frens 10 introduced the way to tune NPs size (between few nanometers up to one hundred nanometers) by controlling the operating parameters such as temperature and amount of surfactants. Additionally, by switching the choice of the experimental conditions and additives (such as surfactants, reducers agents) the shape of the particles can be easily tuned (especially for elongated particles such as golds nanorods). 23 In wet-chemical synthesis, stabilization of the zero-valent nanoparticles is achieved using various ligands, surfactants, polymers, and biological molecules as protective agents, which offer excellent control over morphologies of the nanocolloids.

b. Modes of stabilization

Nanoparticles in suspension do not represent a thermodynamically stable system. They tend to coalesce and agglomerate to form solid metal, less energy entity, which precipitates in solution. 24 Therefore, suspension needs to be stabilized. There are generally two types of stabilization: electrostatic and steric ones.

Steric stabilization represents a method commonly used in colloidal suspension. It Electrostatic stabilization is achieved by introducing ionic species in solution such as carboxylates. Indeed, Van der Waals forces lead to an attraction between NPs in suspension. To relieve this phenomenon and stabilize NPs, the addition of ionic compounds that will adsorb on the surface of NPs leads to formation of a NPs protective layer. This surface electrostatic repulsion will insure repulsive forces between NPs and drive to the stabilization of the nanoparticular suspension as displayed in figure1.1.0.3. The stability of a colloidal solution results from the balance between attractive and repulsive interactions acting on the particles. These interactions also depend on various parameters such as temperature and pH of the solution. In addition, stabilizers combine these two phenomena and are entitled electrosteric ones.

In this work, nanoparticles will be stabilized by surfactants (charged or not). However, obtaining pure Au nanoparticles in suspension is highly difficult due to their high susceptibility to coalesce at nanoscale. Their size will vary from few nanometers up to one hundred nanometers, and their shape will be mainly controlled by addition of reducers / surfactants or operating conditions such as temperature. 10,25,26 In the following paragraph, we will introduce the synthesis and functionalization of spherical and rod nanoparticles as well as their characterisation using techniques such as TEM and UV-vis spectroscopy.

Gold Nanospheres

Many efforts were devoted to synthesize colloidal gold nanospheres. Indeed, the method pioneered by Turkevich 9 in 1951 and refined by Frens 10 in 1970s, is the simplest available one. It is used to produce modestly monodispersed spherical gold nanoparticles suspended in water of around 10-20 nm in diameter. It involves the reaction of small amounts of hot chlorauric acid with small amounts of sodium citrate solution. After dissolving HAuCl4, the solution is rapidly stirred while a reducing agent is added. This causes Au 3+ ions to be reduced to neutral gold atoms. As more and more of these gold atoms form, the solution becomes supersaturated, and gold gradually starts 25 S. J. Oldenburg, , R.D. Averitt, S.L. Westcott, N.J. Halas, Chem. Phys. Lett., 1998, 288, 243. to precipitate in the form of sub-nanometer particles [figure 1.1.1.1]. The rest of the gold atoms that form stick to the existing particles, and, if the solution is stirred vigorously enough, the particles will be fairly uniform in size. A second method was proposed by Brust and Schiffrin in the early 1990s. 28 It involves the reaction of a chlorauric acid solution with tetraoctylammonium bromide (TOAB) solution in toluene and sodium borohydride as an anti-coagulant and a reducing agent, respectively. It is important to note that TOAB does not bind to the gold nanoparticles particularly strongly, so the solution will aggregate gradually over the course of approximately two weeks. Additional techniques have also been proposed using reducing agent such as carbohydrate or proteins. Panigrahi et al. reported sugar assisted metallic nanoparticles synthesis. 29 Spherical nanoparticles of approximately 1, 3, 10 and 20 nm sizes were prepared reproducibly for gold, platinum, silver and palladium, respectively. They addressed the effect of three different sugars (glucose, fructose and sucrose) as reducing agent on the sizes for different metal nanoparticles synthesis. 27 H. Bonnemann, R. Richards, Eur. J. Inorg. Chem., 2001, 10, 2455.

28 M. Brust, M. Walker, D. Bethell, D.J. Schiffrin, R. Whyman, J. Chem. Soc., Chem. Commun., 1994, 801.

29 S. Panigrahi, S. Kundu, S.K. Ghosh, S. Nath, T. Pal, Journal of Nanoparticle Research, 2004, 6, 411. Yokota et al. succeed to synthesize gold nanoparticles from tetrachloroauric acid through a novel redox reaction in an aqueous N-methylmorpholine-N-oxide (NMMO) solution, which is a well-known solvent for structural carbohydrates such as cellulose. 30,31 Dhar et al. used "Gellan Gum" as a reducing and stabilizing agent for the synthesis of gold nanoparticles. 32 These nanoparticles display greater stability to electrolyte addition and pH changes relative to the traditional citrate and borohydride reduced nanoparticles. Finally, a different process based on ultrasound (sonochemical synthesis), 33,34 has been also proposed. The mechanisms for the reduction of HAuCl4 still remain unclears; the ultrasound induced reduction is a consequence of acoustic cavitation in solution. It sounds that the high temperatures and pressures that occur within a collapsing bubble due to acoustic cavitation may cause hemolytic dissociation of water and other species to produce reducing radicals. 35 This previous paragraph enables to summarize the various wet-chemical processes, and particularly those by chemical reduction of metal salts to synthesize Au nanoparticles and control their size, and spherical shape. However, their surface modification is also crucial. In the following part, we present ones of the most commonly works carried out on Au particles surface functionalization using thiols molecules.

Au NPs Capping -Thiol functionalization

Conventional Nps functionalization methods are tuneable and allow improvement of the modification of Nps surface functionality by adjusting the step procedure numbers: from one step (in-situ synthesis) up to serveral ones (ex-situ), if necessary. The stabilization of gold NPs with alkanethiols is a direct result of advancement in the passivation of two- dimensional gold surfaces using alkanethiols in the late 1980s and early 1990s

(resulting in the formation of self-assembled monolayers on gold substrates). 36 -One-step procedure

The first report regarding the capping of Au NPs with alkanethiols was made by Giersig and Lulvaney in 1993. 37 Because of the increasing demand of improvement of NPs coating, capping agent exchange has been performed by replacing it with more stable molecules such as thiols ones. Indeed, one needs to attach new further functionalities to the as-synthesized NPs to maintain simultaneously their size and shape and to improve the performance of fabricated advanced materials based NPs.

-Two-step procedure Two-step procedures have been developed to exchange Au NPs coating functionalities.

For instance, Manna et al. reported the synthesis of gold NPs surface-confined by hybrid self-assembled monolayers; he proposed to replace dendrimer-passivated NPs coating by dodecanethiol. 40 The hybrid particles were also separated into domains of small and large spheres. This also indicates that the replacement may be dependent on the particle 36 M.G. According to literature, the terminal functionality of NPs can be easily controlled using thiols as stabilizers. The NPs functionalization can be easily achieved either in one-step synthesis method or in a two-steps approach by exchanging the ligand of the assynthesized NPs with thiols molecules, which facilitate the versatility of the system.

Among all the various methods of NPs synthesis and functionlization used in wetchemical techniques, we will present in the following paragraph, the procedures we have chosen to synthesize Au NPs of diameter varying from 5 up to 100nm as well as their functionalization and their chemical and morphological characterization.

a. Synthesis of gold colloidal nanospheres

The source of gold used in the laboratory is a solution of Gold (III) chloride trihydrate [HAuCl4, 3H2O ]. 42,43,44 The technique proposed to prepare 10-50 nm diameter gold NPs is the Frens' one. Ions will be reduced and/or stabilized by a salt such as sodium citrate dihydrate (Na3-citrate) [HOC (COONa) (CH2COONa)2 . 2H2O] and heating at optimal temperature to obtain the NPs requested size.

To produce smaller NPs, additional salts will be used such as Sodium Borohydride

Mechanism of formation of gold colloidal NPs

HAuCl4 is dispersed in water, reduced by Na3-citrate who will also stabilize Au NPs Stronger reducing agents produce smaller seed nuclei, which generate smaller size particles.

Synthesis of various sizes of spherical Au NPs ranging from 2 to 35nm diameter and their TEM characterization have been carried out. In the following section, we will focus on their functionalization with thiols molecules to control their terminal functionality and their surface chemistry.

b. Functionalization of gold colloidal nanospheres

The modification of NPs surface chemistry enables to tune the functionalities of the as- This two steps procedure is also appropriate and relevant to graft thiols molecules presenting hydrophilic end-groups onto gold NPs.

We here presented the results of the characterization of each freshly prepared Au suspension by TEM with their synthesis protocol. In the following paragraph, we will focus on the characterization of the different synthesized NPs suspensions using UVvisible spectroscopy.

c. Characterization of Au NPs suspensions

We here present the results of the characterization of each freshly prepared Au NPs suspension by UV-visible spectroscopy, and show the method used to determine their concentrations. All the solutions have a comparable weight concentration of the order of 0.005 % and their volume fractions are around 2.55 x 10 -4 . However at a constant volume fraction, particles number in the suspension slightly decreases with their average diameter.

The following paragraph presents the UV-vis characterization of the different suspensions presented in the previous table.

c.2. UV-vis spectroscopy

Dependence on particle size

Suspensions A (35 nm), B (25 nm), C (15 nm), D (3 nm) and E (5 nm) have been characterized by UV-spectroscopy and the variation of absorbance has been measured versus the size of the particle and reported in Figure 1.1.1.9. The maximum absorbance peak is characteristic of the size of the NPs. We observe in figure 1.1.1.9 that the 15 nm diameter NPs display a band with a maximum absorption peak at 570 nm, which is in agreement with literature. 47 We have extracted the wavelength at the maximum absorbance peak for NPs diameter ranging At the end of this section, we notice that the UV-vis technique is complementary to TEM characterization. Whereas TEM images enables to detect the morphology (size and shape) of NPs, the UV-vis spectra display their maximum absorbance peaks and their dependence on the NPs sizes.

In this first section, we have shown the synthesis of different sizes of spherical NPs, their functionalization and their characterization with TEM and UV-vis techniques. The next section will discuss the synthesis, the functionalization and the characterization of asymmetrical Au NPs, and particularly elongated gold nanorods (GNRs).

Gold nanorods

Since rod-like gold particles were observed as byproduct of spherical nanoparticles in 1992, 50 many efforts have been made to move beyond conventional spherical growth to achieve shape control. In the first observation of rod-like gold nanoparticles, UVirradiation was used as a reduction path and with alkyltrimethylammonium chlorides as a stabilizer. section diameter) less than 5 were obtained. 53 However this method has a limitation to produce a large amount of nanorods since the reactor size was limited. Hereafter, various approaches have been attempted to produce gold nanorods (GNRs) such as top down techniques as electron beam lithography, 54 or bottom up ones as electrochemical, 55 bio-reduction, 56 growth of nanorods directly on mica surface, 57 and chemical reduction. 58,59 The simplest and common method developed still remains the chemical reduction method and, in particular, the seed mediated synthesis. This method corresponds to a two step procedure. First, gold nanospheres are produced by chemical reduction of a Au salt using a strong reducing agent such as sodium borohydride; these seeds are then added to a growth solution of gold salt including a weak reducing agent and cetyltrimethylammoniumbromide (CTAB). Jana et al. modified the seed-mediated 60 synthesis of nanospheres to obtain nanorods by changing the concentration of surfactant and adding AgNO3. 58 This last seed-mediated procedure enables to provide rods with higher aspect ratios than those prepared with other methods. This method was used in this work.

The stability of the NPs suspensions will strongly dependent on the functionalization of the NPs and the solvent medium. As it has been shown in the previsous section, citratecapped spheres (terminated with COO -groups) are dispersed in water due to the hydrophilicity of citrate periphery. On the contrary, NPs covered with non-polar alkyl chains are mainly hydrophobic and need to be dispersed in non-polar solvent. The same approach can be adopted for Au nanorods. The control of the structural and chemical modification of Au NPs have a strong impact on the functional properties and performance of fabricated advanced materials based on nanorods, which depend greatly of the composition and arrangement of rods. However, literature on asymetrical Au NPs is nowadays rich but remains poor on the way to adjust their functionalization. The main difficulty comes from the strong attachment of the CTAB molecules (bilayers) on their surface. To avoid a tough work of removing strongly attached CTAB bilayer to the rods, different approaches have been proposed. A wrapping up process of nanorods in an anionic polyelectrolyte such as polyacrylate (PA), can be achieved through electrostatic interaction with cationic CTAB molecules. 61,62,63 The research has been extended to layer-by-layer coating on gold nanorods by using PA and polyaniline derivatives.

However, additional techniques have been suggested using thiol compounds. 64 Hydrophilic thiol compounds such as mercaptopropionic acid (MPA), cysteine (Cys) and thiol terminated poly(ethylene glycol) (PEG-SH) are mainly used. Small MPA and Cys molecules prefer to be adsorbed on the edge of gold nanorods, leading unique edgeedge aggregation via hydrogen bond between carboxyl groups. Biocompatible gold nanorods can be obtained by PEG-SH modification due to the biocompatibility of PEG, and the PEG-modified gold nanorods are applicable to living cells with the aim of cell staining. In addition, inorganic coatings based on silica have also been reported. 65 Hereafter, we will propose a new technique based on a two steps process quite similar to the procedure to functionalize spherical particles described in previous section. This section will describe the synthesis of two different aspect ratios nanorods (2.6 and 14), their functionalization, and their characterization with TEM and UV-vis spectroscopy.

a. Preparation of gold nanorods

The synthesis of Au nanorods is quite similar to the synthesis of large spherical particles as it requires the preparation of a seed solution, but it still remains more complex as this procedure is a multiple-steps process to allow the growth of the asymetrical rods along its longitudinal axis.

Mechanism of growth

The orange colour of the gold salt in the CTAB solution disappeared when ascorbic acid was added. This colour change is attributed to the reduction of Au 3+ to Au + by ascorbic acid. Further reduction of Au + to Au 0 occurs when 1.0 mL of the seed solution is mixed with sample A (step 1). This is evidenced by a rapid development of red colour to the solution in sample A, which earlier was colourless, thus indicating the formation of gold nanoparticles. After 15 s, 1 mL of sample A was mixed with sample B (step 2). This leads to a colour change in sample B, indicating the generation of gold nanoparticles. The reduction in this case is slower compared to that in step 1. 5 mL of sample B was further added to sample C after 30 s (step 3). The colour of this solution slowly changed to purple. In all cases, each flask was gently stirred to homogenize the solutions. The solution in flask C was kept at 25 °C for a period of 16 h.

In the following we describe the new two-step process proposed to modify the assynthesized Au nanorods.

b. Re-functionalization of Au nanorods

The process is based on a two-step method. The first part allows to remove the stabilizer surrounding the as-synthesized NPs and then to exchange the possible residual molecules by the desired ones. The re-functionalization of Au nanorods approach is described in the following paragraph.

10 mL of the initial solution were centrifuged with a speed of 10 4 rotations per minute, for 20 minutes, 3 times. The supernatant is removed each time and 10 mL of milli-Q water were added under ultrasonic vibrations for several minutes. To oxidize and eliminate residual organic layer, few drops of H2O2 solution (37% weight in water) is added. This last solution was then centrifuged again as previously and redispersed in the more convenient solvent. The final step is by adding 1 mL of 10% 11-Mercapto-1undecanol (prepared in ethanol) under ultrasonic vibrations for several hours to allow the grafting reaction to reach completion. The resulting Au nanorods are functionalized with COO -termination functionality (hydrophilic particles). The volume fraction of the resulting solution was about 3.5x10 -4 (determined by differential weighing between defined volumes of suspension drops and their resulting dried NPs residue as described in previous section 1.1.2/c.1). Similar procedure can be achieved with hydrophobic terminated-thiols molecules coated NPs dispersed in an organic solvent.

The following paragraphs describe the characterization of the GNRs deposited onto rigid substrate and will emphasize the importance of the purification of the suspension (removal of the excess of additives).

c. Characterization of Au nanorods

The as-synthesized, centrifugated and functionnalized nanorods were characterized by TEM and UV-vis spectroscopy.

C.1. Transmission Electron Microscopy (TEM)

This section describes the characterization of the morphology and cristallinity of the synthesized short and long nanorods by TEM, as well as their organisation onto TEM grid. Then, high resolution TEM study has been performed on nanorods to better understand the multi-step removal procedure of CTAB bilayer coating (by centrifugation). This characterization is necessary since the CTAB free GNRs obtained from this procedure are used to graft new functional coating on these bare GNRs. of nanorods aligned parallel to each other. This is due to self-assembly of the CTAB bilayer on the gold surface that induces the self-ordering of nanorods. 67 Moreover, surfactant-mediated interactions between high aspect ratio gold nanorods having uniform shape and size results in liquid crystalline like ordered arrays in the concentrated suspensions, driven by a side to side arrangement. 68 However, TEM images (d), (e), and (f) of smaller nanorods synthesised with the addition of silver nitrate, show a tendency to fill the available space by forming all sorts of assemblies, such as end-to-end and side-to-side, exhibiting essentially short-range orders.

Morphological and cristallographic study of as-synthesized nanorods

Growth mechanism

The length of nanorods that were synthesized using AgNO3 is shorter than the one of nanorods synthesized without silver ions addition. These two methods follow two different mechanistic pathways.

1. The long nanorods synthesized without silver ion have a different crystallography than those made with silver ion. Gold nanorods synthesised without silver ion have pentrahedrally twined structure, in which five (111) triangular facets were on the ends, and (100) facets on the long sides of the rods. 71 Murphy and co-worker proposed that the CTAB head group preferentially adsorb on the gold existing along the sides of pentahedrally twinned rod as compared to the faces at the tips. 72 It is believed that wellorganized CTAB bilayer on the gold surface follow the "zipping" mechanism and favour the formation of one-dimensional growth along the axis by approaching the gold ions and ascorbic acid to the seed particles, leading to a long rod like structures. 73 2. Short gold nanorods made in the presence of silver ions are single crystals, with (111) facets on the long side of the rods. Silver ions form silver bromide with the bromide ion from the CTAB, and they can also form thin films epitaxially on Au (111) that can undergo reconstruction. 74,75 First, bromide adsorbs to the gold seeds, and the presence of silver, forms silver bromide at the gold surface. The subsequent in slowering of the kinetics results in single crystalline growth of the gold nanorods. The rod morphology arises from that presence of a silver bromide layer on the (111) faces of the gold nanocrystal, which displaces the gold reduction on the other faces, producing a rod with (111) facets on its long axis.

Dependence of CTAB removal on centrifugation parameters

High Resolution TEM images of isolated gold nanorods such as those displayed in Figure Finally, this TEM study displays the importance of the centrifugation step before any exchange of molecules at the NP surface. This cleaning process can be improved by the addition of H2O2 molecules to oxidize and eliminate the residual organic coating on the NPs.

The following paragraph will characterize the optical signature of as-synthesized short and long nanorods by UV-vis spectroscopy.

c.2. UV-vis spectroscopy

This paragraph mainly focuses on the UV-vis spectroscopy response of GNRs and its dependence on their morphological features (diameter, length and aspect ratio). This UV-vis Spectrocopy study has enabled to confirm the monodispersity of the assynthesized GNRs suspension. Moreover, it has revealed the presence of two plasmon bands (longitudinal and transverse ones) for GNRs compare to the single one for spherical NPs. This particular signature of GNRs and its modulation with the aspect ratio is highly interesting for optical applications (especially surface enhanced Raman scattering). This specific behaviour of GNRs has promising applications as anticancer agent, near-infrared filter, storage media, biological labeling, biomedical imaging, and image-guided therapies. 77,78,79,80,81 1. 1.3. Conclusion This first chapter of this first part was focused on a short historical reminder related to gold NPs, the different approaches that have been proposed in literature to synthesize 77 X.

Gold nanospheres 65  5 nm in diameter:

65 nm diameter gold nanospheres are prepared by mixing the three freshly prepared aqueous solutions:

-Solution 1: HAuCl4 (0.01 % by weight)

-Solution 2: Na3-citrate (1 % by weight).

-Solution 3: Seed solution of gold nanospheres of 5 nm in diameter (solution E).

1 mL of solution 1 is added to 100 mL of water, the mixture is heated to boiling, while stirring, 0.4 mL of solution 2 and 15 μL of solution 3 are then added. The stirring at the boiling temperature is kept for a few minutes and then the solution was left without stirring at room temperature for several hours. The suspension is stored in a dark bottle at 4 ° C. The synthesis of 65 nm diameter gold nanospheres (big particles) recquires specific operating condition such as high temperature (boiling) and use of a seed solution.

Indeed, high temperature induces the fracture of ligands surrounding the seed particles.

Other forms of gold NPs

Octahedron or network shaped gold nanoparticles were obtained by mixing two freshly prepared aqueous solutions:

-Solution 1: HauCl4 (0.01 % by weight)

-Solution 2: Na3-citrate (1 % by weight). The solution was prepared at boiling temperature using a small amount of surfactants (compared to previous recipes). A possible mechanism inducing the formation of these arrays may be the diffusion of seed particles. Indeed, this diffusion is favored by both heating and stirring processes. However, the final morphology of Au NPs or clusters will be controlled by the competition between Au atomic diffusion to the seed, the growth The growth of the net-like structure is particularly remarkable as shown in figure N1. 1.4b, where we observe the formation of a half triangular particle at the beginning, whereas the growth of the particle continues at one extremity to form a net-like structure.

Introduction

Most NPs-based functional coatings and devices are structured as mono or multilayers, assembled onto rigid substrates. However, the ability to tune intrinsic NPs properties by controlling their size, shape and surface coating represents a major step to control their organization in well-defined structures. In addition, to control the adsorption and the topological arrangement of these NPs (driven by their intrinsic functional properties), it is also crucial to adjust the chemical and physical properties of the substrate to the nature of the NP. One of the most effective and simple way to achieve this, is the implementation of self-assembled molecular films (SAMs) onto a substrate.

Self-assembled monolayers (SAMs) offer a unique combination of chemical and physical properties that allow fundamental studies of interfacial chemistry, solvent-mediated interactions and self-organization onto a substrate. The ease of tuning the terminal functionality of SAMs makes them ideal model systems used in a large range of fields.

Indeed, SAMs are invaluable substrates for friction and adhesion (MEMs, fluidics), in bioanalytical, organometallic and electrochemistry. 1 SAMs are formed when molecules spontaneously adsorb in a monomolecular layer on surfaces. Ulman, in his book "An introduction to Ultrathin Organic Films: from Langmuir-Blodgett to self assembly", summarizes the work on Langmuir-Blodgett and self-assembled molecular films. 2 There are different methods that lead to SAMs: organosilanes on hydroxylated surfaces, alkanethiols grafted onto the surfaces of gold, silver and copper, alcohols and amines on platinum and carboxylic acids on oxide of aluminium and silver. In all cases the interactions between the substrate and the organic films are sufficiently strong (physical or chemical binding) to insure its physical and mechanical stability.

In this work, we will focus on the formation of either homogeneous or heterogenous self-assembled organosilanes monolayers on oxidized silicon substrate as displayed in figure 1.2.0.1. These substrates will represent model substrates for controlling the organization of NPs synthesized in the first chapter of this part. In the following we will describe the two main procedures used to prepare homogeneous and heterogeneous alkylsilane monolayer films, as well as their characterization. The physical state of thin molecular films is influenced by a number of forces including intermolecular interactions between molecules making up the film, interfacial bonds with substrate and technical parameters (solvent or vapor phase deposition, chemical affinity between solvent and molecules, concentration, temperature, etc…). The structural characteristics of organic thin films (molecular conformation, packing arrangement and chemical composition) directly influence their intrinsic properties.

Elaboration procedure

The performance of the self-assembled monolayers is also directly dependent on the efficiency of the anchorage to the surface. Granick and co-workers 3,4 have shown the importance of surface and density of grafting sites to form well-packed monolayers of SAMs. The substrates used in this work are silicium wafers bearing their native oxide layer (SiO2) of about 2 nm thick as determined by ellipsometry.

a. Cleaning and surface activation of the substrate

The cleaning step enables to eliminate any contamination on the surface, and the hydroxylation treatment enhances the density of surface silanols group (Si-OH) for the grafting reaction.

The cleaning step consists in a sonication of the substrate (Si wafers) in an organic solvent (cyclohexane, chloroform) for about 10 min to remove excess organic surface contaminant.

The hydroxylation step involves immersing the substrate in an oxidizing "piranha" solution, composed of a mixture of 70% sulfiric acid [H2SO4] and 30% hydrogen peroxide [H2O2], and heated to 70 ° C for 30 minutes. Then, the sample is thoroughly rinsed with milli-Q water, dried under nitrogen flow and immediately used for grafting of the organosilanes.

b. General preparation procedures of SAMs

Two procedures which have been successful for forming well-ordered SAMs, are available. On the one hand, the organic molecules are dissolved into a solvent, 5 and on the other hand, they are dispersed in a paraffin oil and deposited under vaccum (~5.10 -3

Torr, 45 min to 1 h) [figure 1.2.1.1]. For both proccesses organic molecules diffuse or are transported to the surface where they self-asssemble, first into discrete nanodomains 6 , which will grow in a second stage up to confluence and form a thin and continuous organic layer. The surface coverage and structure of the resulting SAMs depend on several experimental parameters such as the reaction time, the temperature, the hydration state of the substrate, 7 the nature and polarity of the solvent, or the pressure (vacuum) for vapor phase deposition. Particularly, Sagiv et al. 8 have shown the correlation which exists between the adequacy of the solvent and the packing density of thin molecular film for the solvent phase procedure. These experimental parameters as well as more intrinsic ones have a strong influence on the structure of the monolayer. Indeed, the structural state of the thin film is mainly defined by its uniformity and packing density.

In the following section, we will first emphasize the preparation of molecular homogeneous thin films; particularly, we will address the influence of terminal endgroup of the assembled molecules, the packing state of SAMs and the operating conditions onto the formation of these ultrathin films. Then, we will focus on the important issue of model heterogeneous molecular surfaces and more precisely of micro-patterned surfaces that will be prepared by microcontact printing technique.

Homogeneous molecular surfaces

The homogeneous molecular surfaces are formed by the assembly of a single type of molecule onto the substrate. The influence of the terminal and head groups of embedded molecules on the chemical and physical properties of the surface were also investigated by contact angle measurements, Atomic Force Microscopy and ellipsometry.

a. Preparation of the molecular films

The preparation can be performed either in liquid phase or in vapour phase, as described in the previous section. Because the terminal end group of the molecular film controls the surface reactivity, wetting, adsorption and adhesion, these terminal groups will be chosen to precisely adjust these surface properties (hydrophobic/hydrophilic).

a.1. Hydrophobic SAMs

The hydrophobic molecular films were formed from organosilanes presenting methyl (-

Solvent phase deposition

The method consists in immersing the hydroxylated Si wafers in an organic solution of HTS or OTS of 1 mM in concentration. The appropriate solvent used in this work is a b cyclohexane. The cleaned and activated Si wafers are immersed in the solution containing the molecules to be grafted for a minimum of 6 hours (overnight usually), at a temperature of 20 °C. After the completion of the adsorption and grafting step, the sample is removed from the solution, and sonicated in cyclohexane for one minute. This last operation is aimed at desorbing any excess of aggregates or molecules physisorbed onto the surface.

Vapour phase deposition

The hydroxylated surfaces are hanged above a mixture of paraffin oil-organosilane contained in a polystyrene cup (100 L of molecules in 3 mL of oil / equivalent to ~ 4% in volume fraction). Previous to mixture, the pure paraffin oil is de-aired under partial vacuum (10 -3 Torr) using a rotary pomp. The whole system (mixture + sample) is placed then under partial vacuum. Organosilane molecules react with the surface after their extraction from the mixture and transport through out the vacuum. The samples were removed after 1 hour, and sonicated for one minute in cyclohexane or chloroform to desorb any aggregates or physisorbed molecules on the surface.

Remark: the PFS SAMs can't be prepared in a solution phase due to a lack of availability of an efficient solvent to dissolve these molecules. Indeed, none of usual solvent dissolves efficiently these PFS molecules to avoid the presence of aggregates in the solution, and hence on the surface (substrate). However, the functionnalization with PFS was successfully achieved using the vapour phase technique.

a.2. Hydrophilic SAMs

The hydrophilic molecular films were formed by using organosilanes with amine (-NH2) terminated function and ethoxy tail groups. The molecule is the following one: To check for the completion of the grafting reaction (formation of the SAMs), and to determine their chemical properties, the samples have been characterized by contact angle measurements and ellipsometry.

b. Characterization

Each self-assembled monolayers sample has been characterized for the physical and chemical state of the molecular films. Contact angle measurements were performed to confirm the chemical properties, and ellipsometry has been carried out to verify the compactness of grafted molecular films.

b.1. Contact angle measurements

Wettability of SAMs represents an easy way to control the chemistry of the surface as well as their structural properties, especially their molecular compactness. Average equilibrium ( e), advancing ( a) and receding ( r) contact angles of dozens of 2 µL water

Physical adsorption Hydrolysis

Covalent The homogeneous SAMs have surface energy characteristic of the corresponding terminal group. The surface chemistry of these molecular surfaces corresponds directly to the silanes terminal function 13 and their surface energy can be characterized through the contact angles of liquid droplets, especially water, which are highly sensitive to the interfacial interactions between the SAMs terminal groups and the molecules of the liquid drops. As expected, the highest equilibrium contact angles with water are observed for the more hydrophobic substrates (PFS, HTS and OTS), with the PFS exihibiting the most hydrophobic character. The lowest equilibrium contact angle being observed for the polar and H-bonding amine-terminated SAM (-NH2).

In the same way, the highest advancing contact angle ( a =117°) corresponds to the wellpacked fluorinated long-chain monolayer. 13 HTS and OTS monolayer displayed both similar results as they correspond to a methyl close-packed molecules carpet. Amine terminated SAMs show a lower advancing contact angle ( a =60°), characteristic of a hydrophilic monolayer as well as a high hysteresis of wetting (θa -θr) compared to previous layers. This last result can be correlated to a low grafting density or a disordered molecular films. 14,15,16 Indeed, receding angle is on the one hand, sensitive to the chemical nature of the end-group that is in direct contact with the liquid and exchange molecular interactions (adhesive forces), and on the other hand, is sensitive to the density and thickness of the monolayer (frictional forces). As described in the literature, receding angle is particularly low with short chains of less than eight carbons.

Longer chains, stabilized by Van der Waals (VdW) attractions form more compact, solidlike layers which are less sensitive to hysteresis or structural origin.

These results of contact angle characteristics of the chemical and structural properties of the SAM coatings have been completed by ellpisometry measurments as described in the following paragraph.

b.2. Ellipsometry

The ellipsometry is an optical technique for surface and thin film analysis, based on the measurement of the modification of the light polarization state after reflection on a flat surface. This technique allows determine the optical properties (refractive index in particular) and the thickness of the organosilanes films grafted onto silicon substrates.

Null-Ellipsometer (Multiskop, Optrel, Germany), equipped with a 532 nm (Nd-YAG laser) wavelength laser was used. The refractive index (n) of the organosilanes monolayer is of the same order of the refractive index of silica SiO2 (n=1.45) [figure 1.2.2.5]. Thus, the first step of the procedure consists in estimating the oxide layer thickness overlying the silicon substrate, and then determinating the total thickness of the film. The thickness of the organic (organolsilanes) monolayer is then calculated by subtracting to the total thickness, the value (thikness) measured for the silica layer SiO2. 14 M. Sastry, Chem. Mater., 2002, 14, 1678. The inorganic layer consisting of the silicon oxide forming at the air/silicon interface is around 3.6nm. This value is in agreement with the average native silicon oxide layer that grows on silicon substrate (< 5nm). Then, thicknesses of organic silanes films were estimated according to the procedure described in the previous paragraph. Values found for hydrophobic molecules (HTS, OTS and PFS) are in agreement with expected value of chain length of each organic molecule supposed to be grafted on silicon substrate in a well-ordered state . However, the experimental value for the hydrophilic (NH2 thin film) is lower than the simulated one; this result allows concluding the presence of some disorder in the grafted molecular hydrophilic film.

These ellipsometric results thus allow to characterize the structure and organization of the grafted molecular films, in particular their compactness.

c. Conclusion

We have presented two different methods of elaboration of homogeneous SAMs, in solution and in vapour phase. The wetting properties (hydrophilicity or hydrophobicity) of the embedded self-assembled monolayer have been adjusted by the proper device of the terminal end group of the alkylsilane molecule, and the grafting density. After their elaboration, the chemical nature of the SAMs as well as its compactness have been investigated by ellipsometry contact angle measurements.

The following section will describe the elaboration of heterogeneous SAMs and their characterization.

Heterogeneous molecular surfaces

Nanoscale surface patterns are considered as potential templates and building blocks for nanotechnology. 17 As for nanomaterials in general, these nanoscale surface structures have been of increasing interest in recent years, due to their unique properties. Different techniques such as electrochemical stripping, 18 hot embossing lithography, 19 nanoimprint lithography, 20,21 edge transfer lithography, 22 laser patterning monolayers process, 23 dip-pen nanolithography 24,25 as well as photolithography techniques 26 are commonly used to fabricate accurate and geometrically controlled micro and nanostructures. However, although these techniques make it possible to produce a variety of patterns, those are often limited to well-defined regular geometries (square, circle, strips), with typical sizes still higher than 100 nm, except for a few timeconsuming and rather expensive techniques. And yet, random patterns of nanoscale heterogeneous surfaces either composed of the discrete distribution of nanoscale domains of one molecular compound in the continuous phase of the second 27 or characterized by the formation of a bicontinuous structure of the two molecular phases 28,29 represent another way to nanostructure surfaces.

The fundamental issue in this type of nanoscale heterogeneous patterns is the way the chemistry, topology and surface fraction can affect or be used to adjust the nanoscale surface properties of such thin heterogeneous molecular films. These nanoheterogeneous surfaces also provide model systems for the understanding on the fundamental level of nanoscale chemical heterogeneities (2D size effect) on recurrent interface phenomena and processes (wetting, de-wetting, nucleation, etc).

This section will focus onto the preparation of patterned substrates with specific shape, size and spatial distribution. These nanoscale-structured binary surfaces are made of molecular films presenting antagonist wetted/ non-wetted domains regularly controlled using the microcontact printing technique.

Microcontact printing

Micro and nanopatterned surfaces were prepared by microcontact printing, 30,31,32 pioneered by G.M. Whitesides and S. Chou. 33,34 Microcontact printing (µCP) involves the use of an elastomeric stamp with micron or submicron sized relief features on its surface to print molecular inks onto a substrate that has a higher affinity towards the ink molecules than the stamp. In figure 1.2.3.1, we present a Tapping mode AFM phase image of the as-prepared, wellorganized heteregeneous surface. The bright squares correspond to the hydrophilic domains. Their average size is around 4µm and the interdomain space is of the order of 6µm. The continuous phase is then made of vapor-deposited hydrophobic HTS molecules. However, this technique is not perfect, as we can observe the presence of local defects due to either an excess of transferred molecules from the stamp to the surface or pre-existing defects on the stamp.

The following results will show that these templated-self-assembly patterns provide interesting systems for studying self-assembly behavior under 2D confinement, as well as a platform for innovating nanofabrication methods. In particular, these well-ordered SAM patterned surfaces represent model surfaces for studying the self-assembly behaviour of NPs from drying nanocolloidal suspensions.

Conclusion

Precise control of molecules is essential to assemble complex two-or three-dimensional structures. In this second section, we have first presented and described two effective

methods

Conclusion

This first part of the dissertation was dedicated to introduce this PhD work (state-theart, scientific issues and motivation), and at describing and discussing the synthesis, the elaboration and the characterizations of nanomaterials that will be used (next two parts).

In this context of emerging nanoscience and nanotechnology, the nano-objects that we have chosen to manipulate are gold NPs as they are the most stable metal NPs, and they offer fascinating aspects such as their ability to assemble in a multiple ways leading to specific structures presenting either discrete or collective NPs. Nanostructured molecular surfaces were also prepared as model and controllable substrates that will support the NPs.

The first chapter focused on Au NPs synthesis based on wet-chemical methods. The procedure we have developed was based on the chemical reduction of metal salts. It involves a simple approach and provides well-controlled NPs with tunable size and shape, morphology and surface state. Spherical Au NPs were synthesized from a few nanometers up to one hundred nanometers diameters. The precise control of operating conditions such as temperature, nature and amount of surfactants or reducing agent has enabled to tune accurately the Au NPs morphological and chemical parameters.

Asymmetrical Au NPs such as elongated ones (rods) have been synthesized using a seed mediated approach. This method corresponds to a two-step procedure. First, gold nanospheres are produced by chemical reduction of Au salt using a strong reducing agent such as sodium borohydride; these seeds are then added to a growth solution of gold salt including a weak reducing agent and cetyltrimethylammoniumbromide (CTAB). This seed-mediated procedure has enabled to provide rods with aspect ratios varying from 2 to 15. The control of the structural and chemical modification of Au NPs have a strong impact on the character and performance of NPs assembly; hence a two step procedure for the exchange of the NPs coating has been proposed to tune their chemical functionality. Finally, the morphological and crystallographic parameters of Au NPs as well as NPs suspension stability have been carried out by TEM and UV-vis spectroscopy measurements. In particular, UV-vis spectroscopy analysis has demonstrated that gold spherical particles exhibit only a single plasmon band in the visible region, and colloidal solutions of gold nanorods exhibit two strong surface Plasmon bands, one in the visible region caused by the transverse oscillation of electrons, and the second in the near -infrared caused by longitudinal oscillation.

The control of the adsorption and the topological organization of these NPs was achieved by finely-adjusting the chemical and topographical structure of the substrate to the specific nature of the NP. In this context, self-assembled monolayers (SAMs) have offered a unique combination of physical properties that allow fundamental studies of interfacial chemistry, solvent-mediated interactions and self-organization.

Then, the second chapter has focused on the formation of either homogeneous or heterogenous self-assembled organosilanes monolayers on oxidized silicon substrate.

First, homogeneous SAMs were prepared either in liquid phase or in vapor phase. They were characterized by contact angle measurements and ellipsometry to confirm their chemical properties (hydrophobic or hydrophilic) as well as their compactness. In addition, micro-heterogeneous molecular binary surfaces presenting a regular geometrical (spatial) order were carried out using a two-steps procedure. The molecular domains were first deposited using stamps-transferred solution (ink) by microcontact printing technique, and the remaining free area surrounding the domains was filled with a second molecule. The heterogeneous SAMs films were then characterized by AFM for the domains size and distribution. These nanopatterned surfaces provide a model system (such like a controlled and tunable playground) to study the organization of Au NPs in the aim to better understand the interplay between 2-D structuration, and the control of interfacial phenomena.

The following parts of this work will focus on the study of drying-mediated assembly of Au NPs onto model homogeneous and heterogeneous surfaces. In Particular, we will study in the second part the wetting and drying-mediated self-assembly and structures formation, including complex dendrite and ramified patterns from NPs-based suspension drops. The last part will then focus on the aging of these complex aggregates.

Finally the cooperative mobility of Au NPs has been studied to understand the mechanisms underlying the morphological reconstruction of these metastable patterns.

In addition, manipulation of single Au NPs has been performed by AFM to contribute identifying the main interfacial parameters driving the Au NPs motion, and thus to better account for the aging and dislocation of the NPs-based aggregations structures.

Introduction

Wetting and drying of heterogeneous liquids on solid substrates are of great importance in biology (biodispersions) and basic technologies (emulsions, suspensions and polymer solutions). 1,2,3,4 The solvent evaporation and the drying stage required by the film processing may either result in random and featureless aggregates or lead to the formation of well-defined complex fractal and meso-structures at the surface. 5,6,7,8,9,10,11 For instance, bacterial colonies have been shown to spontaneously grow in complex aggregation morphologies, 12 whose topological features are determined by the local environmental conditions (chemotacticity, gradients in nutrients, etc.). In the same way, crystallization of proteins at a substrate may also result in complex aggregation patterns, depending on the specific properties of the surface-solution interface. More interestingly, the drying of a drop of human blood which exhibits coupled physical mechanisms, (such as Marangoni flow, evaporation and wettability) showed that the final morphology of the dried blood drop reveals regular patterns that reflect the fine composition of the blood and hence the health of the person. In particular, experiments on anaemic and hyperlipidaemic people result in different patterns. Anemic blood does not have the big cracks visible on a drop of normal (healthy) blood, and in the case of hyperlipidemia, the drop of blood has an external fatty thick layer, as well as small plates in the central part [figure 2.1]. 13 Therefore, understanding the underlying mechanisms and key parameters which govern the formation of these structures may provide an interesting route for the controlled elaboration of complex surface assemblies, which are of both fundamental, technological and biotechnological importance. that vary only according to the composition of blood. 13 The formation of complex patterns in flowing liquids in general, and especially in colloidal dispersions, was discovered about a century ago and known to be driven by hydrodynamic instabilities which develop in the moving interface. In this part, we will show first that complex fractal aggregation structures can readily emerge during the drying of colloidal dispersions at chemically homogeneous and topologically uniform substrates. The mechanisms and critical parameters which control the formation and the organization of these aggregates are investigated during the drying of nanocolloidal suspension drop. In the first chapter of this part, we will discuss results of a model study on the interrelation between the occurrence of complex aggregation patterns in drying nanofluids, the size of the constitutive Au nanoparticles (from 3 to 35 nm), the drying temperature (from 20 to 100°C) and the surface properties of the underlying substrate. Finally we will discuss the role of presence of ionic synthesis residues in the suspensions on the formation of these patterns. After the formation of aggregation patterns at planar and texture-free model surfaces, we will move toward the directed assembly of these NPs in functional 2D-nanostructures, through the introduction of soft-deformable nanotemplates (nanodroplets / nanobubbles ) in the drying system. In the second chapter we will present a drying mediated self-assembly process of nanorings of NPs, using immiscible nanobubbles and nanodroplets "templates" either grown in situ or purposely introduced in the suspension, respectively. Then, we will characterize the singular exaltation of the surface Plasmon in these nano-objetcs and their related SERS (Surface Enhanced Raman Spectroscopy) properties.

Finally, as specific and interesting applications of NPs-based structures and patterns, we will introduce biopolymers (alginate) in the suspension. The drying-mediated assembly of these binary alginate/NPs system will be studied in the chapter 3 of this part. In this chapter, we will show the emergence of large-scale ramified patterns, and we discuss the conditions for the formations of these complex aggregation structures starting with the effect of the residual ions in the mixed solution on patterns topology, and going through the influence of alginate concentration (versus NPs volume fraction) to that of NP size in the mixture.

In addition we will discuss from a phenomenological standpoint the emergence of such structures, highlighting in particular the hydrodynamic structuring effects acting during the drying of these solutions. From these highly-ramified, large scale dendrite patterns, resulting from the drying-mediated co-assembly of NPs and alginate, we have derived a capillary fabrication technique of lab-scale composite hydrogel microfibers (alginate/ Au NPs). At the end of this chapter, we will go deeper into the nano and molecular scale structures of nanoaggregates composed of a few alginate chains and Au NPs. This study is carried out to understand the possible interactions between alginate/residual ions/NPs and the resulting morphological organization at the mesoscale. The studied parameter for these investigations involves the alginate chain length.

68

Chapter 1

Complex aggregation patterns issued from drying nanocolloidal suspensions

Introduction

Drying of suspensions is familiar, ubiquitous in many daily and technological processes, and deceptively simple. As the solvent evaporates, the suspensions undergo a fluid to solid (sol-gel) transition, leaving a film that is familiar to anyone who has spread a coat of paint or spilled a drop of coffee. However, when examined closely, this simple process displays a rich phenomenology, presenting a plethora of intriguing and important questions. Deegan et al. described the mechanism of the evaporation and drying of liquid drops. 1 When a spilled drop of coffee dries on a solid surface, it leaves a dense, ring-like deposit along the perimeter. The coffee initially dispersed in the entire drop becomes concentrated into a tiny fraction of the drying area. These coffee stains patterns are characteristic of the specific evaporation dynamic of the suspension drops. Indeed, the ring-like deposit results from the outward flow that takes place inside the drop and carries the dispersed coffee grain at the edge. This mechanism predicts a power-law growth of the ring mass with time -a law independent of the particular substrate, carrier fluid or deposited particles, and given by M(t) ~ t 3/4 for small contact angles (Ѳ < 1rad). These hydrodynamic processes that depend on the evaporation of the solvent, wetting properties of substrate-dispersion, as well as the volume fraction  V and the viscosity  of the dispersion, leads in most cases to the growth of an annular aggregat on the periphery of drop. In general, two distinct cases can be considered to describe the drying of a drop of dispersion: drying at variable contact area, and drying at fixed contact area. where D is the diffusivity of the solvent molecules and CVAP is the concentration of solvent vapour. J(z, r) is maximum at z=0 and r= R, resulting in a r) between the edge and the center of the drop such that (r=R) > (r.

The rate of accumulation of particles at the periphery depends on the competition between the evaporation rate, which confines the particles to the wall and impedes their transport, and the receding velocity of the drop. Finally, the two main parameters that govern the transport of particles to the periphery are both the evaporation of the solvent and the density of particles in the drop. Many theoretical models have been developed to understand the growth dynamics and the final topology of these complex aggregation structures. These theoretical approaches are based, essentially, on the topological description of the aggregate during growth, in terms of fractal. Mandelbrot coined the word fractal in 1975 from the Latin "fractus" which describes a broken stone-broken up and irregular. 4 Fractals are geometrical shapes that, contrary to those of Euclid, are not regular at all. First, they are irregular all over. Secondly, they have the same degree of irregularity on all scales (scale invariant structures). 5 Fractal geometry is a structure identical to itself, whatever the scale at which we consider this arrangement. The fractal nature of an object is characterized by a dimension D, the fractal dimension, or Hausdorff dimension of the pattern/structure.

In this chapter, we first present a theoretical description of multibranched complex pattern formation. Then, we present and discuss results of a model experimental study on the interrelation between the occurrence of complex aggregation patterns in drying nanofluids, the size of the constitutive Au NPs (from 3 to 35 nm), and the drying temperature (from 20 to 100°C). Finally, the role of presence of ionic compounds on the formation of these patterns will be described in the last section.

Theoretical viewpoint vs. experiments

Theoretical model

Here we present a theoretical model for describing a cluster topology and correlate it to the fractal dimension D of the object.

We consider an aggregate consisting of N particles, each particle occupies a fixed position r in the space. The correlation function of relative density in this set of particles is defined as:6

    A r o r     eq 2.1.1.1
where  (r) and  (0) represent, respectively, the particle density at position r and the origin (r = 0). The exponent A is related to the Hausdorff dimension D (or fractal dimension) as: D = d -A, where d is the dimension of vector space.

The density correlation function that relates the radius of gyration R of the aggregate to the number of particles N is given by equation 3:

7 D A d d R R R r d r N ) ( ) 0 ( ~    eq 2.1.1.2
Depending on the size of the space, many aggregation structures obey a law of growth rather general called Diffusion-Limited Aggregation, or DLA, which characteristic fractal dimension is D ~ 1.7 in the two-dimensional space. The growth dynamics of a twodimensional aggregate obeying this model is described as follow: Consider a particle "seed" at the origin of the structure. Another particle diffuses and comes close to this seed. Under these conditions, this particle has a sticking probability p Part 2: Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 1: Complex aggregation patterns issued from drying nanocolloidal suspensions 74 such that 0  p  1. A third particle follows the same way and so on. The result of this assembly is a two-dimensional aggregate which size can theoretically grow indefinitely.

The growth of the aggregate is controlled by the probability u (s, k) for the particle k that diffuses to reach the adsorption site s on the aggregate. In the DLA growth mode, the sticking probability or capture of particles at the periphery of the aggregate is higher than those of adsorption sites located within the aggregate.

The dependence of the probability u (s, k) vs. time is related to the density of sites and stages of adsorption k, according to the equation 4:

8 u D t u diff ²     eq 2.1.1.3
where Ddiff represents the diffusion constant of the particle in the system.

For a given aggregate, the growth velocity Vn according to the perpendicular direction to the periphery n  of the aggregate is defined by the gradient of the probability u (s, k), according to the equation 5:

u n D V diff n     eq 2.1.1.4
The growth rate of the aggregate, in the DLA model is therefore proportional to the diffusion of particles in the system, i.e the transport of material, but also depends on the probability of encounter of the particle with the aggregate.

Experimental analysis

Hereafter, we display the analysis of dendritic structures in the aim to evaluate their fractal dimension and understand the growth mechanism of these complex structures. A Minimum of 5 complex aggregation structures were captured after their occurrence [figure 2.1.0.1] using an optical microscope, (Olympus optical microscope coupled to a COHU CCD camera operating at 25 images/s). The microscopic images were then analyzed by a public version of the Image J software developed by the National Institute of Health USA. This software, in particular, allows thresholding, binarization and counting the number N of particles, or their area fraction in 2 dimensions. The analysis process was the following. The colour image is first converted to gray scale and the contrast is adjusted to optimize its resolution. Then, the second step is a thresholding and a binarization of the image in black and white pixels to discriminate respectively the absence and the presence of particles [figure 2.1.1.1]. Finally, a technique of "boxes" (boxcounting) is applied to evaluate the fractal dimension of the complex structure from the dependence of N on the box sites R. The image is divided into a series of circles of increasing radii R centred at the origin of the aggregate. At each step of this analysis, we report the number of white pixels, corresponding to the complex structure inside the drawn circle as well as the diameter of this circle. The fractal dimension D obtained was 1.8. This value is very close to that of a DLA aggregate which has a theoretical fractal dimension D= 1.7. However, obtaining a fractal dimension, which corresponds to that of DLA growth mechanism, does not necessarily mean that the growth process of our NPs aggregates follows diffusion limited aggregation process. For instance quasi two-dimensional aggregates of fractal dimension larger than 1.7 (from 1.8 up to 2) are known to be more open structures that DLA aggregates, and to be characteristic of a growth process in which "multiple attempts" of sticking are required for the formation of a new cluster (low sticking coefficient). The following paragraph will discuss some of the reasons that explain the inherent limitation of certain theoretical models to account for the morphogenesis of the complex patterns arising from drying nanocolloidal sessile drops.

From a theoretical point of view, the work of Rabani et al., 9 who used an "extended" coarse-grained model to calculate and predict the emergence and topological features of drying-mediated NP aggregates, represents probably one of the most complete approach in this domain. Interestingly, using an Hamiltonian H (equation 6) involving mainly adjacent particle/particle, particle/solvent and solvent/solvent interactions, 9 some of the basic experimental drying patterns (discrete clusters, wormlike and polygonal networks) were closely captured by this model, depending on the evaporation regime (homogenous vs. heterogeneous). But, although dynamic aspects like solvent fluctuations induced by evaporation are included in this model.

For a particular configuration of the liquid (solvent) cells associated to a variable (li), that is roughly proportional to solvent density at lattice site i and of the NPs associated to a variable (ni), that describes NP density on the lattice:

where is the attraction strength and is the chemical potential.

There are recurrent phenomena that have been shown experimentally to critically determine the topology of the occurring patterns, which are absent from this model.

These include the particle/substrate interaction controlling the balance of NP sticking vs. sliding, and hydrodynamic induced shear stress at the interface. Depending on whether the contact line (CL) retires or not, or on whether the residual drop (film)

confining the concentrated particles ruptures or not, these two parameters determine the ultimate topologies of the networks through the late-stage hydrodynamic events and related shear restructuration of the NP assemblies at the interface. 3,10,11 Indeed, experiments show that several of these drying-mediated complex patterns clearly exhibit fingerprints of the local flow and hydrodynamic shear experienced during their formation (axi-symmetric vs. anisotropic aggregates) 2,6 underscoring the crucial role of these interfacial parameters.

If hydrodynamics plays such a crucial role via the viscous shear at substrate interface, to determine the ultimate morphology of the aggregate in the late-stage of the suspension drop drying, thus knowing the state of the nanocolloids within the residual film (more or less connected spherical-shaped or wormlike clusters) becomes equally important. The pre-existence of such "more or less open" aggregates in the concentrated residual thin drop/film, before any restructuring shear stress is applied, is well supported both by experiments 3,10 and model simulation 9,11,12,13,14 (although the latter contains no explicit interaction potential or shear field between the substrate, and the particulate aggregates).

In addition, most of the numerical simulations do not incorporate explicitly the synthesis residue compounds like salts-ions and organic compounds that can co-exist with NPs in the colloidal solution drop. Our experiments highlight the importance of these factors on the occurrence of complex aggregation patterns.

It thus appears, from both a theoretical and experimental viewpoint, that deeper insights into this drying-mediated pattern formation, this parameter and the other ones are greatly required for a reliable description of the genesis of the complex aggregation structures arising from the "spontaneous" assembling of NPs in drying nanofluids.

The following section describes and discusses the results of a model study on the interrelation between the occurrence of complex aggregation patterns in drying nanofluids, the size of the constitutive Au NPs, the drying temperature, and the surface properties of the underlying substrate.

Complex drying patterns of "as synthesized Au NPs"

solution-Dependence of structure formation and aggregate stability on NPs size

In this section, we focus on the interrelation between the size of the NP, the drying temperature and the substrate-controlled drying dynamics, to determine the occurrence of the complex (dendritic) aggregation patterns through size-dependent effects.

Experimental methods

An ensemble of three model homogeneous surfaces has been used, a cleaned bare clean silicon substrate bearing its native oxide layer (SiO2), and two silicon supported selfassembled monolayers (SAM) of organosilane molecules: the NH2 hydrophilic and the HTS hydrophobic surfaces prepared as described in the first part of this work.

Citrate stabilized suspensions of spherical gold NPs of 3, 15, 25, 35 nm in diameter were prepared as described in part 1.

The experiments have consisted in depositing 20 µL drop of suspension on the substrate in a thermally equilibrated chamber (T°). The drying and resulting structure formation was followed under a video-microscope (Olympus optical microscope coupled to a COHU CCD camera operating at 25 images/s). The drying kinetics was followed by measuring the variation of the contact angle and the diameter of the drop, using a Krüss G2 contact angle analyser. The relative humidity in the experimental chamber was kept constant at 33% ±2. The drying and structure formation for each individual sample was investigated of the four sizes of Au NPs at drying temperatures of 20°C (~ ambient), 45°C, 75°C and 100°C. The complex aggregation structures were captured in the final drying spot, generally at half-way between the centre and the border of the final drying spot.

Results and discussion

The Otherwise stated, the patterns of arborescent dendrites systemically occur on hydrophilic substrate, regardless of the NP size and drying temperature, within the limit of the studied particle sizes (3 to 35 nm) and temperatures (20 to 100°C). This latter result highlights the importance of the drying dynamics and hydrodynamic events on the structure formation, as well as the the nature and wetting property of the substrate.

This influence of the wetting properties and related hydrodynamic events that determine into a large extent the occurrence of the structures is illustrated in figures 2.1.2.5a and 2.1.2.5b. These two figures compare the typical drying kinetics on SiO2 and NH2 for identical particle size (25 nm) and drying temperature (75°C). The sole parameter that modulates the drying dynamics in this case is the nature of the substrate.

This (substrate/suspension) boundary/interfacial constraint crucially determines the whole drying dynamics and the occurrence of the dendritic aggregation structures on NH2 terminated substrate, while these are totally absent on SiO2. To partially conclude, it appears that the occurrence of the complex dendritic structures in drying nanofluids is governed by a coupling between particle size on the one hand, and the wetting properties of the substrate on the other, both being temperaturesensitive parameters. While the particle size clearly dominates and controls the temperature dependent structure formation at the partially wetted SiO2 and non-wetted HTS surfaces, the occurrence of these structures at the wetted NH2 surface is primarily dominated by the substrate wetting properties, for all the studied particle sizes. Because the growth of dendritic structures from drying suspensions is essentially a colloidal crystallization process, one may expect, a priori, these crystallization mechanisms to account for the observed drying-mediated structure formation in general and in particular for its dependence on particles size on SiO2 and HTS surfaces. Assuming such a colloidal crystallization mechanism to predominate and drive the structure formation, regardless of the nature of the substrate, the size of the particle or the drying temperature, one should expect at high evaporation rates (high T°) to promote the crystallization of the smallest (ion-like) NPs, versus larger ones. Indeed, at high evaporation rates, the timescale allowed for particles to encounter each other and to aggregate into crystal-like structures is much shorter, and therefore promotes the crystallization of smallest particles of higher mobility. The corollary of this colloidal crystallization mechanism is that the structure formation should no longer depend on the nature of the substrate, but only on the particle size at a given drying temperature.

And this is obviously not the case, as displayed by our results. The growth of the dendritic structures not only depends on the drying temperature and particle size, but also in a more crucial way on the nature of the substrate. Indeed, the occurrence of the highly ramified dendritic patterns on NH2 over the entire range of drying temperature (20 to 100°C) and particle sizes (3 to 35 nm) shows at least that neither the size of the particles nor the temperature prevail the formation of the structures in this case.

The following paragraph will show, from simple physical considerations that these structure formations are consistently accounted for by the coupling between the wetting properties of the substrates on the one hand, and most importantly the size-dependent cohesion of the particle aggregates in the drying drop, on the other hand.

a. Wetting properties of the substrate and related hydrodynamic events

The following discussion aims at showing in what, wetting properties determine on NH2

(hydrophilic) substrates an occurrence of the complex aggregation structures that spans the entire range of nanoscale particle sizes and drying temperatures, at the difference of (partially-wetted) SiO2, and (hydrophobic) HTS substrate in particular. A first answer toward this lies in the surface chemistry that determines the strength of the particle/surface interactions at interface. At NH2 coated substrates, these interactions involve both hydrogen and electrostatic bonds between the citrate (COO -) stabilized NPs, and the surface amine or ammonium NH3 + (after protonation). where r is the receding contact angle and Ln a logarithmic factor, typically of order 10. 15 Under our conditions, r (SiO2) ~ 13° ~ 0.23 rad, r (NH2) ~ 6° ~ 0.11 rad, and a viscosity of the residual drop that is comparable for both NH2 and SiO2 in that last half drying time, the above velocities give a relative magnitude of the shear forces at the moving edge of the drop at NH2 and SiO2 substrates of, (F (NH2) F (SiO2) ) 10 -2 . This simple estimate shows that the seed-aggregates present at (SiO2/drop) interface should withstand a shear force which is about two orders of magnitude higher than on NH2, indicating that these seed-aggregates that otherwise would create structures must be fully or partially dislocated on SiO2. In addition, the instantaneous shape reconformation of the drop on SiO2, the contact angle of which rises to 55° upon retraction, creates an instantaneous increase in the internal pressure of the drop, which also contributes to collapse the existing seed aggregates. Indeed, when the drop (assumed spherical) goes from the pinning point with a radius of curvature Ri to the transient state with a radius Rf(Rf <<Ri) after depinning, the capillary pressure varies by:

Pc = 2n(1/Rf 1/Ri)~nR/RiRf), eq 2.1.2.2
where n is the surface tension of the nanofluid. This pressure jump then contributes an additional destabilizing compressive pressure (equivalent to an excess compressive energy per unit volume), to which the aggregates seeds that may already exist in the evaporated drop will be submitted. These drying dynamics thus account for the non occurrence of the structures on SiO2 (and HTS too) for certain combinations of particle size and temperature, indicating that for these substrates, the wetting events and the resulting structure formation are highly sensitive and strongly modulated by the couple (particles size/temperature) of parameters. This is nicely corroborated by figure 2.1.2.1

where the occurrence of complex structures on SiO2 increases as the particle size decreases, irrespective of the drying temperature, achieving for the 3 nm particles a systematic occurrence at all temperatures (20 to 100°C). What comes out finally from the above discussion, and especially from the behaviour of the NH2 substrates, is that simulations of drying-mediated aggregation structures that do not involve hydrodynamic events, and at least, sticking strengths (coefficients) for (substrate/particles) interactions can hardly produce experimentally generated patterns.

b. Size-dependent cohesion of the aggregates (within the residual drying drop)

The occurrence of complex structures on SiO2 and HTS, for smallest particle sizes and increasing drying temperatures is rather an unexpected result which clearly points out a size effect at nanoscale. Indeed, whereas one could expect from a simple physical intuition, an increase of thermal energy kBT (kB is the Boltzmann constant) to oppose to the ordered assembly and the formation of large scale aggregates in general, the damping of this thermal disordering for smaller particles is rather unexpected, and a priori counterintuitive. Indeed, if one assumes a rough scaling between the thermal energy, on one hand, and the kinetic energy imprinted to the particle, on the other, it is the thinner particles (of lower mass) which would have the higher thermal mobility defined by,

   ~ (DT / kBT), eq 2.1.2.3
where kBT ~ mv 2 (v is the particle Brownian velocity) and the thermal diffusion coefficient DT of particles of diameter d, moving in a fluid of viscosity and temperature T is given by (Stokes-Einstein),

DT = kBT / 3d, eq 2.1.2.4
where the denominator represents the ratio of the resisting drag force Fdrag = 3vd to the particle Brownian velocity v. Substituting (kBT / 3d) to DT in the expression of   above, and dropping the viscosity that is similar for all particles, then leads to a thermal mobility that naturally scales with the particle size as,   ~ d  1 . Since particle aggregation develops in a large extent in the evaporating drop (solution), 3,9,10,11,12,13,14 before the late stage hydrodynamics (restructuring interface shear) determines their ultimate shape, 3,10,13 one would have rather expected the higher thermal agitation and mobility (  ) of the thinner particles to impede their assembly in stable aggregates. Therefore, the observed stability of the complex aggregates formed by thinner particles, at temperatures where these disappear for larger particles, might account for the higher cohesion of these aggregates, and thus their greater resistance to thermal agitation and to the shear forces at the moving edge of the drop.

We here propose a simple phenomenological approach towards this size-dependent cohesion, assuming the particle cluster to be in the minimum of a potential which is dominated by van der Waals (VdW) interactions, and thus, the cohesive energy density (ced) of the cluster to arise essentially from this interparticle attractive VdW forces. 16,17 This assumption is actually quite reasonable since we consider the particles in their aggregated state. Indeed, this implies a posteriori that the repulsive electrostatic forces of the interaction potential (DLVO for instance)(Derjaguin, Landau, Verwey, and Overbeek), 18 are sufficiently low or negligible to allow aggregation (cohesion) under the action of the sole predominant VdW attractive forces.

For clusters differing only by the size of the NPs, this attractive VdW term of the total potential which may be for instance that of DLVO suffices from a phenomenological standpoint to account for the size-dependence of the cluster cohesion, when the particles are in the minimum of that potential. In such a cluster of "bare" monodisperse Au nanospheres, the VdW interaction energy between two particles is given, in the pairwise approximation, by UVdW = HR/12e, 18 where H is the Hamaker constant (H > 0 for attractive forces), R the radius of the monodisperse nanospheres and, e the equilibrium separation between two nanospheres in the potential minimum. The surrounding medium of the core particles issued from the dried nanofluid being identical for each particle size, the Hamaker constant of the "particle/medium/particle" interaction is at a good approximation identical for all clusters. Now let n be the average number of nearest interacting nanospheres in a randomly packed cluster, which represents a more realistic picture for drying aggregates. The ced of the system is defined by the ratio between the molar amount of the interaction energy, and the molar volume Vm of the interacting units which are molecules in general, and nanospheres here. 16,17 For the above pairwise VdW attraction potential (UVdW), this gives, at first order, a cohesive energy density defined by,

(ced) (-NA.nHR/12eVm), eq 2.1.2.5
where NA is equivalent "Avogadro's number" for the interacting nanosphere units.

Observing that Vm = NAvnanosph., with vnanosph = (4R 3 /3), we arrive to an expression of the cohesive energy density which scales with the size of the nanosphere as, 16 Assuming n ande (in particular) to be independent of the size of the sphere, 19 the size dependence of the ced finally scales as, (ced) ~ H/R 2 . Interestingly, but not really surprising, we can recognize in that last expression an adhesion energy (in J/m 2 ), which when reported to the "thickness" of the equilibrium separation between nanospheres (e) gives rise to a conjoining adhesive pressure, Padh ~ -H/eR 2 , which is nothing else but the (ced). The same phenomenological reasoning provides a third physical quantity tightly bonded to the previous two (ced, Padh.), and which similarly accounts for the observed size-dependent stability of the NP-based aggregates. This is the frictional resisting force that may occur between the nanospheres under thermal agitation for instance. This frictional force Ffrict, or more specifically, its strength per unit volume of cluster, F * frict = (Ffrict / V), is related at a first approximation to the internal area density in the cluster of volume V (area/volume = A/V) as, Ffrict ~ A / V, where is the internal shear stress. Observing that  is locally related to the adhesive pressure by, ~ µfrictPadh ~ µfrict (-H /eR 2 ), eq 2.1.2.7

where µfrict is the internal static friction coefficient, and that (A/V) ~ (1/R), we arrive to a density of frictional resisting force which now varies with the size of the nanopshere as,

F * frict ~ (1/R 3
). This last scaling relation more specifically accounts for the stability of smaller size particle aggregates. Indeed, these small size particle aggregates can readily withstand the pressure variations within the residual drying drop, and especially the restructuring hydrodynamic shear induced by the retracting contact line, within the confined drop edge.

Finally, these results have shown that the cohesion of NPs-based structures (clusters, aggregates, nanostructures) is strongly dependent, and crucially determined by the size of the constituent NPs, regardless of whether these structures form spontaneously (selfassembly), or not. This size effect in the nanoscale range follows a quite simple rule that 19 That assumption amounts to neglect here, within the range of particle sizes studied (from 3 to 35 nm), the curvature dependence of the thickness of the "citrates and hydration" layer adsorbed on the NPs.

Part 2: Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 1: Complex aggregation patterns issued from drying nanocolloidal suspensions 90 can be stated here as follows: "the smaller the NPs are, the higher the cohesion and hence the thermo-mechanical stability of the nanostructures are", independently of their organization inside the structure (see General Annexe). It is worth noting that such size effects (amplification) resulting from the "surface-to-volume" ratio is well known for MEMs and NEMs devices, where they determine the reliability of the mobile parts that experience relatively high adhesion and frictional forces. More closely related to these results and to that general issue of size and confinement effects is the work of Keten et al., 20 which reveals that confined -sheet silk nanocrystals achieve higher stiffness, strength and mechanical toughness than larger nanocrystals. The present section sheds light on the mechanisms by which size effects control in general the physical properties of NPs-based structures, and particularly, thermal and environmental stability. In this respect, it provides key parameters for elaborating reliable nanostructures, with physical properties that can be adjusted for specific applications. A possible illustration of this would be "size-adjusted" structures that lose their percolating morphology, and hence the related conduction, above a certain temperature as a result of a weakening of the cohesion (thermomechanical instability threshold).

Conclusion

In this section, a model study on the interrelation between the occurrence of complex aggregation patterns issued from drying of NPs suspension, the size of the constitutive NPs (from 3 to 35 nm), and the drying temperature (from 20 to 100°C) has been developed. Besides the substrate wetting properties which we here firmly established, the results show that the emergence of the large scale and well-defined aggregation patterns was controlled by the size of the NP, for a given temperature within the explored range. In addition, the thermal stability and hence the occurrence of the complex patterns were enhanced for the smaller particles. Though this may appear a priori counterintuitive, owing to the higher thermal mobility of smaller particles, we showed that these results actually account for the size-dependence of the cohesion of NP-based structures. Clearly stated, this size effect is highlighted by the fact that assemblies of small NPs have higher cohesion than those made of larger ones, independently of their spatial organization (see General Annexe). Using a rather simple phenomenological picture of the cohesion energy density of a NP assembly based on VdW forces, we showed that the thermomechanical stability of the aggregate scales with the size R of the NPs, either as R -2 (i.e. as the cohesion energy density) or R -3 (i.e. as the internal resisting frictional force).

In the following section, the role of the presence of salts in the suspensions in the occurrence of these complex patterns will be discussed.

The role of salts in the formation of the complex NPsbased structures

As described in part 1, the preparation of colloidal suspensions requires the use of reducer and surfactant agents to reduce gold ions and to stabilize NPs. This second section investigates the influence (role) of compounds that are present in the suspensions as residues on the formation of NPs complex aggregation structures.

Experimental Methods

A cleaned bare silicon substrate bearing its native oxide layer (SiO2) is used in this section. Citrate stabilized and amine (-NH2) functionnalized spherical gold NPs of 25 nm in diameter were prepared as described in part 1.

The solutions are then dialyzed through NADIR membranes provided by ROTH, displaying pores of average size: 2.5-3.0 nm diameter. These membranes are treated before any use as followed. They are immersed ca. To demonstrate the role of the synthesis residues (salts, surfactants) on the formation of complex aggregation structures, a series of drying experiments has been performed.

-First, 5 µL drop of NPs suspension (before and after dialysis) has been deposited on two distincts substrates in a thermally equilibrated chamber at 20°C and 33 % of RH.

-Then, for the dialyzed drop which has a much lower NPs concentration compared to the "as-synthesized" one, the following procedure was used to compensate for that too low particle concentration which can also impact the structure, regardless of the presence of synthesis residues (salt in particular). This procedure consists in adding to the initial deposited drop volume (5 µL) successive volumes of 5 µL after about 5 minutes of evaporation, i.e., just before the evaporating drop starts to retract, ensuring this way a drying at constant contact area. This procedure of drop addition was performed 100 successive times, allowing the final drying drop of dialyzed suspension to achieve the NP concentration of the "as-synthesized" solution. This method is referred to as "multisteps concentrated drop". However, this approach suffers from some drawbacks, namely the perturbations that are inherent to the successive volume additions, and the possible memory effects of previous evaporation stages. Therefore, we have used a second approach consisting in concentrating the dialyzed solution 100 times, prior to the drying. This was achieved by centrifugation (at 20000 rpm for 40 min) of a volume of 10 mL of dialyzed solution to which all the supernatant was carefully removed, leaving a 100 times concentrated bottom phase of 100 μL. This concentrated solution was sonicated to disperse homogeneously the NPs, and 5 μL was deposited on the substrate for a single step drying. This approach is reffered to as "one-step concentrated drop".

The complex aggregation structures were captured in the final drying spot, generally at half-way between the center and the border of the final drying spot.

Finally, Scanning electron microscopy (SEM) and Energy-dispersive X-ray spectroscopy measurements of the samples were performed to observe the aggregation patterns and characterize the existing organic and inorganic compounds present in the complex aggregation structures.

Results and discussion

Complex patterns arising from the drying of both raw and dialyzed solution drops have been investigated in this section. Then, the drying patterns of the concentrated, dialyzed NPs drops ("multi-steps concentrated drop" and "one-step concentrated drop")

have been discussed, versus the raw solution, in terms of the absence/presence of synthesis residues, and of salt in particular.

Images of figure 2.1.3.1a and b display respectively, the occurrence of complex patterns in 5 µL drying drops of citrate stabilized and amine functionalized NPs suspensions on SiO2 substrates, before dialysis. Ramified dendrites patterns appear at both the periphery and at the center of the drying area. These drying aggregates that are more stretched at the periphery become essentially axi-symetrical at the center of the drying area. although the difference of NPs concentration in the two solutions can also impact this structure formation. To elucidate the parameter that predominates the formation of these complex patterns, we have increased the concentration of the dialyzed drop by addition of volume increments at constant contact area during the drying, as described previously ("multi-steps concentrated drop"). These last experiments and results seem to point out that a threshold NPs concentration in the deposited has to be reached to ensure complex patterns formation. This drop accumulation method allows to compensate the lost of particles by dialysis (volume fraction decreased by a factor of 100 after dialysis). to generate some structures in the final spot, this NP concentration does not seem to be the only parameter that acts on the structure formation and its extent, when we compare these results with those produced by drying drops of as synthesized solutions.

However, and as discussed in the experimental methods of this section, this approach suffers from some drawbacks, namely the perturbations that are inherent to the successive volume additions, and the possible memory effects of previous evaporation stages. Therefore, we have used the second approach described in the experimental methods and referred to as "one-step concentrated drop". This approach did not lead to complex dendrites structures, the drying area showing only a random distribution of featureless and discrete particles aggregates as shown in figure 2.1.3.4. To indentify possible missing key parameters, SEM (Scaning electron microscopy) and EDX (Energy dispersive X-ray spectroscopy) to characterize finely the morphology and composition of the structures. and the chlorine (Cl -). Indeed, after successive 100 additions of 5 µL of the dialyzed suspension to the initial deposited 5 µl dialyzed drop, the NPs concentration increases as well as that of the residual ions that are present in milli-Q water (K + and Cl -). The In this case, where the concentration of water residual ions is not increasing (comparable to the nominal dialyzed drop), we did not notify any dendrite structure even in the final drying drop. The occurrence of these complex NPs aggregation patterns thus seems to be assisted by the co-crystallization of these pre-existing salts in the solvent and suspension.

To conclude, this series of experiences highlights the role of the ions (cations and/or anions) in the formation of complex patterns. The counterions of the reactive compounds (Na + and Cl -) participate via a co-crystallization process with NPs to the occurrence of the dendrites-like structures [figure 2.1.3.1] during the dyring of the suspension drop. The low probability of occurrence of these complex patterns [figure 2.1.3.2 and 2.1.3.4] with a too low or negligible amount of salts ions in suspensions (after dialysis), seems to support this hypothesis.

To better corroborate the influence of residual salts on the formation of these complex aggregation patterns. We will consider here some basic models and relations and relations of ions-mediated colloids interactions, from which we will discuss our results.

b. Simple theoretical account of the crucial role of residual ions

Let us consider the case of amine stabilized NPs. The surface charge of these NP at the solution pH (acid) is positive and the surface electric potential will be noted φ0. In the presence of salts in the solution, a layer of negative ions can adsorb on the surface of the particle. Hence, the particle is mainly surrounded by an ionic cloud consisting mainly of negative (Cl -) and positive (Na + ) ions. This is called Stern layer. Beyond that, we are dealing with a diffuse layer (Gouy-Chapman) (EDL), characterized by an electrical potential corresponding to that of a modified surface. This potential can be calculated The Debye length calculated for the raw amine stabilized Au NPs (of 25 nm in diameter) is ca. 1nm. In the raw solution, each NP is stabilized through electrostatic interactions within a virtual "shell" between NPs of the order of (called for this reason "screening length"). The Debye length increases with the decrease of the salt concentration (after dialysis). For dialyzed suspensions, the debye length is ca. 26.5nm. Furthermore, we can compute the interaction force between two charged spherical particles distant of h in the solution from the Poisson equation and the Maxwell-Boltzmann expression as follows.

The first law of thermodynamics gives that the relation between the differential of the particles momentum and that of its potential as:

dp + ρdφ = 0, Assuming that the surface potential of the particles φ0 is constant, the interaction potential between two particles of radius R is Vr= 2πε ( ) e -K(h-2R) with γ = tan h (

), where z is the particle charge and h the center-to-center distance between the particles.

From the above relations, it comes that the intensity of the repulsive force between the particles is stronger and of large extent when the particle surface potential is higher.

Indeed the potential of the modified surface is φ = φ0 e -x/ , where in the case of dialyzed suspension is much higher than in the case of raw suspension [table 2.1.3.3] consequently φ is much higher and the intensity of repulsive force between the particles is much higher in the case of dialyzed suspensions.

These repulsion forces between the particles prevent their close contact and the formation of the aggregation seeds in the evaporation drop, explaining the extinction (low probability of formation) of the fractal patterns on the solid surface after the drying.

Conclusion

This section has focused on the role of residual ions of synthesis and of milli-Q water solvent in the occurrence of complex NPs aggregation patterns. The emergence of these multibranched structures was shown to be assisted by the co-cristallisation of salts ions pre-existing in the suspension. Consequently, when the amount of these residual ions is too low, the probability of appearance of these complex patterns, and more precisely fractal structures is very low, as attested dialyzed NPs suspensions. Finally, these results

have revealed that the interplay between several physical parameters among which the hydrodynamics (wetting) and the residual ions effects is required for the emergence of the complex aggregation patterns.

So far, we have characterized (morphology and composition) these ramified dendrite aggregates and studied the key parameters and underlying mechanisms that control and drive their occurrence. However, there is an important question which remains 104 concerning these complex aggregation patterns: are they stable or metastable (kinetically arrested) structures? And how they evolve along the time? These questions will be evoked in the last part of this work.

General Conclusion

Imposed anisotropy of either physical or geometrical origin is known to be a determining parameter in the emergence of complex patterns (fractals, dendrites) in organizing matter (crystallization, growth of bacterial colonies). In such systems, any local gradient in a physicochemical parameter or broken symmetry may result in complex growth shapes. In contrast, the formation of self-organized complex patterns at molecularly smooth and chemically homogeneous surfaces in a uniform and structureless solution of monosized particles constitutes an interesting phenomenon. In this chapter, we have investigated the formation of complex aggregation patterns based Au NPs and proposed a mechanism that explains their spontaneous growth at chemically and anisotropy-free surfaces.

We first showed a model study on the interrelation between the occurrence of complex aggregation patterns in drying nanofluids, the size of the constitutive NPs (from 3 to 35 nm), and the drying temperature (from 20 up to 100°C). Besides the substrate wetting properties which we here firmly established, the results have displayed that the emergence of the large scale and well-packed aggregation patterns was controlled by the size of the NP up to a certain temperature threshold. More specifically, clusters and relatively well organized drying structures were found to form at higher drying temperature only for NPs of size smaller than 10 nm for which we showed that the cohesive energy density was higher than for larger NPs.

The second section of this chapter was focused on the investigation of the effects of NPs synthesis residues in the suspensions on the appearance of these spontaneous selforganized complex patterns. The role of these synthesis residues such as the residual ions from the metal (Au) salt and the reducing agents, as well as those stemming from the aqueous solvent was highlighted in the occurrence of the complex NP aggregation patterns. Indeed, the emergence of these patterns is assisted by the co-crystallization of these residual salts existing in the "as-synthesized" NPs suspensions. Where the presence of these ions is minor, the probability of patterns formation, and more that by their promising nanotechnological applications 1 which are related to the functional properties of those objects that are highly sensitive to the arrangement of the unit blocks. Among these functional arrangements, nanorings patterns can serve for instance as nanometer-scale sensors, resonators and transducers, or provide a unique platform for biological and pollutants analyses at small scales. 2 The first particle nanorings obtained by a spontaneous process (self-coiling of nanobelts), was zinc oxide nanorings discovered by researchers at Georgia Institute of Technology less than 10 years ago. 3 nanoparticles into rings which can be formed by two different mechanisms: dipoledirected self-assembly (typically 5-12 particles, ring diameters between 50 and 100 nm), and evaporation-driven hole formation in viscous wetting layers (ring diameters ranging from 0.5 to 10 µm). As a result of that intense activity toward nanorings, a number of metal particles nanoring structures have been created either with nanolithography (such as e-beam, 9,10 capillary force lithography 11,12 ) and templateassisted techniques (µ-contact printing 12 and porous membrane 13,14 ).

However, new alternative approaches relying on self-assembly processes and especially drying-mediated techniques are still being developed for the fabrication of nanoparticles rings. For instance, Govor et al. 15,16 have proposed an approach based a combination of phase separation in a thin film of a binary (polymer and nanoparticles) mixture, leading to a bilayer structure, the subsequent decomposition of the top layer into droplets, and finally the deposition of the CoPt3 nanoparticles at the edges of the evaporating droplets. Liu et al. 17 , have used pre-patterned surfaces edges of the evaporating droplets prepared by phase separation of a polymer film to direct the assembly of nanoparticles.

Other methods using evaporation-assisted assembly have also been studied. Ohara et al. 18 have proposed a method that is based on the dewetting of a thin suspension film from a substrate, which leads to the formation of a peripheral particle accumulation (coffee ring), around opening holes. This approach often leads to the formation of micrometer size rings. The work developed by the Pileni's group in this field rather uses Bénard-Marangoni instabilities, 19,20 and related convection cells in the drying suspension drop to self-assemble the nanoparticles into nanorings. Finally, Zubarev et al. 21,22 have succeeded to use condensed water droplets on a nonpolar solvent as template to self-assemble dense arrays of polystyrene coated gold nanorods on solid supports. It thus appears from these studies that drying-mediated techniques represent a simple and flexible route toward the self-organization of nanoparticles into large scale nanoring arrays. 23 Here, we developed a system that uses confined immiscible nanobubbles and nanodroplets "templates" either grown in situ or purposely introduced in the suspension and allowing a flexible control of both the size and distribution of the resulting nanorings patterns. In that sense, the approach we propose here is a templateassisted method that essentially takes benefit of simple interfacial phenomena, namely the confinement of naturally occurring or purposely prepared nanobubbles or nanodroplets, embedded at the interface between a hydrophobic substrate and a nonmiscible liquid drop. At the difference of the drying-mediated assembly and nanoring formation described above, especially the closer methodological approach of Zubarev et al. 22 , the method we here report has the following distinctive feature. Indeed, it allows a more flexible control of the size and spatial distribution of the nanorings, as well as the organization of the nanoparticles within the ring, through the introduction of calibrated nanodroplets template, and their confinement that prevents them from an evaporationinduced destabilization. In addition, this topic of nanobubble-related interface phenomena has appeared recently to have strong relevance to many of the current technological issues, including the wall slippage in microfluidic devices, the hydrophobic interaction, the stability of colloidal systems, 24 as well as nanoholes formation in drying thin organic films 25 ).

A representative illustration of these nanobbuble-related interface phenomena is given here in figure 2 silicon wafer. This often undesired but observed nanoring defects in organic thin films can also be tuned into an opportunity to form well-defined and organized nanoholes (nanoporous) structures. We here describe an unexplored use and application of these confined nano-bubbles and -drops, as well as the underlying mechanisms involved in their formation in drying nanofluids. Nanobubbles (nanodroplets) laying on a hydrophobic surface and surrounded by an immiscible nanoparticles suspension (solvent) represents an ideal platform to selfassemble chemically coated nanoparticles. As the nanoparticles adsorb at the nanobubble/solution interface, the drying of the surrounding suspension drop and the subsequent rupture of the nanoparticles-coated nanobubble (nanodroplet) interface leads to the formation of a peripheral ring of particles on the substrate. Clearly, the above description requires that the NPs adsorbing at the nanodroplet/nanobubble interface with the suspension be insoluble in the nanodroplet (liquid). This method also requires two interfacial conditions for the particles nanorings patterns to form: i) a NP suspension and a contact angle between the suspension drop and the substrate that allow drop slippage on the substrate and, ii) a short evaporation time of the suspension drop to ensure a rapid retraction of the contact line under non-pinning conditions.

These interfacial (wetting) and evaporation conditions are achieved for an organic NPs suspension drop and a hydrophobic substrate which are elaborated below, together with the nanodroplet and nanobubble templates.

Experimental methods

The hydrophobic surfaces were self-assembled molecular films of methyl-terminated nhexadecyltrichlorosilane Cl3Si (CH2)15CH3 (referred to as HTS), formed on silicon wafers bearing their native oxide layer (SiO2). These self-assembled molecular films (SAM)

were prepared as described in the first chapter of the first part of the dissertation.

b. Nanobubbles

The NPs were dispersed in THF for nanobubbles assisted ring assembly as mentioned previously. In this case, the suspension was deposited onto the HTS surface and allowed to dry at 75 °C and 33 % of relative humidity. Under these conditions, the nanobubbles will grow spontaneously at the solution/solid interface. Indeed, the vapor pressure of THF increases non-linearly with temperature according to the Clausius-Clapeyron relation. The boiling point of THF is 66°C which is the temperature where the vapor pressure equals the ambient atmospheric pressure. Increasing the drying temperature above 66 °C (drying temperature = 75 °C) allows the vapor pressure to overcome atmospheric pressure, triggering the in-situ growth of nanobubbles.

Results and discussion

For our particular systems (volatile organic solvents) and operating conditions, the high evaporation rate does not allow a strong pinning of the contact line for the convective transport and accumulation of the suspended particles (nanobubbles, nanodroplets, NPs) in the wedge of the drop to develop notably. Indeed, by using low boiling point solvent such as cyclohexane (boiling point at 80.74°C) and tetrahydrofuran (boiling point at 66° C), the evaporation rate (90 sec for the drying of the cyclohexane suspension drop, and a few sec for the THF one) is increased and the timescale to reach the receding contact angle is shortened before peripheral particle accumulation definitively impedes the retraction. In addition, a short evaporation This table shows that pure water nanodroplets are not relevant in this case, due to the combination a low evaporation rate and a too high contact angle which would make these water nanodroplets unstable and easily entrained (collected by the evaporating suspension drop).

a. Early stage of the drying

At the early stage of the drying, nanoparticles-coated nanobubbles/nanodroplets of small size are entrained at the periphery of the suspension drop whereas bigger ones mainly settle slowly in the center due to the predominance of the gravitational forces. At the difference of the large nanodroplets, the drainage of the small ones inside the wedge is favored by both the convective outward flow generated by the evaporation gradient along the drop 26 and the low resisting hydrodynamic force proportional to the size of the nanodroplets.

The dewetting dynamics of the evaporating suspension drops were then investigated for the formation of the NPs coated nanobubbles and nanodroplets arrays, as a function of both the solvent (THF, cyclohexane) and receding velocity of the retracting drop. These two parameters determine the competition between, (i) the magnitude of the shear stress that NPs covered nanobubbles (nanodroplets) experience during the receding of the contact line and, (ii) the attachment of the nanoparticles to the substrate surface, versus their retention in the bulk solvent. The balance between these two forces determines either the detachment or drainage of the nanodroplets, or their morphological distortion under the shear stress exerted by the receding wedge of the evaporating drop. The magnitude of the shear stress within the wedge of thickness h, receding with an average velocity U is at first order proportional to the viscosity η of the suspension drop flowing past the wall, and given by, σ ~ η(U / h), for enough small thickness h, and assuming no-slip at the interface. That no-slip boundary condition has to be satisfied here by the nanodroplets (nanobubbles) attachment to the substrate.

For our particular systems, U is of the order of 25 µm/s for cyclohexane and three times more for THF drop, with receding contact angle θr of 11±1° for both THF and cyclohexane suspension drops (comparable wedge thickness h). Since the viscosity of these two solvents are comparable, one can assume from these data that the shear stress experienced by nanobubbles in the wedge of THF drop is about three times larger than for nanodroplets in cyclohexane. The confinement of the ethanol/water (E/W) nanodroplets in the wedge of the receding cyclohexane suspension drop and the shear force they experience from the contact line, induce their local morphological distortion. But at the difference of nanobubbles, the L-R vdW forces act to stabilize the cyclohexane suspension film against rupture due to the polar nature of the (ethanol/water) mixture, which now invert the sign of the Hamaker constant in this system (A -0.5x10 -20 J < 0). 27 This leads to a disjoining pressure (-A / 6πh 3 ) > 0 that tends to maintain the (nanodroplet/suspension film), and (suspension film/surrounding air) interfaces away.

As previously, we still consider the assumption that no nanoparticles remain locally at the apex under the confinement condition and right before the complete destabilization of the nanodroplet. In the same time, the evaporation which physically reduces the thickness of the suspension film at the apex of the nanodroplet leads to a local distortion, 28 although the nanodroplet would prefer for the above interaction free energy reason (sign of A) to be covered by a suspension film of finite thickness. To circumvent this ineluctable evaporation-driven reduction of the suspension film thickness against the disjunction pressure, the nanodroplet proceeds through the unique freedom that characterize soft matters, the local and small deformations of the interface which for these systems has a low energy cost. This local deformation that takes place at the apex of the (nanodroplet/suspension film) interface toward the centre of the nanodroplet (depression) physically amounts to a local thickening of the solvent film that stabilizes this latter against rupture, until the wedge of the drop crosses the nanodroplet, as shown in figure 2.2.2.3b. As already mentioned above, this arises from the balance between the gravitation and the outward convective flow during the drying of the suspension drop that generates a fractionation between large and small NPs-coated nanodroplets/nanobubbles, as well as a depletion of small ones in the center of the drop. As a result, small nanorings structures are highly concentrated in the vicinity of the contact line. This high nanoparticles-coated nanodroplets (nanobubbles) density can even create a complete line pinning and confinement of the residual suspension drop in the late-stage of its evaporation.

The following section will focus on the study of the physico-chemical parameters governing the formation of these ring-like structures. These main parameters are first the concentration of NPs in the suspension, then the NPs shape (from sphere to rod) and finally, the structure of the substrates (prepatterned surfaces). When the NPs fraction in the suspension drop increases, the number of particles at the suspension/nanodroplets (nanobubbles) interface becomes too high and the particles collapse inside the nanodroplets during the instability phase, filling the whole ring in a disk-like structure after the explosion of the nanobubbles (nanodroplets).

c.2. NPs shape effect

The procedure to self-assemble spherical Au NPs into ring-like structures has also been tried with Au nanorods. The as-synthesized nanorods which were then chemically coated with hydrophobic molecules as described in part 1, have been used to produce ring-like structures using the nanodroplets templates. The results displayed in Figure 122 2.2.2.8 prove that the anisotropic particles also spontaneously self-assemble into ringlike superstructures, although the ring distribution in this case is more random and of lower surface density. Independently of their shape, (spherical or anisotropic), nanoparticles can self-assemble into ring-like structures under our experimental procedure. In addition, this selfassembly in ring-like structures has also been observed onto partially wetted TEM grids as shown in figure 2.2.2.9. Because of the shape inhomogeneity in the "nano-rod" suspension and because of their irregular shape, the organization of the Au NPs in the ring-like structures is also more random, as observed on the TEM images shown in the figure 2.2.2.9. The size of the rings based on this technique can be controlled by modifying substrate domains size. Indeed, the average size of rings formed on domains of 4 µm diameter is about 1µm. Figure 2.2.2.12 displays the formation of bigger rings on larger domains.

This image also displays the increase of density of NPs rings onto patterned substrates.

The average size of rings diameters formed on 60 µm hydrophilic domains is about 6 µm. As compared to existing nanofabrication techniques relying mostly on templates and lithography, our method undoubtedly presents the advantage of being capable to produce in a few seconds a large amount of well-defined nanorings of adjustable size, and which can be organized in various shapes and spatial distribution (arrays). These nanorings in general, and those prepared here by self-assembly can find potential and direct applications in nanotechnological areas. And beyond that useful tuning of nanobubbles towards the creation of functional metal nanoring patterns, this study also contributes understanding the undesired growth of nanoholes defects from dissolved or spontaneously nucleated bubbles in coatings that are prepared from polymers or suspensions solutions.

The following paragraph will highlight the potential application of these nanorings (on rigid substrate) as highly sensitive optical sensors.

d. Nanoring-based Surface Enhanced Raman Spectroscopy (SERS)

The optical properties of the ring-like structures have been investigated and discussed in this following paragraph. Particularly, the optical SERS sensitivity of the NPs aggregates versus the constitutive particles assembly was assessed, using the alcane thiols grafted at the NPs as model analyte molecule. These results were discussed for their dependence on NP organization on the substrates. The results clearly display the variation of the Raman spectra intensity versus the organization of the NPs assembly. The first trivial observation is the weak signal of the thiol molecules on the reference sample corresponding to a random distribution of Au NPs onto the hydrophobic substrate, compared to the strong response on the two other NPs structures. The SERS characteristic peaks of thiols molecules are displayed in Table 2.2.2.2. The evolution of the maximum peak intensity vs the organization of Au NPs accounts for the strong effect of the coupling between the NPs and their cooperative plasmonic response. This coupling over the localized plasmons of the discrete and close-packed Au NPs strongly influences their Raman response. This SERS enhancement effect of the NPs aggregates [figure 2

Wave number (cm -1 ) Assignments (vibrations)

C-H of CH3 aliphatic

C-H of -(CH2) n-

CH2 of CH2-S-

C-C of -(CH2) n-

.2.2.13b] has also been observed and extensively described in the case of Au NPs multilayers deposited onto a rigid substrate (General Annexe).

Whereas the random discrete NPs distribution provides a very weak Raman response, the nanoring-like structures strongly enhance this response. But more interestingly, if we compare the Raman spectrum of an alkane thiol molecule adsorbed onto a shapless NPs aggregate to the one adsorbed on a ring-like structure as displayed in Figure 2.2.2.13 d, it appears that the Raman signal can be strongly enhanced by the spatial organization of the NPs (ring-like structure), for a much lower NPs density! The amplification of the main peak at 1465 cm -1 corresponding to the C-H deformation vibration of CH3 aliphatic is particularly well defined, and its SERS enhancement factor is of the order of 5 in favour of the ring-like structure. This result particularly underlines and well emphasizes the effect of the NPs organization on their optical response in general, and especially on their SERS properties.

As already shown by simulation by Aizpurua et al. 6 , nanoring assembly provides a specific electric field enhancement. Figure 2.2.2.13a displays the near-field vector distribution and field enhancement of a nanoring. 6 The electric field is substantially enhanced inside the ring cavity (green and yellow regions). The field distribution in a plane that contains the ring axis [figure 2

.2.2.13b]

shows that a uniform enhancement is maintained through most of the cavity region. The enhancement factor reaches the maximum at the upper and lower ends of the ring, indicating a buildup of charge at these ends which supports the field enhancement uniformly in the cavity. In this context, nanorings could serve as resonant nanocavities for holding and probing smaller nanostructures, such as biomolecules or quantum dots.

Conclusion

The formation of nanoring-like patterns mediated by drying nanofluids drops confining nanobubbles and nanodroplets templates has been studied in this chapter. Compared to previous techniques, this drying mediated method avoids direct replication from prefabricated templates, taking advantage of naturally occurring interfacial phenomena such as the formation of nanobubbles embedded at hydrophobic surfaces or nanoemulsions. During the drying of the NPs suspension drop, the confined nanodroplets and nanobubbles lying at the surface of a hydrophobic substrate adsorb a NP coating at their interface with the suspension drop. The formation of the nanorings Scale bar 129 was well accounted for by the confinement and the destabilization of the nanobubbles (nanodroplets) within the receding wedge as the contact line of the evaporating suspension drop crosses them, and ultimately the migration of the nanoparticles along the nanobubbles (nanodroplets) to their periphery with the substrates. Beyond predictable parameters like the evaporation rate, the receding velocity of the suspension drop or the adhesion of the nanobubbles to the substrate, we showed that the destabilization (rupture, evaporation) of the nanobubbles/nanodroplets was controlled by the disjoining pressure in the suspension film at their apex. Furthermore, our system and mechanistic description reveal to well extent beyond the spontaneous nanoring formation, accounting also for the often observed (and unwanted) formation of nanoholes in drying polymer thin films. In addition, physico-chemical parameters governing the formation of ring-like structures were studied. These main parameters were the concentration of NPs in the suspension, the NPs shape (from sphere to rod) and finally the heterogeneity of the model substrates (prepatterned surfaces) that enabled the organization of NPs rings onto specific surface area. Finally, these wellorganized structures of Au NPs have proved to be an effective analytical tool when used to detect very low amount of organic molecules adsorbed on the structures, by Surface-Enhanced Raman spectroscopy (SERS). Furthermore, we showed that the SERS sensitivity of the Au NPs was significantly enhanced by the organization of the building units into ring-like structures, bringing a clear evidence of assembly effects in nanostructured materials. The combination of pre-patterned substrate with the control of shape, size and organization of nanocolloidal metal particles in general, and of Au nanocolloids in particular, provides a new and effective tuning parameter towards the improvement of the stability and sensitivity of nanostructure-based devices.

These first approaches of drying-mediated assembly of the colloidal NPs into complex patterns and ring-like structures, and the study of the main parameters controlling their organization (concentration, evaporation-wetting dynamics, temperature...) have pushed our investigations towards even more complex systems composed of biopolymers (sodium alginate) and NPs for more applicative sysptems. The following chapter will indeed focus on the drying mediated assembly of such binary (alginate/NPs) systems, going from their drying-mediated structures to the capillaryassisted fabrication of lab-scale composite hydrogel microfibers. precise patterns. Chemical self-assembly, 1 scanning probe lithography, 2,3,4 photolithography 5 and microcontact printing 6 have been developed to assemble NPs onto rigid surfaces. However, Templated Self-Assembly (TSA) approaches for the fabrication of well-defined patterns represent a new opportunity to realize long-range and large scale arrangements of chemically produced metallic clusters. 7 Interestingly, biological materials such as proteins 8,9 and viruses 10 have emerged as potential templating materials. 11 Among the nanoworld diversity, metallic nanomaterials present particularly interesting optical, electronic and magnetic properties (see chapter 1 of part 1). 12 Such inherent physical properties make them suitable for creating biosensors, diagnostic agents and novel nanostructured materials. The sizes of metallic NPs, tuneable from 3 nm up to 100 nm (see chapter 1 of part 1), also provide large surface area to volume ratio for efficient interaction with biomacromolecules. The surface properties of NPs can also be easily adjusted by the covalent grafting of organic molecules with appropriate terminal functionality (see chapter 1 of part 1), offering a certain polyvalence in the creation of surface-specific receptors. Indeed, several recent review articles (focusing on nanoparticle-biomacromolecule interactions) have reported the large field of applications of NPs hybrids as biological and diagnostic sensors. 11,13,14,15,16,17,18 However, the preparation and stabilization of metallic NPs represent a highly and crucial issue at the nanometric level, as their aggregation is also associated with the loss of their specific nanoscopic properties. For instance, low concentration polyelectrolytes solutions, such as polyphosphate, polyacrylate, poly (vinyl-sulfate), poly (ethyleneimine), 19,20,21 and poly (allylamine), 22 have been extensively studied to stabilize NPs suspension and prevent microscopic aggregates formation. The NPs supension stabilization is mainly insured by electronic interactions between polymer functional groups and metal particles.

Assembly of NPs through biomolecules templating has also been investigated. For instance, deoxyribonucleic acid (DNA) 23 Highly selective base-pairing interactions between complementary single-strand DNA chains represent ideal attachment point to generate well-defined nanoassemblies.

Native double-helical DNA can directly interact with metal ions and their complexes to build NPs based materials. Hidenobu et al. 24 developed a simple method to create highly ordered structures of gold NPs embedded along DNA chains deposited onto rigid substrates. They achieved these well-aligned and long-range organized assemblies according to two approaches: the first one consists in stretching and fixing DNA onto the surface, and then depositing gold NPs. The second one was carried out by first grafting nanoparticles to DNA chains in solution phase, and then stretching and fixing the system on the surface. This second technique might be transferred to the fabrication process of metal NP plasmon "waveguides", 25 insuring energy transport along a NP chain over a short distance. Wang et al. 26 have also studied the specific assembly of gold NPs coated with cationic "trimethyl (mercaptoundecyl) ammonium" monolayers on DNA. Their results showed that positively charged NPs are closely packed along the anionic groups of the DNA template to afford one-dimensional chains. The distance between NPs is directly determined by the biopolymer monolayer thickness. These highly organized 24 Haidara et al. have demonstrated that polysaccharides can self-assemble into complex aggregation structures by drop evaporation-drying dynamics. 46 They showed that the structures which grow exclusively within the final drying spot arise from the ordered assembly of the concentrated polysaccharide (sodium alginate) chains mediated by the condensation of cations trace present in the system. These residues of cations, dragged with the polysaccharide chains and concentrated by the drying process inside the residual spot, mainly come from the ultrapure water used as solvent. Additionally, wetting-assisted formation of NPs based-complex aggregation patterns was also observed in the previous chapters of this part. The mechanisms and the parameters that underlie the emergence of such assemblies were discussed versus NPs size, substrate effect, drying temperature, residual ions in the suspensions, hydrodynamics (see

chapter 1 of part 2).
Beyond the fundamental aspects of self-assembly, either mediated by wetting and related hydrodynamics or induced by ions, the co-assembly of biomolecules with heavymetal cations or with charge-stabilized nanosized particles, 47,48,49 towards functional nanostructures still faces many challenges. We may ask for instance the following basic questions:

-Is there a specific relation between the characteristic features of the drying structures on the one hand, and the size and the density of the surface charges of the particles or the valence of the ions, on the other hand 50 The present chapter addresses this issue of drying-mediated co-assembly and complex pattern formation in such binary systems, using anionic sodium alginate (SA) and amine stabilized gold NPs (Au-NPs). These two species can, in particular, exchange electrostatic bonds through their carboxylate and ammonium end groups (COO /NH3 + ) for a certain pH. The emergence of large fractal patterns, and the physico-chemical conditions required for their formation (effect of the residual ions and NPs size, influence of alginate concentration, vs. NPs fraction in the suspension) have been investigated. In addition, the phenomenology of the emergence (or not) of such structures, and the hydrodynamics acting during the drying of the solutions have been discussed. These nano-aggregates composed of alginate and NPs have been characterized by atomic force microscopy (AFM). This nanoscopic study was carried out to better structure of these nano-aggregates from the mesoscale, down to the molecular scale, and their dependence on the drying conditions and solutions parameters (alginate/NPs interactions, residual ions...). Finally, these highly-ramified, large scale dendritic patterns, have also driven the opportunity to develop a lab-scale fabrication method of composite hydrogel microfibers, made of alginate/Au NPs.

Experimental Methods

Silicon wafers bearing their native oxide layer (SiO2) have been used as substrates for the drying experiments. These wafers were cleaned by sonication in chloroform and dried under nitrogen flow before use.

Amine (-NH2) coated colloidal gold NPs referred to as "as-prepared" (as-synthesized or raw), of 25 nm in diameter were prepared as described in part 1. A part of this "asprepared" NPs solution was dialyzed for ~3 days to remove the ions excess and nonreacted synthesis residues, as described in the experiment methods of the section 2.1.3 of the first chapter of this part. Both NPs solutions, the "as-prepared" and "dialyzed"ones, were characterized to determine the size and volume fraction of the particles, as well as for the pH and the ionic conductivity of the solution. These characteristics are summarized in table 2.3.1.1.

The sodium alginate was purchased from Sigma-Aldrich, and described as a medium viscosity polyuronic acid (viscosity 2 Pa.s at 2 wt% in water), composed primarily of anhydro--D-mannuronic acid residues with 1 4 linkage. As given by Aldrich, the average molecular weight of this anionic SA1 polysaccharide was in between 80 and 120 kDa, for an average Mw~100 kDa. The calculation of the linear length of single chain gives an average value of ~200 nm. An Aqueous solution (SA1) of 1 wt% (10 In addition, alginic acid of a molecular weight of approximately 240 000 g/mol was also purchased from Sigma-Aldrich. As previously, an alginate solution referred to as sodium alginate solution (SA2) was prepared by mixing alginic acid and sodium hydroxide (NaOH) in the ideal 1/1 stoichiometry between the carboxylate groups of alginic acid chains and the sodium atoms of NaOH. The linear chain length of this alginic acid dispersed in solution SA2 is of the order of 480 nm; this value is twice the SA1 one.

Remark: Alginic acid is not water-soluble, and experience showed us that the minimum quantity of introduced sodium hydroxide should be at least equivalent to the amount of carboxylic groups of alginic acid to achieve dispersion of the polysaccharide.

Drying experiment

The drying experiment was performed in ambient conditions (21°C, ~40% RH) by depositing 5 L drops on substrate, under an optical video-microscope (Olympus microscope), equipped with a COHU solid state CCD camera operating at 25 images/s.

The evaporation-drying kinetics of the drop was followed in real-time on top-view configuration and recorded using the resident video/image capture software (Open Box Ver.1.8) on the driving PC. In parallel to these top-view captures of the drying kinetics and morphologies, the wetting parameters of the drops (contact angle and diameter)

were characterized in similar conditions (T, RH), using the Krüss G2 contact angle analyzer. For the 5 L drops used in these drying experiments, the average nominal contact angle of both the single-component and mixed (SA/NPs) solutions on the partially wetted SiO2 substrates was ~47°3.

Results and Discussion

The first part of this paragraph is dedicated to the characterization of the binary solutions using Transmission Electron Microscopy (TEM) before their deposition on the appropriate surfaces. Then, we will present the results on the occurrence of dryingmediated structures of composite (SA/NPs) at microscopic scale. We will discuss the Identical TEM characterization has been performed on both single and bi-co component solutions of SA2 and NPs. These characterizations have strictly led to structural and morphological organization similar to those of SA1/NPs system, and are not therefore redundantly shown here.

drying
After the structural characterization of these single-and bi-component solutions, the following sections will describe the drying experiments involving these solutions, focusing on the morphogenesis of the complex aggregation patterns in these systems on one hand and the fine structural and morphological characterization of these drying structures at both the meso-and nanoscale, on the other hand. The configuration and the critical steps of the drying dynamics of the wetting film of Naalginate solution can be summarized as follow:

-First, the large wetting film of the polymer solution (drop) slowly evaporates and dries before it reaches the receding angle required for the wetting front to retract.

-Then, the drop starts to recede at a certain velocity depending on the thickness and viscosity of the film.

-Finally, the retraction of the drop, driven by its evaporation ends by the formation of complex structures that appear spontaneously and quite instantaneously during the drying of the final tiny residual spot. 46 Owing to the above determining influence of salt, even as traces, on the formation of dendrite-fractal aggregates and crystallization patterns in drying solutions of NPs and biopolymers, 46 we have implemented reference drying images by the drying pattern [figures 2.3.2.2g-i] of a mixed solution of SA and Sodium Borohydride (NaBH4), before studying the binary "SA/NPs" systems. Indeed, these binary systems composed of the asprepared NH3 + stabilized-NPs and the sodium alginate also contain a significant amount of residual NaBH4 salt (Na + cations). These residual cations can co-react, or even preferentially react with the anionic SA1 to form (SA/salt) co-crystallization structures on drying. 46 A reference drying pattern of a mixed (SA/NaBH4) solution drop, containing identical NaBH4 concentration than the NH3 + stabilized-NPs solution, will serve for differentiating these salt-induced SA1 assembly structures from those arising eventually from a predominating (NH3 + stabilized NPs/SA1) interactions and co-assembly patterns.

The concentrations of the SA1 is of the order of 10 -6 M and ~ 2. It is worth mentioning that this latter statement is based on our direct, real-time observation of the growth kinetics of these patterns, as shown in the panels of figure Initially (early stage), the growth of the complex pattern follows an exponential function of time. Then, the kinetics decreases slowly toward the end of the growth process due to the lack of feeding matter. The overall profile of this kinetic curve is thus characteristic of a "sigmoidal" growth process.

Growth mechanism and SA concentration effect

SA concentration effect

Unlike the two high SA1 concentration mixtures (10 -6 and 10 The following paragraph describes and highlights the essential differences in the dynamic events which arise from the concentration difference of the SA mixtures, and account for their characteristic drying behavior and pattern. Whereas the drying patterns of the two SA1 concentrations drops are different, the total time to reach a dried state are almost identical. In other words the two SA concentration drops have similar evaporation rate. And for a given drop, and irrespective of the presence of solute particles or not, this evaporation rate is given by the solvent flux J(r)

[figure 2.3.2.9] at the drop/air interface, as described in chapter 1 of this part 2.

Fick's first law, which connects the diffusive flux to the concentration field, by postulating that the flux goes from regions of high concentration to regions of lower one, with a magnitude that is proportional to the concentration gradient can be written as followed:

J(r)= -D∇Cvap(r) eq 2.3.2.1
where D is the diffusion coefficient, and Cvap is the (water vapour) concentration gradient.

This flux J(r) of water in the environment (air) is maximum at the drop edge (r = R), and minimum at r = 0 (drop center). For evaporating drops containing solutes particles, this difference of evaporation rate between the wedge and the center of the drop will drive a a b solvent, and thus a solute flow toward the drop edge, leading to a concentration gradient of solutes within the drop solutes R) > solutes . As a result, an osmotic pressure associated with this concentration gradient will grow, tending to smooth that gradient by further solvent transport to the drop edge, as:

П ~ (r), where Fd is the resisting viscous force acting on the particle, and d is the particle's diameter.

The viscosity of the system, lower for the lower SA1 concentration (10 -7 M) will result in a higher mobility u of particles and residual ions, compared to the 10 Finally, these above results have demonstrated the role of the SA concentration in the mixed (NPs/SA) suspensions on the occurence of complex patterns. In particular, we showed that the hydrodynamics of the drying, and the associated convective transport of material to the periphery, or its drainage in the final spot, are among the crucial mechanisms that drive the occurence (or not) of these complex aggregation structures.

We have discussed above the growth mechanism of aggregation patterns in drying of binary (SA/NPs) solutions, the hydrodynamics and the effect of the concentration of SA in such drying process. In the following, we investigate the role of some critical compositional parameters, and in particular:

-The role of the synthesis residues (salts in the form of reducing agents) in triggering the formation of the drying-mediated complex aggregation structures in binary (SA/NPs) system [the effect of ions was shown for the single component both NPs (see chapter 1 of part 2) and SA 46 solutions].

-The relative size of NP-to-SA chain that determines the steric/topological accommodation, and the NP/SA chain interaction.

Previous results have shown that in the range of SA1 concentration (10 -7 to 10

Compositional analysis of the drying patterns-relation to synthesis residues

Patterns composition

The chemical composition of the patterns were first investigated by Energy-dispersive X-ray spectroscopy (EDX ) and Surface Enhanced Raman Spectrosopy (SERS) analysis, in the aim to determine the presence, and thus the role of the salts residues. Additionally to these components, the presence of sodium (Na) in the case of SA1/ asprepared NPs is noticeably detected. NPs within the SA chain all along the receding path.

Further along salt effect

The following paragraph will focus on the effect of the addition of salts to the binary (SA/ dialyzed NPs) solution on the appearance of the highly ramified structures. Figure This latter result definitely shows the crucial role of salts in the binary solution to induce highly ramified structures. By removing or adding the salt, we can clearly tune the occurrence of the ramified complex aggregation structures. This parametric investigation on the role of the salt on the emergence of ramified patterns in drying binary (SA/NPs) mixtures was completed by a second investigation that considers NP size effect on the genesis and the morphology of the structures.

(NP/SA) chain interaction-possible role of NP size

Dependence of drying patterns on NPs size

The relevance of the possible role of the NP size in the formation of highly ramified aggregation patterns in drying (SA/NPs) solutions drops was investigated. We first centrifuged the as-prepared NPs solutions, and collected separately the large NPs rich phase laying at the bottom of the tube, and the small NPs rich supernatant. These small and large NPs rich solutions of identical volume fraction of 2x10 -4 were used to prepare (SA1/as-prepared NPs) mixtures of 10 -6 and 10 -5 M in SA1. The results of the drying of these mixed (SA1/as-prepared NPs) solutions drops which contain all the required compositional ingredients and differ only by the NP size are detailed in figure 2.3.2.15.

1. The 2 nm NPs mixtures [figure 2.3.2.15a-b] display the appearance of dendrite aggregates rather close to the border of the drop, which here dries in a quasi-complete pinning mode, whereas a dense, though highly connected deposit form at the center of the drying area. As in figure 2.3.2.3c-e, the pinning of the drying drop here arises from the small size of the NPs (radius rNP~1nm) and the correspondingly low Stokes resisting drag force, Fη= -6 rNPv, (eq 3) and gravitation-driven sedimentation force, Fg~ (4/3) π .g.(rNP) 3 , which both enhance the convective outward flux (number/m 2 s) of NPs and residual salts. As a result, the compositional conditions required for the formation of the complex ramified aggregates are achieved at that location (drop border), where the dendrites patterns effectively occur. The morphology of these two structures seems to suggest a size determining relation between the NPs size and the thickness of the dendrite branches, which are in average much finer for the 2 nm NPs. However, regarding the emergence of these complex dendrites structures, these results do not show any size scaling relation or topological constraint in the studied range, between the SA1 chains (average linear length of ~ 260 nm) and the NP (from 2 to 25 nm).

NP/SA chain interaction

Comparing figure 2.3.2.15c-d and figure 2.3.2.15e-f clearly reveals the impact of the SA1 concentration on the compactness of the dendrite patterns, the ramification density, and the length and thickness of the branches, which both increase from 10 -6 M SA1 to 10 -5 SA1, for identical NPs concentration and size (25 nm). This is the result of the presence of more matter More precisely they point out an effect of this complexation which hinders more or less the conformational flexibility, while favoring the long-range "quasi-1D" connection (assembly) and cohesion of the complexes into fibrillar branches.

Indeed, different parameters can affect the conformation flexibility due to the NP/SA chains interactions. One of these parameters is the ratio (NPs/SA monomers). Two possible configurations of NP/SA chain interactions can be pointed out.

1. The first configuration can be obtained when the ratio (NPs/SA monomers) is high enough to saturate the SA chains with NPs [figure 2.3.2.16b-d]. This condition leads to an increase of chains stiffness.

2. The second configuration is obtained when the number of the SA chains is much higher than that of NPs. In this case, the complexes are not completely blocked with particles, which can guaranty a certain flexibility in SA chains [figure 2.3.2.16c-e].

These last results show a proportional relation between the (NPs/SA monomers) ratio and the stiffness of the (SA/NP) complexe. However, our experimental data mainly involve a (NPs/SA monomers) ratio << 1, as for the binary (SA/NP) system of 10 -6 M SA1, where the ratio was of the order of 10 -7 M. A second parameter affecting the conformational flexibility of the SA chain in the binary solutions is the size of NPs. The polymer chain probability to wrap around relatively small NPs (2 nm) in solution, is lower than for bigger ones from an energetical consideration. Indeed, we have observed previously that the morphology of the structures issued from the 25 nm NPs mixtures (SA/NPs) and the 2 nm NPs mixtures, suggests some size determining relation between the NPs size and the thickness of the dendrite branches. The aggregation patterns are thinner for the 2 nm diameter NPs. This experimental result strengthens this trend of a relation between the NPs size and the flexibility of the (SA/NP) complexes.

The emergence of these highly ramified dendrite patterns induced by drying of "alginate/Au NPs" solutions drops has been investigated in the previous paragraph.

Crucial parameters have been highlighted. However, the stability of these complex structures which are actually metastable structures, and as such highly susceptible to morphological evolution with the time, is also as important to understand as their genesis.

The following paragraph dresses this issue. Furthermore, our attempt to stabilize these (SA/NP) fibrillar patterns has seeded a labscale fabrication method of composite

b.3. From fundamental understanding to functional nanomaterials

The highly ramified drying (SA/NPs) structures are kinetically arrested structures and as such are metastable against variation of relative humidity, and may evolve through time-dependent reconstructions. The instability and reshaping of the dendrite branches will be fully and deeply addressed in the first chapter of part 3. But yet, this instability has led to the following simple idea, for preserving these highly ramified fibrillar dendrite patterns. Indeed, since SA readily forms a gel in contact with CaCl 2 solution, dipping the structures in the solution, or covering them, with a drop of this solution, will induce the gelation of the SA phase, leading to a (SA/NP) hydrogel network of higher viscoelastic modulus that stabilizes the whole dendrite pattern against aging (shape reconstruction). The results will be shown in the next part of this dissertation. However, once these fibrillar dendrites branches that constitute effective (SA/NPs) composite microfibers were made stable over months (in ambient conditions) upon gelation (hydrogel), it was practically impossible to detach and collect them from the substrate and the under-layer film, for any use at the lab-scale. To achieve this, we used a microgrooved PDMS support as a template. The grooved PDMS template was treated by an H2O plasma (to activate the surface) and stamped on a glass-supported thin liquid film of hexadecyl-trichlorosilane (in cyclohexane). Upon this pretreatment, the surface palteau in between each groove that were in direct contact with the silanes are hydrophobized, whereas the deep valleys retain the hydrophilic character induced by the plasma, and required for the capillary suction. The principle is based on capillarydriven suction and filling of such microchannels by SA1/NPs solution [figure 2.3.

2.17a]

that is placed at their front. After this capillary filling, the microchannels containing the solution were covered with a CaCl2 drop for gelation during a few minutes. The dendrite patterns can be stabilized against ageing and shape-distortion by the higher viscoelastic modulus of the (SA1/NPs) "hydrogel" network since the SA readily forms a gel by dipping the structures in a CaCl2 solution or by covering them with a drop of this solution, (see chapter 1 of part 3). The hydrogel microfibers were removed from the template by sonication in water, and collected either on a TEM grid or a coverslip for observation and characterizations. Figure 2.3.2.17b shows such composite (SA1/NPs) hydrogel microfibers networks resulting from the above microfabrication that was fully inspired here by a fundamental study aimed at understanding the genesis of the complex aggregation structures (highly ramified dendrites) produced by drying of nanocolloidal and biomacromolecular solutions. This study did not allow for further functional characterization (electrical conductivity for instance) of these microfibers, due to the very low volume fraction of NPs and the formation of clusters, as shown in the high resolution TEM images of figure 2.3.2.17c-d. Actually, even if one had a percolating distribution of Au NPs within the composite hydrogel microfibers, the presence of a too large non-conducting organic gap (SA) between these NPs or clusters would impede such electronic conductivity. Nonetheless, figure 2.3.2.17 shows definitely the effectiveness of this microfabrication process, while attesting a posteriori for the presence of the NPs in the dendrites branches, either embedded as single NPs or as finite-size clusters. These preliminary results show that an optimization of the method can potentially provide a flexible tool for fabricating small amounts of such composite microfibers (SA/magnetic NPs, quantum dots) for lab-scale functional characterization and optimization, before proceeding to large-scale production (spinning for instance) of these materials. Finally, these fibrils can have additional potential applications as a carrier for various therapeutic materials such as chemical drugs, cells, and recombinant proteins for the treatment of disease, a microscaffold for regenerative medicine, and an actuating or sensing element that can be integrated into the microfluidic device, 53 and for nerve regeneration and tissue scaffold…

Identical drying experiments and microscopic characterizations have been performed on both single and bi-component solutions of SA2 and NPs. These experiments have strictly led to

structural and morphological organizations similar to those of the (SA1/NPs) system. The results are not therefore redundantly shown here.

b.4. Conclusion

We have studied, from a model experimental approach, the drying of pure and mixed SA polysaccharide/Au NPs solutions, focusing on the role of the compositional parameters (residual salts especially) and NP size on the formation of the complex, dendrite aggregation patterns. Unlike single-component drops, which are either free of any organized structure (SA), or form at most small dendrite aggregates (NPs) for the used experimental conditions (concentrations, ionic force, partially wetted substrate…), mixture drops of the oppositely charged SA (COO ) and NH3 + -stabilized Au NPs lead upon drying to large size dendrites patterns, with an unusually high density of fibrillar ramifications. Besides the complexation between SA (COO ) and NH3 + -NPs, we showed that the genesis of these highly ramified drying-mediated assemblies was crucially determined by the residual salts. Finally, we have demonstrated that a facile, templatedirected microfabrication process of composite hydrogel microfibers, intended for labscale functional characterization and optimization of such nanomaterials could be developed from the results of this study.

In the following section, the morphology of the alginate chains and gold particles in the composite deposited onto the surface has been investigated at the nanoscale to better understand how they both interact and are organized in the aggregation structures. Very low (dilute) concentration of SA solution (10 -7 M) has been chosen for these drying experiments, with the aim to discriminate, and observe isolate or finite size clusters of Au NPs, SA and (NP/SA) complex.

c. Nanoscale aggregation structures

Nanoscopic aggregation structures obtained by drying-mediated organization of mixed SA polysaccharide/Au NPs solutions have been investigated at the nanoscale. Highly dilute solutions of SA (10 -7 M) have been used to improve the resolution of the aggregates (SA chains, NPs). To simplify the system, all the studied structures at this scale were carried out using the dialyzed solutions of NPs. The whole following AFM images were realized at an equivalent distance between the edge of the dried drop, and the final spot at drop center.

Images of both reference drying patterns of pure NPs and pure SA solutions have been studied. Then, binary SA/NPs systems using the two different chain lengths of SA (SA1 ~ 200 nm and SA2 ~ 480 nm) have been characterized by AFM. The following section displays AFM and EFM (electrostatic force mode) images of surface structures induced by drying drops of SA2 solutions. EFM was used to either enhance the probe signal provided by metallic NPs, or to annihilate those from alginate chains. Additionally, if we compare AFM Tapping mode images of figure 2.3.2.21e-f-g to those of figure 2.3.2.20c-d, we notice in both cases the presence of globules all along the interconnected sub-structure, the EFM phase contrast of which is low, accounting for a weak interaction between the tip and these globular objects. The conformation of SA chains in pure, single component solution (SA1 and SA2) evolves between that of a highly stretched, and that of a coiled chain, depending on the ionic strength (concentration of ions) of the solution. Between these two extremes, the SA polysaccharide chains may adopt more or less elongated shape with a higher chain flexibility. This higher chain flexibility corresponds to a decrease in the chain persistence length, due to the counterions condensation along the chains which reduces both inter-, and intra-chain electrostatic repulsion mediated here by monomer carboxylates (COO -). Indeed, the persistence length Lp of polysaccharide (SA) results As discussed above, single alginate chains in SA solutions are coated by positive counterions (Na + ). This counterions condensation along alginate chains affects the conformation of the chains. However, this organization differs when counterions are replaced by charged nanoparticles forming a binary SA/NPs system depending of the adsorption of particles or their exchange by already condensed ions along the chains.

Globule Globule a a' b length did not show any effect at the microscopic scale (scale of the fractal aggregation patterns), it appears that it has a strong effect on the structuration of the (SA/NP) complexe at the nanoscale.

Conclusion

We have first studied, the structural characterization of pure and mixed SA polysaccharide/Au NPs solutions, as well as their critical physicochemical characteristics such as NPs volume fraction, pH and conductivity of the solutions. Then, the main morphological features of these solutions were characterized by TEM after the drying of a solution drop on a TEM grid. The binary SA/NPs components reveal the presence of small NPs (2 nm) collected by the SA chains in addition of the expected NPs size (25 nm in diameter). Then, a model experimental approach, based on the drying of pure and mixed SA polysaccharide/Au NPs solutions was developed toward the understanding of the drying-mediated structure formation in these mixed (polysaccharide/NPs) systems, especially the formation of the complex ramified aggregation structures.

We first focused on the role of the compositional parameters (residual salts especially)

and NP size on the formation of the dendrite-like patterns. We showed that unlike single-component SA and NPs solution drops, which are either free of any organized structure (SA) or form at most small dendrite aggregates (NPs) for the used experimental conditions (concentrations, ionic force, partially wetted substrate…), mixed drops of the oppositely charged SA (COO -) and NH3 + -stabilized Au NPs lead upon drying to large size dendrites patterns, with an unusually high density of fibrillar ramifications. Besides the complexation between SA (COO -) and NH3 + -NPs, we showed that the genesis of these highly ramified drying-mediated assemblies was crucially determined by the residual salts. We have also discussed the growth mechanism of such aggregates, highlighting the hydrodynamic events which contribute to their genesis in the late stage of the drying. Finally, inspired by these spontaneously emerging fibril-like, dendrite aggregates, we have developed a facile, template-directed microfabrication process of composite hydrogel microfibers (SA/NPS), for lab-scale functional characterization and optimization.

Secondly, a study at the nanoscale of the aggregation structures has brought us to propose a model of interaction between SA chains, ions and NPs. This model was based on the effect of SA chain length on the structuration at the surface of either the single SA or the binary (SA/NPs) systems at the nanoscale, whereas any noticeable effect of this chain length (200 nm and 480 nm) was observed at the scale of the optical microscopy on the dendrite aggregates.

Conclusion

The wetting and drying of complex fluids generally lead to the genesis of structures whose richness and aesthetics reflect not only the unique bulk properties of these fluids (different sizes and lengths characteristics), but more importantly, the coupling between these bulk properties, and those of the substrate surface (interactions, containment, hydrodynamics). Through the case of NP solutions (Au), and polyelectrolyte (polysaccharide), we have tried to understand the mechanisms and critical parameters that govern the genesis of complex aggregation structures (fractals and dendrites in particular) resulting from drying drops and films of these fluids. Unlike the famous ring left by drying drops of suspensions and described by Deegan ("coffee-ring"), this work investigates the crucial role played by the coupling between on the one hand, the properties of the fluid volume (kinetic phase changes), and in another hand, the hydrodynamic effects at the substrate (shear-induced ordering) in the emergence of complex aggregation structures in these drying fluids. In this second part of the thesis, we have discussed the importance of this issue, both for the fundamental understanding of the self-organization processes, and for the elaboration of new and functional composite mesostructures.

First, we have investigated the formation of NP-based complex aggregation patterns, and tempted to propose a growth mechanism allowing to explain their spontaneous formation at chemically and anisotropy-free surfaces. The first chapter of this part focused on the interrelation between the occurrence of complex aggregation patterns in drying single NP component solutions, the size of the constitutive NPs, and the drying temperature. The wetting properties of the substrate showed an important role in the occurrence of the aggregation patterns. Beside these properties, the results have revealed that the emergence of the large scale aggregation patterns was controlled by the size of the NP up to a certain temperature threshold. In addition, the formation of stable NPs self-assemblies was favored for NPs of size smaller than 10nm, the cohesive energy of which is higher than for assemblies made of larger NPs. The first chapter was focused also on the investigation of the main parameters governing the appearance of these spontaneous self-organized complex patterns. In particular, the role of the residual ions of synthesis was highlighted. We showed that the emergence of these patterns was assisted by the co-crystallization of the salts and ions existing in the solution with NPs.

We found that the probability of patterns formation, and more precisely of fractal structures is very low for drying solutions of a too low ions concentration.

The use of templates in the drying solution drops was discussed towards the formation of functional and regular NP structures at the mesoscale. Going from the spontaneous (template-free) emergence of complex aggregation patterns using simple drop casting technique, we were interested in the second chapter of this part, to the possibility of producing nanoring-like patterns through confined nanobubbules and nanodroplets introduced in the suspension. Indeed, during the drying of hydrophobized (grafting) NPs suspension drop, the interface of the nanodroplets and nanobubbles are coating with adsorbed NPs leading to their settlement at the surface of a hydrophobic substrate. The formation of such nanorings during the drying of the drop and the destabilization of the confined nanobubbles (nanodroplets) within the wedge of the receding drop was successfully achieved. These nanorings have proved in addition to be an effective analytical tool when used to detect very low amount of organic molecules adsorbed on these structures, by Surface-Enhanced Raman spectroscopy (SERS).

Finally, based on the finding (that we have here confirmed) that the same drying dynamics could lead to the formation of self-assembly aggregation structures in pure polysaccharide alginate solutions, we were drawn to a question of both fundamental and practical importance. This is the relationship between the drying patterns of singlecomponent solution drops (NPs and alginate), and those emerging from the compounding of two such pure components, for similar drying conditions. The issue of drying-mediated co-assembly and complex pattern formation in such binary systems, using anionic sodium alginate (SA) and amine stabilized gold NPs (Au-NPs) has been investigated in the third chapter of this part. Unlike single-component drops, which are either free of any organized structure (SA), or form at most small dendrite aggregates (NPs) for the used experimental conditions (concentrations, ionic force, partially wetted substrate…), mixture drops of oppositely charged SA (COO ) and NH3 + -stabilized Au NPs lead upon drying to large size dendrites patterns, with an unusually high density of fibrillar ramifications. The genesis of these highly ramified drying-mediated assemblies was crucially determined by the residual salts through two mechanisms. The first is the counter-ion condensation along the SA chains and on the NPs that leads to a strong reduction of the Debye screening length. The second is the co-crystallization of these salt traces within the assembling SA and NPs. Whereas the first of these salt-controlled effects increases chains flexibility by lowering their electrostatic persistence length, and makes the attractive vdW interactions predominant and almost the unique force that drives the self-assembly, the second provides cement for the assembled materials.

Finally inspired by the spontaneous formed fibrillar patterns, we have developed a facile, template-directed microfabrication process of composite hydrogel microfibers (SA/NPS), for lab-scale functional characterization and optimization. In another hand, a study at the nanoscale of meso-aggregation structures has brought us to propose a model scheme of the interaction and complexation between SA chains, ions and NPs in the solution. This scheme was based on the effect of SA chain length in the structuration at the surface of either the single SA or the binary (SA/NPs) systems at the nanoscale.

So far in this work, we have synthesized colloidal Au NPs and model surfaces, focusing on the spontaneous or template-directed structure formation in drying drops of either the pure NPs suspension, or in their mixed solution with sodium alginate polysaccharide. However, as for almost all nanostructures, the time and environmentdependent stability (aging) of these drying structures is of crucial importance regarding their possible functional properties and applications. The next part of this thesis addresses this issue of the aging of these complex aggregation patterns.

Introduction

On a technological level, the characterization of the cohesion and adhesion of the constitutive or embedded NPs at macroscopic scale is simply crucial for assessing the stability (reliability) of the functional performance for which these nanomaterials are interesting. And more than for other materials, these functionalities rely on size effects, but also and importantly on the local and large-scale organization and packing (morphology) of the NPs within the aggregates and the whole nanomaterials, both properties being highly sensitive and degradable under "hydro-thermo-mechanical" stresses.

The stability and morphological reconstruction of these NP-based structures are of great interest. 1,2,3 It is well known that surface diffusion of atoms and clusters can strongly affect the performance of these systems. 4 A disruption of an ultrathin metallic film for instance increases the electrical resistance of the circuit. 5 In this context, the third part will focus on the investigation of the aging mechanism of the NP-based aggregation structures which are induced by drying as described in the second part of this thesis.

The first chapter of this third part highlights the effect of different parameters of storage on the evolution of the complex drying patterns vs. time. We will first present the aging of these structures drying-mediated of colloidal NPs solutions. A study on the interrelation between degeneration and reconstruction of these patterns, the size of spherical NPs and the relative humidity of the storage was investigated. In a second part, aging of the complex aggregation patterns induced by the drying of mixed (alginate/NPs) solution drop has been investigated from a physical and chemical point of view. The morphological reconstruction of the patterns was studied and then, a method of long term stabilization based on a gelling process of the ramified dendrite structures has been proposed.

Because of the complex nature (composition/structure) of the arborescent patterns and their time dependent morphological reconstruction, a second approach based on the manipulation of nanoclusters by atomic force microscopy was proposed. Despite the fundamental and practical interest of this problem, systematic investigations on nanomanipulation of nano-objects are still scarce. Some reasons for that are the difficulties in quantifying the dynamical processes occurring while manipulating, i.e.

collisions between probing tip and particles, friction between particles and substrates, electrostatic interactions among them, etc. However, a systematic study has been proposed towards a better understand the mechanisms controlling the mobility and dislocation of our NPs structures during their aging. Different NPs size, morphology and functional coating, as well as various surfaces, opertaing conditions, environments and temperatures have been considered to perfectly tune the interfacial interactions. Hence, this nanoscale contact between (tip/NP) and (NP/surface) has brought additional information relative to cluster mobility due to the formation of capillary condensation bridges.

Introduction

The stability and the morphological reconstruction patterns of ultrathin nanoparticulate films are in fact of great research interest. 1,2 It has been previously shown that ultrathin metallic film deposited onto non-metallic, or low surface energy substrates are typically unstable thermodynamically at quite mederate temperature. 3,4 It is well known that surface diffusion of atoms and clusters can strongly affect the performance of various systems. 5 A disruption or a coarsening of NPs of an ultrathin metallic film for instance may affect the reliability of catalytic converter system. 6 This chapter highlights the effect of storage conditions (T°, RH %) on the evolution of the NPs-based complex aggregation structures, vs. time.

We will first present the aging of the complex structures induced by drying of pure colloidal NPs drops. A study on the interrelation between the degeneration and reconstruction of these patterns, the size of the NPs and the relative humidity of the storage was investigated. Finally we will focus on the phenomenon responsible of the evolution and the morphological degeneration/reconstruction of the NPs based structures.

The second section will address the aging of the aggregation structures induced by drying bi-component mixture of sodium alginate -gold nanoparticles (SA/as-prepared NPs) solution drops. The evolution of these complex patterns vs. time as well as their aging mechanisms were investigated. Finally, a method to stabilize and refine these patterns, based on a gelling via Ca 2+ cations (CaCl2 solution) was proposed. 1 Two distinct mechanisms are generally proposed to be at the origin of these dewetting processes: 1) the heterogeneous nucleation and growth of holes, and 2) the spinodal decomposition of the film/substrate system. 7,8 The second mechanism which is more effective in thin soft films is expected theoretically to arise from the combined effect of long-range forces and thermally-driven thickness fluctuations of the film.

At the differences of these rather current studies on the stability on thin uniform polymer or metallic films, we consider in the following section the stability and time evolution (aging) of structures that are morphologically complex (dendrites-fractals)

and formed of the aggregation of both individual and NP clusters. The role of the NPs synthesis residues (salts in the form of reducing agents) and their mutual interactions in triggering the stability of the drying-mediated complex aggregation structures, the size of NPs forming the structures and the environmental condition (the relative humidity) of storage will be studied.

a. Experimental methods

The NPs suspensions used for these experiments are the raw citrate stabilized spherical Au NPs (chapter 1, part 1). The experiments consisted in depositing 20 µL drop of the suspension on the silicon wafers. The resulting structure formation was captured with a video-microscope. The aging of these structures, vs.

RH (%) 11 %

33 % 75 % t=0 t=0 t=0

As previously, the optical images reveal the influence of humidity on the degeneration of the aggregation complex patterns, vs. time. The time t=0 shows the freshly formed dendrites structures upon drying of the suspension drop at 21 °C, 33% RH. The complete alteration of the patterns is also reached here after 9 days at 75% RH as for the 25 nm NPs structures. However, unlike the 25 nm NPs structures, the degeneration of the patterns stored at 33 % of RH doesn't start before 9 days of storage. The evolution rate of these patterns of 15 nm NPs is slower than that of 25 nm particles. Here, experiments were performed with 45 nm NPs coated with citrate. After the drying of the colloidal NPs suspension drop on SiO2 wafer and the formation of the dendrite structures, the sample was stored at 21 °C and RH~23%. x 2 = 2.10 -18 t -1.10 -13 .

In other words, the root mean square x varies as t 1/2 , as expected for diffusion dominated migration process. In addition, it is important to precise that the studied migrating cluster occupies a contact area of ca. 3.948 µm 2 and moves from the principal branch of the dendrite structure toward free surrounding place, as shown in figure 3.1.1.6. This cluster mobility can be described through the Einstein relation of diffusion:

x 2 = 2Dt = , eq 3.1.1.1
where D is the diffusion coefficient, kB is Boltzman constant, T the absolute temperature and, a term corresponding to friction.

From our experimental data, the slope of the linear curve gives an approximate value of the diffusion coefficient of the cluster on the hydrated substrate. This is of the order of D=10 -18 m 2 /s.

The mean square displacement at t=o which is of the order of 10 -13 , corresponds to the square of an initial distance X0 2 between the cluster and the branch from which x is measured just after the break of the bridge that connects them.

The mobility of the Au NPs cluster is directly related to their interfacial properties:

adhesive and frictional forces at the surface, and among them. In particular, friction forces that undergo the Au clusters is mainly governed by static friction related to adhesive intermolecular forces and to the external force resulting from the aggregate inertia (mass). Hence, the threshold lateral force Ff (friction force) required to slide the This short analytical model corresponding to the mobility of Au cluster inside complex structures induced by environmental aging is mainly governed by a diffusion mechanism. This phenomenon is strongly favored by the formation of an ultrathin water condensate film adsorbed around and between the Au NPs, and which may act as lubrication layer.

c. Conclusion

The investigation of aging and the degeneration of NPs-based complex structures formed at the solid surfaces has highlighted the fact that water vapor or more generally, the relative humidity, represents a critical parameter that controls the stability and aging of these complex structures. This degeneration was underscored by a dislocation of the branches of the ramified structure, which results in a decrease of particle density in the dendrite. In addition, the results have confirmed, for the second time, the sizedependence of the cohesion of these NP-based structures: assemblies of smaller NPs have higher cohesion than larger ones. The precise analysis of the desintegration of a branch of a complex structure has enabled understanding the mechanism of disassembly of NPs and the associated degeneration of the dendrite patterns. These last results have shown that this phenomenon was mainly controlled by NPs and cluster diffusion within the aggregate, leading to the disintegration of the whole branches pattern.

In this context, the following chapter in part 3 of this thesis should bring additional information on NPs mobility, and confirm the impact of physical parameters such as NPs interactions and friction coefficient, and environment (RH, T°). The approach of this study is based on the manipulation of single NPs by atomic force microscopy (AFM).

Whereas manipulation of single Au NPs by AFM can provide better understanding of the nanoscale interfacial interactions (NPs/environment), this system is notably different from the previous one. Indeed, the size of the manipulated objects are different (single NP mobility vs. cluster mobility), and the AFM tip induced movement is very different in nature than surface diffusion of clusters within an aggregate.

However, before this single NP manipulation, the second section of this chapter will focus on the aging of the complex drying structures issued from the bi-component (SA/NPs) solutions. This mixed (SA/NPs) systems was introduced to improve the stabilization of the dendrite NPs structures which are instable against variations of the relative humidity, and evolve through time-dependent reconstructions. However, these bi-component drying structures present a second advantage arising from the possible gelling of the highly ramified (SA/NPs) structures through the presence of SA polysaccharide. And this gel-induced stabilization also has potential applications towards functional nanomaterials.

3.1.2. Aging of the complex structures induced by drying of mixed (SA/NPs) solutions

The aging of the complex aggregation patterns induced by the drying of mixed (SA/NPs) solution drops as described in chapter 3/part 2 will be investigated from a physical and chemical points of view. We will show first, how the patterns evolve, vs. time and then, we will propose a method to stabilize these patterns based on a gelling process of the ramifief structures.

a. Stability of the ramified (SA/NPs) structures

The drying induced aggregation patterns of (SA/NPs) system are metastable against variation of relative humidity, and evolve through time-dependent reconstructions (T ~ 23 °C, RH ~ 33%). However, the stability of these binary structures is enhanced by a factor of ~ 20, compared to complex patterns formed of single (pure) NPs. This longtime durability can be explained by the presence of the biopolymer that encapsulates the NPs aggregates and reduce their mobility, which is not the case for single NPs clusters previously studied.

b. Rayleigh instabilities of fibril-like branches -thermodynamical stability

The branches of the ramified structure can be considered as a long cylinder of radius R. The free energy per wavelength of the cylinder is 2πRλγ and the free energy per droplet is 4πb 2 γ, where γ is the (cylinder/environment) interfacial energy. A second assumption in this capillary destabilization is that the free energy of the cylinder is higher than the resulting row of droplets. And this assumption is satisfied if λ>9R/2.

Our ramified structures display long branches of average cylinder radius R ~ 6.25 µm, with an instability wavelength of the order of λ~38 µm. The second assumption is therefore satisfied for our system, as the ratio 9R/2 is equal to 28 µm, a value smaller than λ. From this raw estimation, the degeneration of the branches of the ramified structures can well be driven by Rayleigh instabilities. As a result, one can expect the cylinder to evolve in a row of droplets of a large enough radii. 12

c. Degeneration : competition between dehydratation and instabilities

Because of the competition between this Rayleigh destabilization, and the dehydration of the structure towards an equilibrium swelling state of higher viscosity which stabilizes the fibrillar branches against size fluctuations (bulging), this instability rarely leads to droplets as shown in figure 3.1.2.1c, unlike cylindrical low viscosity liquids.

However, the shape-distortion of the fibrillar branches may be important. The search for a solution to suppress this shape distortion and preserve these highly ramified fibrillar dendrite patterns has led us to the following simple idea. Indeed, since SA readily forms a hydrogel by contact with the CaCL2 solution, the dendrite patterns can be stabilized against shape-distortion and aging (long-term stability) by the higher viscoelastic modulus of the (SA/NPs) "hydrogel" network.

d. Patterns gelling and long-term stabilization

The gelling procedure of the (SA/NPs) structure, has consisted in depositing a drop of 0.1 M CaCl2 on the final drying spot containing the generated ramified patterns for a few minutes, and then rinsing it with pure water.

This gelling procedure is based on the ionic exchange between divalent Ca 2+ cations and the monovalent Na + counterions along the (COO -) groups of the SA chains. As comparable to Na + , Ca 2+ will accommodate both in term of charge and size, the linkage of two (COO -) groups between two SA chains, leading to chains interaction through what is known as the egg-box conformation, and thus to the formation of physical gel (hydrogel). The question that arises from these observations, is why the gelling of the substructure seems to be more important and to dominate that of the pattern branches? Two hypotheses may account for that. -First, the concentration of alginate chains in the substructure is higher than in the complex patterns. More interestingly, the biopolymer chains form a compact film in the substructure, whereas they are more interconnected and less dense in the patterns branches, because of the presence of Au NPs there.

-Secondly, the presence of a high density of gold NPs inside the (SA/NPs) patterns, their interconnection with SA chains, and the low exchange rate between Ca 2+ and positively charged NPs may lower the gelling rate of the patterns. In the same time, that density of Ca 2+ exchange will remain high in the substructure.

However, independently of the density of ionic interaction and exchange between both (NPs/SA) and (Calcium/SA), the gelling process clearly allow a higher stability of the highly ramified structures.

Finally, the structure after gelling shows no evolution at 33% of relative humidity and 24 °C, after 8 months. However the patterns that are kept without gelling, present a strong morphological reconstruction as shown in figure 3.1.2.3. To conclude on this section, it appears that compounding NPs with SA polysaccharide highly increases the stability of the ramified complex drying structures, as compared to pure NPs aggregation patterns. Their mechanism of destabilization is mainly driven by a competition between dehydration of the pattern and Rayleigh instabilities. The complete stabilization as well as a smoothing effect was obtained by a gelling of the ramified structures. Another way to promote the stability of these complex patterns was shown to be the use of bi-component systems. In particular, the association of sodium alginate chains to NPs enhances the stability of the patterns by a factor of 20. Ultimately, the swelling and gellation of this binary system has allowed stabilizing complex patterns against Rayleigh-type fragmentation, deliquescence and aging.

These investigations on the aging of the complex drying structures were extended and highlighted with additional experiments on cluster mobility, namely the manipulation of NPs by atomic force microscopy. This approach has been proposed to characterize the critical parameters controlling the motion of the metallic cluster. The influence of the parameters that are the shape, the size and the coating of the NPs, the surface chemistry and the operating conditions (temperature, humidity and scan velocity), on the manipulation was investigated and discussed in the following chapter. Numerous methods exist for the manipulation of nanostructures and can be classified into two categories as non-contact and contact manipulation systems.

In the former, laser trapping (optical tweezers) or electrostatic or magnetic filed forces were utilized. Yamomoto et al have cut DNA using restriction enzymes on a laser trapped bead. 1 Vonna et al used magnetic tweezers and beads to stretch cells membrane. 2 Stroscio et al utilized electrical forces between scanning tunneling microscopy (STM) probe tip and surface atoms for manipulating Xe or Ni atoms. 3 More precisely, manipulation of NPs (metal nanoscale particles) in non-contact mode was the first approach to manipulate these nano-objects. Historically, the first accurate manipulation studies of NPs have been performed by STM. In a pioneer experiment, Cuberes et al has moved single C60 molecules along the steps of a Cu(111) surface using an STM in UHV. 4 In addition, the majority of the STM experiments were performed at cryogenic temperatures. 5 Unfortunately, despite the accurate level of control obtained with STM, the energy dissipated in the manipulation was extracted from the lateral manipulation of these NPs. 14 These particles were first pushed on a graphite surface by the AFM tips, and then they were manipulated by placing the AFM tip on top of the particles. Above a certain lateral force threshold, particle sliding was observed, which has allowed quantifying the transition from static to kinetic friction. 15 A compromise between the contact and non-contact AFM techniques is the intermittent mode, the so-called -Tapping mode (TM) AFM. Particularly, in TM mode, the phase shift of the cantilever oscillations with respect to the external periodic excitation can be used to estimate the dissipated energy during manipulation. This method was recently used by Ritter and coworkers to manipulate antimony particles on a graphite surface in air 14,15 . Paollicelli et al have manipulated gold NPs deposited on highly oriented pyrolitic graphite using AFM in TM mode. NPs were selectively moved as a function of their size varying from 24 up to 42 nm diameter and energy detachment threshold of NPs was estimated accordingly. 16 Setti and al have also manipulated nanoscale latex particles that were positioned on Si substrates with about 30 nm accuracy. 17 In all these techniques, the major difficulties that arise are related to the quantification of the dynamical processes occurring while manipulating, i.e. collisions between probing tips and particles, friction between particles and substrates, electrostatic interactions among all of them, etc.

The manipulation of NPs and especially gold colloidal ones by AFM can be influenced by the structural characteristics of particle, tip and surface, in particularly the intermolecular interactions between tip/particles or particles/surfaces. In addition, both the physical structure of the substrate (topography) and the operating conditions (environmental 18 and scan velocity of the tip) determine in a large extend the tip/particle/substrate interactions and behavior. Besides the fundamental understanding of the different types of particle motions during manipulation, such as sliding, rolling, stick-slip and spinning, is crucial since the mode of motion of particles determines the energy loss and wear in the contacting surfaces.

In this chapter, the sensitivity of those critical parameters on the mobility of gold NPs during their manipulation using AFM in Tapping mode has been investigated. In particular, the effects of the size and shape and coating of the NPs, the lateral scan velocity, the particle/ surfaces interactions, the environmental conditions, especially the temperature and humidity rate are presented and discussed. The dependency of the energy dissipation during the manipulation was particularly studied versus size, coating of particles and substrate and temperature. Finally, interpretation of the physicochemical mechanisms involved at the both interfaces (tip/particle and particle/surface) during the movement of the particle was proposed and partially verified by modeling; nevertheless additional investigations are still needed.

Experimental methods

Gold NPs were adsorbed onto silicon wafer and manipulated in AFM Tapping mode.

They were either "as synthesized" (citrate coated) or coated with self-assembled monolayers terminated with a hydrophobic (methyl -CH3) or hydrophilic group (hydroxyl -OH). Particles are prepared as described in part 1.

The model substrates are molecular surfaces which were prepared by self-assembling organosilane molecules onto silicon wafers as described in part 1.

a. NPs adsorption

Random adsorption

For the adsorption experiments, a unique concentration of 0.03 wt % of NPs in the aqueous or organic dispersion was used. The experimental protocol basically involved the particle adsorption by immersing the samples for about 20 minutes in the suspension, whose temperature was maintained at 20±1 °C. Upon this initial adsorption stage, the samples were removed from the bath, and the thick dispersion film remaining at the substrates was allowed to dry.

Ordered organisation

Samples were provided by McFarland's group in UCSB. 25 nm diameter Au NPs were synthesized as described in part 1. The Au NPs coated silicon wafer was prepared using a micelle encapsulation method. 19,20 Au NPs were encapsulated by diblock copolymer (Poly (styrene)-block-poly (2-vinylpyridine)). The solution was deposited onto silicon wafer and dried under nitrogen flow. After being dip-coated, the polymer was removed using an oxygen plasma treatment.

b. Manipulation Setup

The images in air were acquired with three commercial AFMs (Multimode: Nanoscope IV where Apiezo is the oscillation amplitude of a piezo element coupled to the cantilever, 0 f , k and Q are respectively the resonance frequency, the spring constant and the quality factor of the free cantilever, and is the phase shift caused by the interaction between the tip and the underlying particles or surface. The first part of the discussion will focus on the influence of the size and shape of the particle on their manipulation. Then, we will examine the effect of functional (hydrophilic vs. hydrophobic) molecules grafted on the Au NPs on their mobility. In addition, we will address the important issue of environmental conditions (T, RH %), surface topography and tip scan velocities on the manipulation performance of gold NPs.

a. Influence of the size and the shape of the particle

Influence of the size of the spherical Au particle

Sizes of gold spherical NPs were tuned from 5 nm up to 65 nm according to the synthesis procedure described in method section. "As-synthesized" Au NPs, meaning NPs covered with citrate stabilizing group (COO -), referred to as "as synthesized NPs" were deposited onto bare and hydrophobized (CH3 terminated coating) silicon wafers, and manipulated using AFM in Tapping Mode.

During manipulation, the oscillation amplitude of the tip, Aset, was kept constant by a feedback loop. In such case, the power dissipation accompanying the tip-sample interaction can be determined using the relation presented in the experimental section.

The calculation of the dissipated power (P) was performed for 5 sizes of Au colloidal particles whose radius (R) has varied from 5 up to 65 nm. Figure 3.2.2.1a and b correspond to a logarithm plot of the dissipated power normalized by the radius of the NP as a function of the radius of the particle, on bare and hydrophobic coated silicon wafers, respectively. These plots actually can be fitted using an approximation of a friction model for NPs rolling and sliding on the substrate. 17,22,23 The red curves correspond to simulated dynamic behaviors of the NPs according to pure sliding [figure 3.2.2.1a] and rotation [figure 3.2.2.1b] models of the NP, after the tap in a typical AFM Tapping mode manipulation as described by Sitti. 17,22,23 According to this model, the force brought by the tip to the particle should be higher than a threshold value, respectively given by 22 A. Those results thus display the dependence of the movement of the particle on both their size and substrate surface chemistry, underscoring in particular the importance of the particle/substrate interactions on the mobility and behavior of nano-objects while manipulated. Although crucial, these "particles/substrate" interactions actually represent one parameter among other important physical parameters. Indeed small and large particles do not undergo the same trajectory during manipulation. This size-dependence of the particle trajectory under manipulation can thus provide a way to fractionate or to separate a mixture of nano-objects. In figure 3.2.2.3 a and b, we can observe that big (a few dozens of nanometer) particles move with a small angle with respect to the normal of the tip fast scan direction, until they reach the bottom of the scan area, whereas smaller ones slide to the edge of the scan area using a shorter path. From this observation it is possible to fractionate and separate small from big particles adsorbed on a substrate.

That size-dependence of the particle trajectory was explained by a simulation which shows that the trajectory of the particle at the same time depends on i) the operating parameter which is the scanning path (zigzag or scattered one) used by AFM [figure 3.2.2.4], ii) the density of scan lines and, iii) the parameter Rtot which corresponds to the sum of the radii of the tip and the particle. Indeed, it has been observed [figure 3.2.2.3b] that two particles that collide at a point and move together can be considered as a single particle. If we compare two consecutive trajectories of the particle before and after collision, the single Au particle (thinner line) moves at a smaller angle, as compared to the case where it meets another particle (thicker line). In this case, the variation of the trajectory can be explained by the variation of the radius of the average cluster Rtot (different sizes move at different angles).

Influence of the shape

The manipulation of spherical and asymmetrical NPs by AFM represents a way to understand and control the motion of complex shaped NPs. For instance, manipulation of elongated objects such as rigid Au nanorods induces mainly sliding and rolling of the nano-objects and this movement varies with the different stages of nanomanipulation time scale. As shown in figure 3.2.2.5, the rods first tend to move perpendicular to their principal direction of motion and then wobble along their longitudinal axis. The average orientation of the rod is perpendicular to its direction of motion. According to theoretical simulation and experience, the torque applied by the tip to the rods results in a wobbling motion, which has no determining influence on the overall direction of the NPs. 24 For triangular and flower shaped NPs, the nanobjects mostly evolve through a translation movement, as well as a rotation along their main perpendicular axis during the manipulation, as shown in figure 3.2.2.5. While asymmetric particles wobble around a fixed angle, they do follow a well defined path with a specific angle. Simulation of the trajectory of these different particles may enable to better understand how to induce a well-defined direction of motion to NPs by adjusting the operating parameters of the AFM. Besides the shape and the size of the particles, the chemistry of the functional grafting surrounding the particle also affect strongly, their movement and trajectory during nanomanipulation. The role of the hydrophobic/hydrophilic character of the interface in the manipulation process was investigated, using gold NPs bearing -OH and -CH3 terminated thiol groups as described in the method section, and moving the particles again a flat bare silicon substrate. The results are summarized in figure 3.2.2.6, which displays the average power dissipation required to induce the motion of the particles. The first observation that directly arises from this figure is that the presence of a hydrophobic interface significantly enhances the mobility of the particles. The energy required to move OHcoated gold NPs, on the other hand, was found to be at least 10 times higher than that for CH3-coated particles. We also observed that the manipulation of hydrophilic coated NPs often results in a damage of the tip due to the high "particle/substrate" adhesion force. This strong adhesion between silicon substrate and hydrophilic coated NPs, which primarily arises from intermolecular interactions, may also involve a contribution from capillary bridges which may form under ambient conditions between the substrate and the NPs on one hand, and between the closest NPs on the other hand (see following paragraph). At the opposite, the thin adsorbed water film which forms on silicon wafer rather acts as a lubricant when confined between the hydrophobized CH3 coated NPs, and the (hydrophilic) substrate, as this has been already observed. 25,26 As we can see here, the eventual role of relative humidity (RH %) which is an environmental parameter, on the contact and NPs manipulation, is strongly dependent on the chemistry of the (NP/substrate) interface. With this relative humidity, another additional environmental parameter, namely the temperature, also affects the mobility of the NPs. The influence of extrinsic (environment) parameter is discussed in the following paragraph. exponential decay of the dissipated power with T which accounts for a thermally activated process. 28 The slopes of these linear fits correspond to ( Eact/k), where Eact represents the activation energy barrier with respect to a reference state E 0 : E act = (E 0 -E act ), E act (T) being the energy input involved in the motion of the particle. This energy variation (slope) is high for the CH3 hydrophobized NPs, indicating a strong decrease of the input energy with the temperature as one could expect for a low (NP/substrate) adhesion strength. Surprisingly, a quite similar behavior (both trend and activation of barrier) of the temperature dependent mobility is observed with the hydrophilic OH coated NPs (strong decrease of input energy with T). An explanation to this result may come at least partly from the complex behavior of the adsorbed (structural) water to temperature in the hydrophilic system. Beyond the observed and rather reasonable general trend which is the strong decrease with the temperature of the energy required for particle movement, the magnitude of the activation barrier for essentially hydrophilic and hydrophobic contacts will certainly need further confirmation experiments, as well as a more extensive interpretation.

c. Influence of the temperature

d. Organization effects

The first and third columns of the series in figure 3.2.2.6a show the threshold power dissipation for the motion of randomly and ordered organized distribution of NPs [figure 3.2.2.7], obtained as described in method section. The power dissipation at different temperatures is comparable in both cases. This result can be explained by the average distance between the nano-objects, which is 70 nm for a b the random distribution and 100 nm for ordered one. At such a scale, the interparticular forces are of the order of long range interactions. The mobility of particles is essentially affected in this limit by electrostatic interactions arising from the residue of synthesis (citric acid) that may be adsorbed on the particles. It is thus normal in the absence of both physical contact and notable intermolecular forces between the particles that their mobility is independent of their organization (random or ordered). In other words, this result means that so long as the particle number density n p is such as the interparticle distance d p ~ (n p ) -1/2 is larger than the range of short-ranged forces, 29 their mobility is not affected by their mutual intermolecular binding and is thus independent of their organization. It is worth noting that this absence of true intermolecular binding does not exclude possible particle/particle interaction through capillary forces arising from nanosize condensation film connecting particles at these separations.

e. Influence of the humidity

The presence of surface contaminants (dust or water) on a surface affects the mobility of NPs as this directly affects the intermolecular interactions between the NPs and the surfaces. As it has been discussed in section 2, a contribution from capillary bridges has also a strong influence on the mobility of the Au NPs during their manipulation. Indeed, capillary forces of water films between both interfaces (NP/surface) and (tip/NP) will depend on the volume and shape (film, vs. droplet) of the liquid condensate present at the interface, as well as the interface geometry. 30 In this section we have studied the mobility of as-synthesized Au spherical NPs coated with citrate and CH3-coated ones. The size of the Au NP is about 25 nm diameter. The substrates are silicon oxide (partially hydrophilic), and CH3 terminated SAM coated silicon wafers (hydrophobic). The measurements in this section were carried out using the Enviroscope from Veeco.

Three models of (NPs/substrate) interaction are studied, with varying relative humidity For each model, the measurements were first performed at 10 mbar and 2 % of RH.

These measurements provide the reference values for moving the NPs on the substrate at with the lowest (quasi-dry) RH in the environment we could access. Then, the measurements were carried out at 10 3 mbar and the RH was tuned between 10 to 80%.

The threshold energy to move NPs under each environment condition were calculated using the equation given in methods section. These AFM nanomanipulation measurements were completed with aditional ellipsometry ones in the aim to determine the effective thickness of the condensed water layer on partially hydrophilic SiO2 at some reference RHs. At low RH (below 40 %), the thickness of the condensed water was not measurable by our system. Although surprising a priori, this result maybe simply accounted for by the threshold nucleation vapor pressure which is known to increase with the equilibrium contact angle of the liquid on the surface. As a result, partially wetted surfaces like solvent cleaned SiO2 have a threshold nucleation/condensation vapor pressure higher than totally wetted surfaces. However, for higher RH values (> 40 %), the thickness of the water film increases to about 130 nm ± 10. This value which is strictly larger than the NPs diameter, allows us to consider that hydrophibilic NPs might be totally immerged in the condensed layer at the surface during both the nanomanipulation and the dislocation of pure NPs aggregates.

Analysis of the graph of figure 3.2.2.8:

First the energy dissipation at 2 % is considered as the threshold energy to move the NP As previously, the 2% RH value is considered as the reference state [figure 3 To conclude, on these AFM assisted manipulation, it appears that in a humid environment, the friction and adhesion forces are strongly dependent on the configuration of the capillary condensation that is determined by the intrinsic wetting properties of the contacting interfaces. As a consequence, the resulting water meniscus (or layer) can either increases friction through increased adhesion in the contact zone (hydrophilic interfaces), or reduces it through a combined hydrophobic/lubricating effect of the water layer. The previous sections have demonstrated the influence of the morphological, environmental and chemical parameters on the mobility and movement of the particle.

The following addresses the influence of the topography of the substrate.

f. Inflluence of the topography of the substrate

Manipulation of gold NPs was investigated on flat bare silicon wafer, as well as on nanostructured ones. We mean by nanostructured (or nanopatterned) silicon wafer, silicon substrates that present nanoscale patterns.

The following experiences were performed using a raster scan path of the tip mounted on a Nanosurf AFM. On flat bare silicon wafer, the direction of motion of the 25 nm diameter gold NPs was initially well defined, but changed after acquiring a couple of images. This makes it much more difficult to move the particles, even for higher values of the drive amplitude, possibly because of the tip contamination. Hence, the idea to modify the topography of the surface was chosen to study the effect of the geometrical surface confinement on the mobility and trajectory of the NPs. Nanopatterned substrates shown in figure 3.2.2.14 were chosen for that purpose. The surface patterns consist of an array of nanopits created by Focused Ion Beam (FIB) milling technique. The width and depth of the pits were, respective, 650nm and 5 nm, and the spacing between two adjacent pits was 125nm. On the patterned surface, the mean direction of motion remains identical (in average), even after a long time of acquisition.

This stability of the direction of the particle movement observed here on the nanopatterned substrates can be attributed to a "self-cleaning" of the tip when its crosses the shallow pits. Considering that the pits had a scarce influence on the particle direction [figure 3.2.2.15], which means that all the particles follow the same direction, this parameter could be ignored in the averaging process, for determining the detection angle.

As a result, patterned surfaces were chosen for this determination, rather than the flat bare silicon surfaces. The simulation of these experiments 24,31 has shown the influence of the angle of deflection, versus the spacing b separating two scan paths. Figure 3.2.2.15b and c display the change in angle for the same surface and identical particles, but for b equals, respectively, to 16 nm and 3.9 nm. The trend of adopting higher angles with lower spacing is clear from these results.

To confirm the topographical effect, as-synthesized Au NPs were also manipulated on different substrates such as nanopatterned silicon wafers presenting grooves, and steeped HOPG surfaces.

g. Influence of scan velocity

The influence of the sliding velocity on friction, which accounts, at least partly, for the dynamical response of the boundary layer, can be exploited to gain insight into the manipulation of nano-objects. 25 35 nm and 60 nm diameter spherical particles (as-synthesized Au NPs) were moved in Tapping mode with Veeco AFM following the previous procedure described in paragraph a. The drive amplitude threshold to move the particle was recorded as well as the phase shift to estimate the loss of energy during the movement of the particles. These experiments were repeated for different scan tip velocities ranging from 0.1 up to 10 µm.s -1 on three model substrates: a cleaned silicon wafer (SiO2), and two other ones, respectively coated with a hydrophilic (NH2), and a hydrophobic (CH3) self-assembled monolayers.

The results of the velocity-dependence of the dissipated power are plotted in figure 3.2.2.16. The dissipated power has been plotted in logarithmic scale allowing a more usual comparison with literature. 11,27 To ensure that the measured power dissipation was representative of the spherical gold NPs motion, several particles (at least 10) were moved in similar conditions.

Our results show [figure 3.2.2.16] that for both NP sizes (35 and 60 nm), the dissipated power during the contact (tip/particle) depends on the chemical nature of the substrate.

The magnitude of the dissipated energy gradually and significantly increases from the more hydrophobic to the more hydrophilic substrate as one could expect from the intermolecular interactions involved at the different interfaces. This dissipated power also increases with the diameter of the NPs as expected from the increase of the (NPs/substrate) contact area.

At the more hydrophobic substrate (CH3), the interactions with the hydrophilic NPs (assynthesized citrate stabilized NPs) mainly involve the London dispersion forces that have a much lower magnitude as compared to the polar, hydrogen and electrostatic bonds involved in the adhesion of these citrate-stabilized NPs, with more hydrophilic (SiO2 and NH2) substrates. The maximum dissipated power appears for the more polar substrates.

It is worth noting that this value can involve a contribution from the capillary water bridges which readily form on more hydrophilic systems under ambient conditions as previously discussed in section e. It is also worth noting that we also verified here that both the surface and the particle were free of any observable damage after each manipulation.

However, independently of the nature of the intermolecular interactions exchanged between (tip/NPs) or (NPs/surface), and independently of the size of the spherical particles, the logarithm of the dissipated power during the manipulation systematically decreases linearly, when the scan velocity increases. This linear dependence is generally attributed to a decrease of the energy dissipation in the contact as the velocity increases, in a way similar to the velocity (frequency)-dependent viscoelastic and/or plastic dissipation in polymers (and metals as well), as this is described for instance through the time-temperature superposition principle for polymers. 32,33,34 However, from this discussion, it appears that further investigations regarding the velocity-dependence of the dissipated power are still necessary on both experimental and theoretical levels.

Conclusion

The manipulation of nano-objects is still a scarce operation. Because micro/nanomechanics have not been well-developed completely, two-dimensional positioning of nanometer-size particles on a substrate in ambient conditions remains a difficult operation depending on critical physical, mechanical and chemical parameters.

However, advances in this domain enable to better control nanoscale manipulation. In this chapter, we have described manipulation of gold colloidal NPs using AFM in Tapping mode. The influence of the structural characteristics of the particle (chemistry, size, shape) and the substrate (chemistry and topography) have been investigated. It has been shown that the mobility of the particles was significantly affected by the nature of intermolecular interactions between (tip/particles) and (particles/surfaces), the particle shape and size, the operating environment conditions (the relative Humidity, RH% and the temperature, T), as well as the tip scan velocity. The dissipated power during manipulation was quantified under various operating conditions (T, RH, tip scan speed). Our experiments show that the velocity dependence of the dissipated power at these nanoscale contacts is by far more complex than what one could predict, based on the sole contribution of the tap energy and capillary liquid bridging adhesive force.

Indeed, the thermal energy produced within the (tip/substrate) contact can induce molecular excitations and structural transitions in the topmost contacting layers, the magnitude of which also increases with the sliding velocity. The direct access to the nanoscale contact between (tip/NP) and (NP/surface) being limited with the current device, any quantitative analysis of these results remain at this stage scientifically debatable. The second difficulty is naturally related to the non-fully understood size effects that show up in nanoscale friction and strongly affect the results. In addition, real-time monitoring of the manipulation process is almost impossible. Most of the time, imaging is offline, and the unexpected problems during pushing cannot be detected.

Another way is utilizing the force feedback information during pushing for reliable manipulation. Because of potential improvements in the mechanical and theoretical fields, more complex and precise manipulations of particles, molecules and single atoms at surfaces using AFM will become achievable and nanoscale manipulations may be of fundamental importance for the realization of nanoscale devices in the future.

Through the AFM assisted manipulation of single Au NPs has allowed a better understanding of (NPs/environment) interfacial interactions at the nanoscale, this system configuration remains different from that of the NPs within the aggregate of the complex drying patterns during their aging. Indeed, the mobility of individual particles (AFM manipulation) does not strictly reflect the self-diffusion mobility of collection of NPs or clusters of within a complex structure. In addition, the AFM manipulation involves a contribution of the AFM tip interaction with both the NP and the environment.

These studies thus point to the necessity to extend these investigations to study the collective NPs movement. Other techniques such as crystal quartz microbalance (QCM) can bring additional information on the mesoscale and collective environment stability of NPs, as well as the interaction between neighbouring particles inside a collection of these particles (clusters, layers, etc...).

General Conclusion & Perspectives

In this Ph-D work, we have dealt with colloidal nanoparticles (NPs), and their drying- The second part of the thesis has focused on the assembly of NPs in mesoscale and complex aggregation patterns assisted by the wetting and the drying of complex fluids (suspensions of NPs, NPs mixed solutions / biopolymers) on homogeneous and heterogeneous molecular surfaces. Indeed, the wetting and drying of complex fluids generally lead to the genesis of structures whose richness and aesthetics reflect not only the unique properties of volume of these fluids (different sizes and lengthscales), but more importantly, the coupling between these properties of volume, and those of the substrate surface (interactions, hydrodynamic). Unlike the famous ring left by the drying drops of suspensions and described by Deegan ("coffee-ring"), this work has investigated the crucial role played by the coupling between on the one hand, the properties of the fluid volume (kinetic phase changes), and in another hand, the hydrodynamic effects at the substrate (shear-induced ordering) in the emergence of complex aggregation structures in these drying fluids. The mechanisms and the critical parameters that govern the formation of these complex patterns (size effect of NPs, drying temperature, surface chemistry of the substrate, and residual effect of ions pH in solutions...) were studied as well as the physical properties of these structures(optical, thermomechanical). The correlation between the occurrence of complex aggregation patterns in drying single -component nanoparticle solutions, the size of the NPs, and the drying temperature was particularly underscored. Furthermore, the wetting properties of the substrate was shown to be crucial in the appearance of the complex drying structures. Besides, we have shown that the emergence of the complex aggregation patterns was controlled by the size of the NP up to a temperature threshold. Selfassemblies of NPs were favored for smaller NPs, which intrinsic cohesion is higher than those made of larger ones (scale effect). In addition, the role of the residual ions of synthesis was highlighted as well.

the swelling and gelling of (SA/NPs) highly ramified fibrillar structures has allowed stabilizing the complex patterns against Rayleigh-type fragmentation, deliquescence and aging. Inspired by the spontaneously formed fibrillar patterns, we have developed a facile, template-directed microfabrication process of composite hydrogel microfibers (SA/NPS), for lab-scale functional characterization and development.

To better identify and characterize the role of the critical parameters that might intervene and control the dislocation of the NPs complex structures through NPs and clusters surface diffusion, a model experimental approach based on single NP manipulation (movement) under AFM has been developed. These results displayed that the mobility of the particles was significantly affected by the nature of intermolecular interactions between (tip/particles) and (particles/surfaces), the particle shape and size, the operating environment conditions (the relative humidity, RH% and the temperature, T), as well as the tip scan velocity. The dissipated energy during manipulation was quantified under various operating conditions. Although this approach allowed us to quantify the influence of the operating parameters on the mobility of single NP, it only partially reflects the collective mobility of NPs and clusters in the degenerating (dislocating) complex drying structures. As a result, additional information relative to the collective mobility of NPs is required. Indeed, the instabilities (aging) of the drying structures due to the environment, and the interaction between the neighbouring particles within the structure can not be fully accounted for by the manipulation technique. In addition, the results of this manipulation necessarily involve some contribution from the AFM tip interaction with environment and NPs, and not only from the (NP/substrate) interaction.

As perspective to this work, we think that simulation models should be of great help in However, it is well-known that dielectric constants are independent of film thickness above a critical thickness, which for gold is around 25 nm. 10 The nanoparticulate film presents voids in between NPs which enables transmission of the light up to the silicon substrate. This sensitivity of the substrate has a strong impact on the value of the global optical constants. The refractive index of the Si substrate (n= 4.23; k= -0.043 for at 532 nm), which seems to be accessible to the laser light creates a composite index of the multilayer. The combined effect of the voids (nair= 1) and of Si substrate underneath results in a in a much higher neffective and a much lower absorbance |keffective| for the Au NPs multilayers, compared to bulk Au film. However we note that our ellipsometry film thicknesses are in average larger by ~ 1-2 nm than estimated from the diameter of the NPs. This may arise from the presence of a few aggregates averaging the outmost layer.

Refractive index n Extinction coefficient k

Au evaporated film 30nm 0.488 -2.4

A8

To compare the effectiveness of our multilayer structure to a standard bulk thin gold film, we have prepared Au thin films by thermal evaporation. Contrary to previous results, the optical constants of Au evaporated thin films are close to those expected for bulk Au material, due to the higher compactness of slowly evaporated thin films.

b-AFM in Tapping Mode

Tapping mode AFM in ambient conditions has been used to characterize both the particle size and the morphology of the multilayers (packing, spatial organization). These functional multilayered structures have been tested for their cohesion and adhesion using mechanical vibrations provided by a sonicator bath for several tens of minutes. AFM images have been carried out before and after the mechanical test. The results (displayed in figure 4) show that the 15 nm size multilayer system starts to delaminate after 20 minutes of sonication, whereas the 5 nm one only presents some disorder in Au NPs packing on the outermost layer. General Annexe: Combined electrostatic-covalent building of Au NPs multilayers, and their size enhanced cohesive and SERS properties

A10

The cohesion of the multilayer elaborated with small Au NPs thus appears stronger than that prepared with larger ones. This finding is in good agreement with what can be expected from size effects in such nanomaterials. Indeed, the total free volume (tetrahedral and octahedral voids) in a close-packed 2D assembly of monodisperse spherical particles (1 or 2 layers for instance) increases with the size of the particles. 14 As a result, one expects the cohesion of the ordered assembly of spherical particles to decrease with the increase of the Au NPs diameter. This size-dependent cohesion of NPsbased structures was confirmed dealing with the thermomechanical stability of drying structures, built with nanocolloidal Au particles presented in part 2 (chapter 1)). 15 These size dependent properties represent an important result that will have a strong impact on the choice of functional surfaces used either in regenerative or lubrication domain.

The multilayered structures were then used in SERS to characterize the effect of both the layering (number of layers) and the NPs size on their Raman sensitivity.

c-Raman spectrometry on multilayer gold particulate film

For the following Raman measurements, the excitation laser wavelength is of 624 nm. Indeed a laser wavelength less than 600 nm and higher than 400 nm would not be a good choice for SERS study with both 15 and 5 nm diameter NPs. The absorption coefficient of these NPs is much higher in this region as shown in the first chapter of part 1. This absorption leads reducing the intensity of the SERS response, and therefore the choice of an excitation wavelength less than 600 nm and higher than 400 nm can "artificially" leads to an exaltation of the SERS response of one particles size compared to the other. To promote the above results towards molecular characterization and detection, the SERS spectra of the bare (as-prepared) nanoparticulate multilayers were recorded (the measurements were performed on each layer before the desorption of the citrate from NPs surface), and compared to standard thermally evaporated gold films, and presented in figure 5. 14 The results of Raman spectra show that there is no signal for the thermally evaporated Au thin film, which thickness is equivalent to 30 nm. For the nanoparticulate multilayer structure, the Raman analysis shows the emergence of signals, the intensity of which depends on the number of layers.

Basically, for the 15 nm sized NPs in this experiment, there is no significant band up to two layers [figure 5a]. Above 3 layers, the intensity of the main band at 1540 cm -1 appears and increases in intensity as shown in figure 5a. The peak observed around 1540 cm -1 corresponds to carboxylic acid surrounding the particles. The enhancement of Raman intensity between one and five layers is of the order of 50. A small shift and a b A12 enlargement of the peak is observed with the increase of the number of layers, due to the coupling between NPs dipoles over a large scale.

For the 5 nm sized NPs system, the same main peak was observed. However, contrary to the larger NPs multilayer, the intensity of the main band at 1540 cm -1 was already significant from the first layer, and increases continuously up to the fourth layer. The enhancement of Raman signal between one and four layers is higher compared to the larger NPs multilayer colloidal system, and of the order of 70. The SERS spectra and the characteristic peaks of MB are displayed in figure 2.2.5. In the spectra of figure 6, the main peak at 1623 cm -1 corresponds to the Alkene C=C stretching vibration of cis (unsat)-CH=CH-(unsat). And at 1398 cm -1 , another peak corresponds to the Sym CH 3 deformation vibration of -N(CH 3 ) 2 . Our results are in good agreement with values previously published. 16 The strong and medium peak at 1190 cm -1 was previously observed on the SERS spectra of the bare structure as shown in figure 5. This peak corresponds to the carboxylate group of the citrate molecules adsorbed onto the Au NPs.

In figure 7a, the spectra show the variation of intensity of the main peak of the SERS spectra of MB (at 1623 cm -1 ) as function of the number of layers in the 15 nm Au NPs multilayer structure. At a constant NPs surface coverage of each layer, and for a constant MB concentration, these multilayer structures were shown to create a strong enhancement of the Raman signal of the adsorbed methylene blue (MB). In figure 7b, the evolution of the intensity of the main peak at 1623 cm -1 of the MB was plotted versus the number of Au colloidal layers. As the number of layers increases, a regular and sharp increase of the Raman intensity of adsorbed MB is recorded. The linear evolution of the maximum peak intensity vs the number of layers is characteristic of the profile commonly observed in LbL assemblies. (A/V) ratio corresponding to their 2D assembly is, and the stronger the optical coupling response is. It is a nano intrinsic effect and it is also the origin of the catalytic effect exalted NPs. And as the surface density of electrons of the NP increases with A/V, it is easy to see that the increase in density (by volume) with electron density in the layer of NPs (NPs mono or multilayer) when this layer is composed of small NPs. As it has been demonstrated in this Annex, the size adjustment of the NPs in multilayered surface structure provides a promising route for elaborating effective SERS active substrate for the detection of very small amounts of organic molecules in either air or solutions. Moreover, the adjustment of the interlayer distance by the chain length of the linker constitutes an additional tuning parameter of this SERS effect. Hence, the cohesive and adhesive properties, the stability and the size effect brought by these multilayered architectures can have an important potential of applications in environmental detection, in bioengineer and medicine, or as sensors and optical devices. 16 This size effect, were evocated in chapter 1 of part 2, confirming that this size effect is the intrinsic parameter playing in the particles-based structures cohesion independently of particles organization.

In this Annexe, a facile fabrication route of a multilayer architecture, alternating organic molecules and gold colloidal NPs onto silicon wafer had been successfully developed.

The robustness of the superlattice structure has been demonstrated by the strong combined electrostatic and covalent binding between molecules and NPs. These interactions enable to insure the compactness of the superstructure and a high surface coverage of each individual layer. These multilayer structures of Au NPs have proved to be an effective analytical tool when used to detect very low amount of methylene blue dye adsorbed on the structures, by Surface-Enhanced Raman spectroscopy (SERS).

Furthermore, we showed that both the cohesion and the SERS sensitivity of the multilayer structures were significantly enhanced by decreasing the size of the Au NPs building units, bringing a clear evidence of size effects in nanostructured materials. The combination of this proved size effect with the shape and the organization of nanocolloidal metal particles in general, and of Au nanocolloids in particular, provides a new and effective tuning parameter towards the improvement of the stability and sensitivity of nanostructure-based devices.

I 2 . 2 .

 22 would like to thank all the European partners Dr. Enrico Gnecco, Dr. Hendrick Höshler, Dr. Akshata Rao, Dr. Rogerio Colaço, Dr. Mykhaylo Evstigneev, Dr. André Schirmeisen, Dr. Rynno Lohmus, Dr. Guido Paolicelli, Dr. Andrzej Kulik, Dr. Santiago Casado, Dr. Sergei Vlassov, Ms. Patrizia Paradiso and Mr. Tobias Meier to all their near or far contributions in this work especially in the subject of the FANAS project (AFM manipulation of nanoparticles). I am thankful to the examination committee members Dr. Serge Stoll, Prof. Claudine Filiatre, Dr. Enrico Gnecco and Dr. Hendrick Höshler for accepting to evaluate my PhD work. I would like to thank the Director of our institute Dr. Catie Vix for being supportive to each personnel of the institute. I am grateful to all the technical and administrative personnel of the laboratory to their technical support, in particular, Dr. Loïc Vidal (TEM), Mr. Hugues Bonnet and Dr. Ludovic Josien (SEM), Mr. Simon Grée (SERS and UV-VIS), Dr. Aissam Airoudj and Dr. Jean-luc Bubendorff (AFM), Mrs. Marie-Paule Hirn (Centrifugation), Mr. Philippe Kunemann (Contact angle measurements system), Mr. Eric Ehrhard (informatics), Mr. Patrick Lamielle (Plant), Mr. Stéphan Knopf (Store), Mrs. Fabienne Sorgato (Secreteria), Mrs. Natalina Muller, Mrs. Joëlle Dangy and Louisa Idiri (Accounting), Mrs. Nathalie Castelein (Library) and Mrs. Sylvie Forget (Reception). Many thanks to Sylvie to the special time and discussions we had in the hallways of the institute. Many thanks to all of them to the social time shared with them. I am also thankful to all the researchers of the institute to each social and scientific time and discussion shared with them. Particularly I would like to thank Dr. Laurent Vonna, Dr. Vincent Roucoules, Dr. Govindasamy Chandrasekar and Dr. Bassel Haidar... I would like to thank all Ph-D students with whom I shared great moments of a social, Results and discussion 139 a.Structural characterization of samples 140 b.The surface microscopic complex aggregation patterns c.Nanoscale aggregation structures Results and discussion a.Influence of the size and the shape of NP b.Influence of the chemistry of NP c.Influence of the temperature d.Organization effects e.Influence of the relative humidity 213

Figure 1 :

 1 Figure 1: Dendritic structure formed during the drying of a drop of spherical gold nanoparticles suspension on Silicon wafer (SiO2).

Figure 2 :

 2 Figure 2: (a) scanning electron microscopy image of a representative AFM tip manipulating gold nanoparticles. Scale: 3x3 microns. (b) AFM phase image (Tapping mode) of NPs and their trajectories (slow scan axis: up). Scale: 5x5 microns.

  4 N.F. Steinmetz, Nanomedicine: Nanotechnology, Biology, and Medicine, 2010, 6, 634. 5 P.G. Tratnyek, R.L. Johnson, Nanotoday, 2006, 1, 44.6 M.D. Sanchez-Garcia, A. Lopez-Rubio, J.M. Lagaron, Trends in Food Science & Technology, 2010, 21, 528.

Figure 1 . 1 :

 11 Figure 1.1: Examples of domains of nanotechnology applications.

  10 M.C. Daniel, D. Astruc, Chem. Rev., 2004, 104, 293.

Figure 1 . 2 :

 12 Figure 1.2: The Lycurgus Cup which dates from the 4th century is displayed at the British Museum in

  solutions are mixtures in the form of liquids or gels that contain finely divided particles in suspension. These colloidal nanoparticles (NPs) or metal objects are entities composed of metal atoms, and have a size small enough so that the solution remains homogeneous. They are intermediaries between suspensions (particle size above than 200 nm) and the ' real ' solutions (particle size below 2 nm) [figure1.1.0.1].

Figure 1 . 1 . 0 . 1 :

 1101 Figure 1.1.0.1: Situation of colloidal solutions. TEM: transmission electron microscopy, SEM: scanning electron microscopy.

  consists to add to the solution an element who presents a large volume, typically a polymer or organic ligand, which adsorbed on the surface of the NPs prevents from agglomeration. These large molecules form a barrier around the NPs and avoid them to coalesce [figure 1.1.0.2].

Figure 1 . 1 .0. 2 :

 112 Figure 1.1.0.2: Steric stabilization of NPs; a) short and b) long surfactant chains.

Figure 1 . 1 .0. 3 :

 113 Figure 1.1.0.3: Mechanism of stabilization of NPs by electrostatic repulsion.

Figure 1 . 1 . 1 . 1 :

 1111 Figure 1.1.1.1: nucleation and growth mechanism of NPs. 27

  The solutions are then characterized with Transmission Electron Microscope (TEM) [figure 1.1.1.2, A-B-C-A'-B'] and Ultraviolet-visible spectroscopy (UV-vis) [figure 1.1.1.9].

Figure 1 . 1 . 1 . 2 :

 1112 Figure 1.1.1.2: TEM images of suspension of Au NPs referred to as A, B, C, A', B' of respectively an average diameter of 35, 25, 15, 50 and 30 nm.

  bearing the negative charge of citrate ions [figure 1.1.1.3] generating repulsive Coulombic forces between particles [figure 1.1.0.3].

Figure 1 . 1 . 1 . 3 :

 1113 Figure 1.1.1.3: Representation of a colloid spherical gold nanoparticle (relative size of molecules and NPs are not at scale).

Figure 1 . 1 . 1 . 4 :

 1114 Figure 1.1.1.4: Chemical formula of THPC.

Figure 1 . 1 . 1 . 5 :

 1115 Figure 1.1.1.5: TEM images of suspension D and E: respectively 3 to 5 nm Au NPs diameter.

  NPs to improve their performance when used in advanced NPs-based materials. This procedure can be achieved in one or two steps. The first one, we have chosen, consists in a reduction of HAuCl4 by NaBH4 in the presence of a thiol, and the second one consists to exchange the initial surfactant by a thiol molecule. b.1. One step procedure Amine functionalized gold nanospheres (hydrophilic surfaces): 400 µL of 213 mM 2-Mercaptoethylamine hydrochloride [C2H7NS] was added to 40 mL of 1, 42 mM HAuCl4, and stirred for 30 minutes at room temperature. 10 µL of 10 mM NaBH4 was added under stirring to 30 minutes in the dark. The solution is stored at 4 ° C in a dark bottle. HAuCl4 is dispersed in water, reduced by NaBH4 and stabilized by C2H7NS (electrosteric stabilization) due to the thiol-gold bound 46 . The size of the particles is around 25 nm [figure 1.1.1.6].

Figure 1 . 1 . 1 . 6 :

 1116 Figure 1.1.1.6: TEM image of amine functionalized gold nanospheres.

Figure 1 . 1 . 1 . 7 :

 1117 Figure 1.1.1.7: TEM image of methyl-functionalized gold nanospheres.

c. 1 .

 1 Concentrations calculationBoth the weight concentration, the volume fraction and particles number of a fresh suspension were determined by differential weighing between defined volumes V0 of the suspension drops of mass m0 and their resulting dried NPs residue of mass mf as shown in figure1.1.1.8.

Figure 1 . 1 . 1 . 8 :

 1118 Figure 1.1.1.8: Scheme presenting deposited supension drop and the corresponding residual NPs after drying.

Figure 1 . 1 . 1 . 9 :

 1119 Figure 1.1.1.9: Absorbance curves of Au NPs suspensions as a function of NPs size (NPs diameter): A (35 nm) dark blue, B (25 nm) green, C (15 nm) red, D (3 nm) brown, E (5 nm) orange.

from 3

 3 up to 35nm diameter and displayed results in figure1.1.1.10. Results show that the absorbance increases quite linearly with the size of NPs (below 100nm diameter). In addition, the absorbance peak shifts to higher wavelengths with an increase of NPs diameter. The colour of the suspension varies from red to pink (C, B, A) with a Tyndall effect for the bigger ones. These are respectively brownish and orange-brown for the small particles suspensions D and E. In accordance with Lorenz-Mie-Debye theory for an arbitrary size of particle, the surface plasmon resonance of the gold particles is redshifted with increasing of particle size (C, B, A, F) [Fig 1.1.1.9]. 48 In the regime where the particle radius r is such as r <<< /2 where  is the wavelength of light (D, E suspensions), Rayleigh scattering contributes to diffuse light, causing continuous absorbance going to smaller wavelengths [Fig 1.1.1.9]. 49 47 U. Kreibig, M. Vollmer, Editors Optical Properties of Metal Clusters, vol. 25 Springer-Verlag, Heidelberg 1995. 48 G. Mie, Ann. Phys., 1908, 25, 377.

Figure 1 . 1 . 1 . 10 :

 11110 Figure 1.1.1.10: Wavelength shifting versus nanoparticle size (nm).

  Cetyltrimethylammoniumbromide (98%) (CTAB), gold (III) chloride trihydrate (HAuCl4), tri-sodium citrate, L-ascorbic acid, sodium borohydride (99%) (NaBH4) and silver nitrate (AgNO3) were used in this work for the synthesis of GNRs. All the chemicals were used without further purification. a.1. Seed Solution CTAB solution (5 mL, 0.2 M) was mixed with 5.0 mL of 0.0005 M HAuCl4. To the stirred solution, 0.6 mL of ice-cold 0.01 M NaBH4 was added, which resulted in the formation of a brownish yellow solution. Vigorous stirring of the seed solution was continued for 2 min. After the solution was stirred, it was kept at 25 °C. a.2. Short gold nanorods (aspect ratio 2.6 ± 0.3) Colloidal gold nanorods solution was synthesised employing the optimized procedure as described by El-Sayed group in 2003. 59 CTAB (5 mL, 0.2 M) was added to 0.2 mL of 0.004 M AgNO3 solution at 25 °C. To this solution, 5.0 mL of 0.001 M HAuCl4 was added, and after gentle mixing of the solution, 70 μL of 0.0788 M ascorbic acid was added.Ascorbic acid as a mild reducing agent changes the growth solution from dark yellow to colourless. The final step was the addition of 12 μL of the seed solution to the growth solution at 30 °C. The colour of the solution gradually changed within 10-20 min. The temperature of the growth medium was kept constant at 30°C. This pathway produces pure nanorod solutions with aspect ratios up to 2.6 ± 0.3. a.3. Long gold nanorods (aspect ratio 14 ± 2.7)A three-step seeding method described by Murphy's group was used for this nanorod preparation.66 Specifically, two 20 mL beakers and one 100 mL beakers (labelled A, B, and C, respectively) were taken. To these beakers were added 9 mL (in flasks A and B) and 45 mL (in flask C) of growth solution containing a mixture of 2.5 x 10 -4 M HAuCl4 and 0.1 M CTAB solutions. To these solutions were added 50 μL (flasks A and B) and 250 μL (flask C) of 0.1 M freshly prepared ascorbic acid, and the resulting solutions were stirred gently.

Figure 1 . 1 . 2 .

 112 Figure 1.1.2.1 shows the TEM images of the as-synthesised gold nanorod samples synthesised with and without the addition of AgNO3. TEM images (a), (b), and (c) show the gold nanorods synthesised without AgNO3 and (d), (e), and (f) with AgNO3. TEM images (a), (b), and (c) of the long nanorods indicate a localized isotropic arrangement

Figure 1 . 1 . 2 . 1 :

 1121 Figure 1.1.2.1: TEM images of (a), (b), (c) high aspect ratio gold nanorods (14 ± 2.7), and (d), (e), (f) low aspect ratio gold nanorods (2.6 ±0.3).

Figure 1 . 1 . 2 . 2 :

 1122 Figure 1.1.2.2: TEM images of a) non-centrifuged nanorod, b) one time centrifuged and c) two times centrifuged.

Figure 1 .Figure 1 . 1 . 2 . 3 :

 11123 Figure 1.1.2.3 shows the nanorods after functionalization with 11-Mercapto-1undecanol, the shape and the size of nanorods are similar to as synthesized ones.

Figure 1 .

 1 1.2.4 shows the UV-vis of the prepared nanorods samples. UV-vis spectrum of the long nanorods (14 ± 2.7) sample shows two different plasmon bands: one due to longitudinal plasmon band at 974 nm, and another one due to the transverse plasmon band at 541 nm. Short gold nanorods (2.6 ± 0.3) shew longitudinal plasmon band at 968 nm and transverse plasmon band at 567 nm. These results are in agreement with those obtained in the literature by Huang et al.76 The sharpness of the bands clearly indicates the monodispersity of the sample in terms of size and shape. The low intensity of the transverse plasmon band may indicate that the amount of spherical particles present in the suspension is minimal. A sudden drift can be observed at around 850 nm in spectrum of both nanorods samples, due to the change of lamp from NIR light to visible light.

Figure 1 . 1 . 2 . 4 :

 1124 Figure 1.1.2.4: UV-vis spectra of long gold nanorods (14 ± 2.7) in smooth line, and short gold nanorods (2.6 ± 0.3) in dashed line.

Figure A1. 1 . 1 :

 11 Figure A1.1.1: TEM image of solution F (65  5 nm in diameter).

2. 1 .Figure N1. 1 . 2 :Figure N1. 1 . 3 :

 11213 Figure N1.1.2: TEM images of octahedron gold nanoparticles: a. mixture of spherical and octahedron NPs b. zoom on individual octahedron NPs.

Figure N1. 1 . 4 :

 14 Figure N1.1.4: TEM images of nanonets of gold. b) Formation of a half triangular particle at the beginning and continuous growth of the particle at one extremity to form a net-like structure.

  kinetics, and the Au atoms or clusters assembly controlled by the low amount of surfactant. Indeed surfactant self-assembles at the periphery of individual Au NPs to a b stabilize them and simultaneously stop the growth process. And yet, the surfactant concentration in such operating condition is not high enough to create individual particles which involve formation of larger cluster such as net depicted in Figure N.1.1.4.

Figure 1 . 2 .0. 1 :

 121 Figure 1.2.0.1: Sketch of self-assembled organosilanes monolayers on an oxidized silicon substrate (relative size of molecules is not at scale).

Figure 1 . 2 . 1 . 1 :

 1211 Figure 1.2.1.1: Scheme displaying the two main procedures to form alkylsilanes SAMs on a hydroxylated silica surface.

  CH3) or fluoro (-CF3) terminated functions. The molecules are the following ones: -Hexadecyltrichlorosilane (HTS) [figure 1.2.2.1a]: CH3-[CH2]15-SiCl3 -Octadecyltrichlorosilane (OTS): CH3-[CH2]17-SiCl3 -1H, 1H, 2H, 2H-Perfluorodecyltrichlorosilane (PFS) [Fig 1.2.2.1b]: C10H4Cl3F17Si

Figure 1 . 2 . 2 . 1 :

 1221 Figure 1.2.2.1: developed molecular representation of a) HTS and b) PFS.

-N- 6 (

 6 aminohexyl)aminopropyltrimethoxysilane (NH2) [figure 1.2.2.2]: NH2-[CH2]6-NH-[CH2]3-Si[OC2H5]3 .

Figure 1 . 2 . 2 . 2 :

 1222 Figure 1.2.2.2: Representation of the hydrophilic molecule ended with an amine terminal group (NH2).

Figure 1 . 2 . 2 . 3 :

 1223 Figure 1.2.2.3: Physico-chemical anchorage mechanism of organosilanes onto hydroxylated silicon.

Figure 1 . 2 . 2 . 4 :

 1224 Figure 1.2.2.4: Sketch of a deposited liquid drop on a substrate-contact angle at the equilibrium.

  15 A.N. Shipway, E. Katz, I. Willner, Chem. Phys. Chem., 2000, 1, 18.

Figure 1 . 2 . 2 . 5 :

 1225 Figure 1.2.2.5: Presentation of the multilayer system with their refractive index and extinction coefficient.

Figure 1 . 2 . 3 . 1 :Figure 1 . 2 . 3 . 1 :

 12311231 Figure 1.2.3.1: Representative scheme of our microcontact printing procedure a) printed hydrophilic domains and b) self-assembling of the hydrophobic continous phase deposited in vapour phase.

Figure 2 . 1 :

 21 Figure 2.1: Drops of dried human blood taken from a healthy individual (left) and an anemic patient (right) that is to say, suffering from a lack of hemoglobin. Drying revealed regular patterns

14 , 15

 1415 The most commonly observed example of these interface instabilities is the formation of fingerlike patterns, described by Saffman and Taylor. These interface instabilities, also known as Saffman-Taylor hydrodynamic instabilities, are essentially governed by the balance between viscous and capillary effects (forces), and expressed by the capillary number Ca ~ (μU/γ), where μ, γ, and U represent the surface tension, the viscosity and the velocity of the moving fluid, respectively. On the other hand, hydrodynamic instabilities leading to the formation of multibranched fractal structures are rarely observed in wetting processes. So far, these fractal patterns have mainly been produced in a confined model two-dimensional (2-D) space represented by two parallel plates (the Hele-Shaw cell), during the displacement of a fluid-fluid interface. Despite their strong topological difference, both Saffman-Taylor instabilities and multibranched fractal fingering 14 H. Van Damme, The Fractal Approach to Heterogeneous Chemistry, John Wiley & Sons Ltd: Chichester, 1989, 199.15 D. Schwabe,; U. Mo¨ller, J. Schneider,A. Scharmann, Phys.Fluids A , 1992, 4, 2368 basically arise from the same hydrodynamic phenomenon described by Darcy's law 14 as follows: eq2.1 where U(x,y) is the averaged in-plane velocity related to the pressure gradient p(x,y) at the moving fluid interface in a two-dimensional flow; h and η denote the thickness (normal to the flow plane) and viscosity, respectively, of the confined fluid interface.

Figure 2 . 1 .0. 1 :

 211 Figure 2.1.0.1: Image of the drainage of glass microspheres during the evaporation of the microcolloidal drop;multiple images were superimposed to illustrate the trajectory of the particles.1

Figure 2 . 1 .0. 2 :

 212 Figure 2.1.0.2: Representative scheme of: a) Pinning-dominated evaporation/drying regime. Here, the drying results in an accumulation of solutes along the drop border, either due to a complete pinning or a pinning for a finite but sufficient time for evaporation-gradient to drive the outward particle transport. In the final stage, the residual fluid may either detach from the peripheral accumulated particles and recede, or dry homogeneously in its depleted central part, or dewet through heterogeneous nucleation (most probable). b) Depinning/receding-dominated evaporation/drying regime. Here, the evaporation leads to the 'early' depinning and receding of the drop, which now collects during its inward motion (shear-drainage) all the solutes that are loosely attached to the substrate. These solutes are then accumulated inside the final drying spot where the structures (when they form) appear essentially.

Figure 2 . 1 .0. 2 :

 212 Figure 2.1.0.2: Light microscopy image of a ring formed by slow evaporation of a drop of an aqueous suspension containing 60 nm nanospheres on mirror quality titanium disk. Ring diameter ~ 4.2 mm.2

Figure 2 . 1 .0. 3 :

 213 Figure 2.1.0.3: Occurring dendritic aggregate of 25 nm spherical gold NPs in a drying nanofluid drop deposited on silicon substrate at 20°C; the structure is captured (optical microscopy) as it appears, immediately after the drying, as attested by the thickness gradient interference fringes of the residual solvent surrounding the aggregate.

  4 B.B. Mandelbrot, Les objets fractals: forme, hasard et dimension; Flammarion, 1975. 5 B.B. Mandelbrot, The fractal Geometry of Nature, Freeman, San Fransisco, 1982.

  Figure 2.1.1.1 depicts the method of image analysis used to determine the fractal dimension.

Figure 2 . 1 . 1 . 1 :Figure 2 . 1 . 1 . 2 :

 21112112 Figure 2.1.1.1: Representation of the technique of "boxes" of fractal analysis of aggregates. a) the original optical microscopy image and b) the corresponding binarized image.

  diagram of figure 2.1.2.1 represents the occurrence of the complex aggregation patterns in the final drying spot of the nanofluid drops on SiO2 substrate, over the whole range of investigated NP size (d) and drying temperature (T).

Figure 2 . 1 . 2 . 1 :

 2121 Figure 2.1.2.1: Final drying patterns of nanocolloids suspensions of varying size on SiO2, at different drying temperatures. For (15 nm; T > 45°C) and (25, 35 nm; T > 20°C), only featureless particle deposits are formed in the final drying spot; the occurrence of the structures is zero for these conditions.

Figure 2 . 1 . 2 .

 212 Figure 2.1.2.2 represents the typical evaporation kinetics given by the time-variation of the contact angle and contact diameter of the drop for conditions where the complex structures are formed on the substrate. This kinetics is shown here in figure 2.1.2.2 for the drying temperature of 20°C and the smallest particle size (3 nm), a case where large and well-defined thick dendrite aggregates occur in this system.

Figure 2 . 1 . 2 . 2 :

 2122 Figure 2.1.2.2: Drying kinetics of 3 nm NP suspension drops on SiO2 at 20°C, typical of most complex aggregate forming systems; ■) contact angle, and ○) contact diameter.

Figures 2 .

 2 Figures 2.1.2.3 and 2.1.2.4 show, respectively, the corresponding occurrences and morphologies of drying-mediated aggregations patterns observed for the hydrophilic NH2-terminated, and the hydrophobic CH3-terminated substrates (HTS). In all cases, the structures and patterns shown are those generally taken at half-way between the centre and the border of the final drying spot.

Figure 2 . 1 . 2 . 3 :

 2123 Figure 2.1.2.3: Dense arborescent patterns arising from the drying of 25 nm particles on NH2 terminated surfaces, at the four drying temperatures (20, 45, 75 and 100°C).

Figures 2 .

 2 Figures 2.1.2.1 and 2.1.2.3 contain all the essential and relevant features of this drying and pattern formation process, the most striking of which is the modulation of the occurrence and morphological features of the aggregates (dendrites) by the temperature (T), the size of the nanocolloid particle, and the wetting properties (nature) of the substrate. The influence of temperature and particle size on the aggregate morphology is well illustrated by the first column (3 nm particles) images of figure 2.1.2.1 where the size and the complexity of the aggregation structures gradually decrease (degenerated dendrites), when the drying temperature and the size of the NPs increase.

Figure 2 . 1 . 2 . 4 :

 2124 Figure 2.1.2.4: Typical dendritic structures (fourfold with secondary branches) observed on CH3-terminated surfaces, for the conditions where these complex aggregation patterns appear on this non-wetted substrate: smallest NP size (3 nm) and drying temperatures of 20~ambient, and 75°C. For any other combination of the NP size and drying temperature, no dendrites or any other fractal structure is formed on this substrate after the drying of the nanofluid.

Figure 2 . 1 . 2 . 5 :

 2125 Figure 2.1.2.5: Drying kinetics for 25 nm NPs suspension drops at 75°C on, a) SiO2 and, b) NH2-terminated substrates; ■) contact angle, and ○) contact diameter. Note that under these conditions, the complex aggregation structures appear on the NH2-terminanted surface, and not on SiO2.

Part 2 :

 2 Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 1: Complex aggregation patterns issued from drying nanocolloidal suspensions 93

Figure 2 . 1 . 3 . 1 :

 2131 Figure 2.1.3.1: Occurrence of complex patterns on SiO2 of 5 µL drying drop of a) citrate stabilized b) amine functionalized NPs before dialysis of suspensions (raw).

Figure 2 .

 2 Figure 2.1.3.2: residual aggregation patterns on SiO2 of drying drop (5 µL) of a) citrate stabilized and b, b') amine functionalized NPs after dialysis of suspensions, after dialysis.

Figures 2 .

 2 Figures 2.1.3.3 a and b display, respectively, the drying areas of highly concentrated drops of citrate stabilized and amine functionalized Au NPs suspensions.

Figure 2 . 1 . 3 . 3 :

 2133 Figure 2.1.3.3: Drying areas and aggregation structures of "multi-steps concentrated" dialyzed drop, after 100 additions of 5 µL of dialyzed NPs suspension to the initial deposited 5 µL drop. Each volume increament of 5 µL was added after ~ 5 minutes time interval to avoid contact line retraction and ensure a drying at constant contact area. a) Citrate stabilized and b) amine functionalized NP.

  Figure 2.1.3.3 displays the absence of multibranched NPs aggregates in the wedge and at middle distance between the wedge and the center of the drying spot. More interestingly, the complex aggregation patterns occur exclusively in the final drying spot for both solutions (citrate and amine b Final spot (drop center) Wedge Middle distance between wedge and center Final spot (drop center) a Wedge Middle distance between wedge and center Part 2: Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 1: Complex aggregation patterns issued from drying nanocolloidal suspensions 97 stabilized NPs). Although these experiments of concentrating the dialyzed drop happen

Figure 2 . 1 . 3 . 4 :

 2134 Figure 2.1.3.4: Typical structures resulting from the drying of a dialyzed NPs solution drop concentrated by centrifugation at a nominal concentration equal to that of the "as-prepared" solution ("one-step concentrated drop"). 5 µL of this concentrated dialyzed solution was used in a single step drying experiment, i.e. in drying conditions comparable to those used for the "as-prepared" solution. The drying areas in this case have never led to any complex aggregation structures or patterns, displaying essentially a random distribution of featureless and discrete particles aggregates.

Part 2 :

 2 Figures 2.1.3.5 and 2.1.3.6 display respectively the scanning electron microscopy (SEM) images and the energy-dispersive X-ray spectroscopy (EDX) analysis on the dried residues of the raw amine-functionalized NPs suspension drop and of the "mlti-steps concentrated" dialyzed one (final spot).

Figure 2 . 1 . 3 . 5 :Figure 2

 21352 Figure 2.1.3.5: SEM image and EDX spectra of 3 analyzed areas on the dried residue of raw amine functionalized NPs suspension.

Figure 2 .

 2 Figure 2.1.3.6: a) HR-SEM image of a complex structure obtained in the final drying spot of dialyzed amine functionalized NPs suspension ("multi-steps concentrated drop"). b) EDX spectra of corresponding area: from the observed struture along the dashed line to the edge, as drawn on the SEM image.

Part 2 :

 2 Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 1: Complex aggregation patterns issued from drying nanocolloidal suspensions 100 receding (retraction) of the aqueous solvent during the drying process drains also the residual ions inside the final spot. The surconcentration of ions in this final spot greatly contribute to the formation of the complex aggregation patterns in the late-stage of the drying as observed in figure2.1.3.6. This assumption was also confirmed by the "onestep concentrated drop" procedure the results of which are presented in figure 2.1.3.4.

  from the Poisson equation and the Maxwell-Boltzmann expression (Debye-Hückel theory) as φ = φ0 e -x / , where is the Debye-Hückel length, and x the distance between the surface of the particle and a point in the suspension. For the two amine stabilized NPs suspensions we are dealing with here (the raw and the dialyzed ones), the 101 residual salt concentrations, and hence the surface potentials φ of the NPs are very different. As a result, and since φ0 is similar, the difference in φ is mainly related to that in their Debye-Hückel lengths . For spherical particles, the Gouy-Chapman model of the EDL leads to the distribution of the electrical potential outside of the surface as displayed in figure 2.1.3.7. The Debye length for such ideal distribution has been estimated as function of the ionic strength ) and given by the following expression: eq 2.1.3.1 where, is the dielectric constant of vacuum, is the dielectric constant of the solvent, 78.5 for water at 25°C, e the fundamental charge |e| ≈ 1,602 ×10-19 C, kB is Boltzmann constant ≈ 1.3806504. 10 -23 J.K -1 , NA is the Avogadro number and i is the charged species of valence Zi and concentration Ci (mol • L -1 ).

Figure 2 . 1 . 3 . 7 :

 2137 Figure 2.1.3.7: Scheme depicting the electric double layer surrounding each individual NP.

  relation (ph -p0) by it integral expression given above leads to the following expression for the repulsive interaction potential,

Part 2 :

 2 Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 1: Complex aggregation patterns issued from drying nanocolloidal suspensions

Part 2 : 2

 22 Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 1: Complex aggregation patterns issued from drying nanocolloidal suspensions 105 precisely of fractal structures is very low, as we showed it for dialyzed NPs solutions. These results may provide a new picture toward a deeper understanding of the 2-D selfassembly and complex pattern formation in drying suspension in general, and in NPsbased solutions in particular.Drying-mediated assembly of colloidal NPs suspensions is an important issue, for understanding fundamental processes of self-organization, and for the "spontaneous" formation of large-scale and complex patterns. Whereas the spontaneous formation of patterns at model surfaces represent an important research issue and area of interfacial phenomena, the directed-assembly of NPs in functional 2D-nanostructures through introduced templates also opens an attractive route for the controlled growth of 2-D networks in nanophysics or biology. The following chapter of this part will focus on an original wetting-assisted method that we developed toward the formation of NPs nanorings. The drying of a nanocolloid suspension drop confining immiscible nanodroplets (or nanobubbles) that are settled on a solid substrate leads to the formation of two-dimensional ring-shaped nanostructures. The originality of this new approach relies solely on self-assembly processes at gas/solid and liquid/solid interfaces, and does not involve any replication techniques, as it essentially takes benefit of simple interfacial phenomena. Part 2: Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 2: Nanobubbles and nanodroplets template growth of particles nanorings in drying nanofluids 106 Chapter Nanobubbles and nanodroplets template growth of particles nanorings in drying nanofluids 2.2.0. Introduction Patterns of nanosize rings have recently attracted intense research interest, driven in

Figure 2 . 2 .0. 1 :

 221 Figure 2.2.0.1: Height AFM images of a dry wetting film of sodium alginate solution of concentration C= 0.2 wt% in water (19.2 μmol/L), deposited by dropcasting on a cleaned silicon wafer. (a) Randomly dispersed nanoholes in the thin wetting film, (b) zoom on nanoholes at the surface. Frame sizes: 5 µm and 2 µm, respectively.

  The nanocolloidal suspension was an aqueous solution of gold nanoparticles that was synthesized from tetrachloroauric (III) acid hydrate ([HAuCl4]•H2O), stabilized with citric acid trisodium as described in the first chapter of part one. The average size of these particles is 25±5 nm (solution B chapter 1 of part 1). In order to disperse these assynthesized citrate stabilized Au nanoparticles in organic non-polar solvents, the NPs were hydrophobized by replacing citrate molecules by grafted methyl-terminated alkylthiol molecules. Methyl-thiol-stabilized Au NPs were prepared according to the process described in chapter 1 of part 1 of this memory. The solution was respectively resuspended in tetrahydrofuran (THF) or cyclohexane for nanobubbles-assisted or nanodroplets nanoring assembly. The volume fraction of Au nanoparticles in the final organic suspension (THF or cyclohexane) was about 7.8 x10 -5 .The formation of the nanoparticles rings on hydrophobic surfaces relies on the nonmiscibility of two fluids: either polar nanodroplets, or nanobubbles dispersed in an organic nanoparticles suspension.a. NanodropletsThe nanodroplets dispersions were prepared as follows. A water-ethanol mixture (1:4 in volume) was added to nanoparticles suspension in cyclohexane. This solution was sonicated with an electrode at 20 kHz during 10 sec (1 pulse/sec), using a sonicator from Bioblock Scientific (VIBRA-CELL, MOD. 72441), operated at a nominal output power of 300 W. Nanodroplets were formed within a few seconds, with both sizes and distribution remaining stable for up to ~30 minutes. The average nanodroplet size in the suspension, characterized by light backscattering measurements using a Turbiscan device was ca. 90 nm.

Figure 2 . 2 . 1 . 1 :

 2211 Figure 2.2.1.1: Scheme of a nanocolloid suspension drop confining immiscible nanodroplets of (ethanol/water) mixture, or nanobubbles that are settled at a solid substrate.

Part 2 :

 2 Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 2: Nanobubbles and nanodroplets template growth of particles nanorings in drying nanofluids 115 For the nanodroplets to remain attached to the substrate when the wedge of the suspension drop crosses them, their adhesion and the related threshold static frictional force required to detach them should be higher than the above shear force developed within the retracting wedge. Otherwise, the nanodroplets are detached and collected within the receding drop. As discussed in the previous paragraph, (ethanol/water) solvent mixture was used for the nanodroplets to prevent their detachment and drainage during the late-stage drying of the suspension drop.b. Destabilization and rupture of the confined nanobubbles and dropletsThe mode of destabilization and rupture of the confined nanobubbles/nanodroplets seems to result from two distinct phenomena, depending on whether nanobubbles or nanodroplets are involved, as depicted in figures 2.2.2.1 and 2.2.2.3. The evaporation of the drop first leads to the decrease of the overall thickness of the drop and further confinement of the nanoparticles coated nanodroplets/nanobubbles in the wedge.For nanobubbles, when the thickness of the THF film covering the nanobubble at its apex becomes comparable to the length-scale of long-range (L-R) vdW forces, the air encapsulated in the bubble and that in the surrounding atmosphere couples and attracts each other, creating an extra-compressive pressure across the suspension (solvent) film. This extra pressure that acts to conjoin the air phases by further thinning the film up to rupture (destabilization) has a magnitude which is related to the Hamaker constant (A) of the (air/suspension film/air) interface (A > 0), and the thickness h of the suspension film as, П ~ (-A/6πh 3 ). It is worth mentioning at this point that we have implicitly assumed that the apex of the nanobubbles (nanodroplet) was no longer covered by the nanoparticles under the above confinement condition, leaving there a configuration of (air bubble/solvent/air) system. Indeed as the suspension film thins down, the local confinement (and fluctuations) at the apex pushes the nanoparticles downward along the nanobubble interface. Typically, the configuration of the receding wedge where such confinement and destabilization process can develop is that for which the size of the wedge (both thickness and width) is of the order of the diameter of the nanobubble. The variation of the Laplace pressure inside the nanobubble, induced by the rupture of the thin solvent film drives the explosion of the nanobubble. Finally, the rupture of the suspension film at the apex and the collapse of the nanobubble provoke the downward drainage of the nanoparticles along the nanobubble/suspension interface, leading to their peripheral assembly (nanoring) as shown in figure 2.2.2.1c.

Figure 2 . 2 . 2 . 1 :

 2221 Figure 2.2.2.1: Scheme depicting the three main steps of the evaporation-drying process of a nanocolloid suspension confining immiscible nanobubbles and leading to the formation of isolated Au nanoparticles rings. (a) Initial nanocolloid suspension drop confining immiscible nanobubbles, (b) decrease of the whole volume of the drop due to the evaporation of the solvent and confinement of the nanobubbles coated with the Au nanoparticles; inset: zoom in on the thinning of the apex of the nanobubbles at nanobubble\suspension\air) interface. (c) rupture (explosion) of the nanobubble and formation of a peripheral particles nanoring.

Figure 2 . 2 . 2 . 2 :

 2222 Figure 2.2.2.2: Height AFM images of 25 nm diameter gold nanoparticles self-assembled into ring-like structures after drying of confined nanobubbles embedded at a hydrophobic surface.(a) Random organisation Au nanoparticles nanorings structures, (b) 3D-zoom-in on a single Au nanoparticles nanoring. Frame sizes: 5 µm and 300 nm respectively.

Figure 2 . 2 . 2 . 3 :

 2223 Figure 2.2.2.3: Scheme depicting the three main steps of the evaporation-drying process of a nanocolloid suspension confining immiscible nanodroplets and leading to the formation of isolated Au nanoparticles rings: (a) Initial nanocolloid suspension drop confining immiscible nanodroplets, (b) decrease of the whole volume of the drop due to the evaporation of the solvent and confinement of the nanodroplets coated with the Au nanoparticles; inset: zoom in on the (nanodroplet\suspension\air) interface at the apex of a nanodroplet. (c) Collapse of nanodroplets and sliding of the Au nanoparticles along their interface, leading to the formation of a peripheral particles nanoring.

Figure 2 . 2 . 2 . 4 :

 2224 Figure 2.2.2.4: Optical microscope images showing the same area imaged at different time intervals (a-f) during the drying of a cyclohexane suspension drop onto a hydrophobic substrate. The sequential images depict the receding of the drop contact line and its local distortion (c-e) due to the presence of ethanol\water nanodroplet embedded at the surface. In images b) and c), the nanodroplet displays local and small deformations at its apex with the suspension film toward the centre (depression). The local thickening of the solvent film resulting from that local depression stabilizes this latter against rupture, until the wedge of the drop crosses the nanodroplet. Frame size: 100 µm.

Figure 2 . 2 . 2 . 5 :

 2225 Figure 2.2.2.5: Height AFM images of 25 nm diameter gold nanoparticles self-assembled into ringlike structures due to the confinement of nanodroplets embedded at a hydrophobic surface. (a) Random organisation of Au nanoparticles nanorings structures, (b) zoom-in on Au nanoparticles nanorings. Frame sizes: 2 µm and 500 nm respectively.

Figure 2 . 2 . 2 . 6 :

 2226 Figure 2.2.2.6: Evolution of Au nanoparticles nanoring size, vs. cyclohexane suspension drop radius(R). The red points () correspond to the experimental variation of the nanoparticles ring size vs drop radius. On the same graph, the columns correspond to the evolution of nanorings density (number/µm²), vs the radius of the cyclohexane suspension drop.

c. Influence of physico-chemical parameters controlling the nanorings formation c. 1 .

 1 NPs concentration in the suspension dropThis paragraph will first investigate the role of the nanoparticles concentration in the suspension drop. We present in figure 2.2.2.7 the formation of filled rings. The nanoparticles overpacking inside the rings gives rise to disks-like structures. These structures were obtained with a colloidal solution of NPs volume fraction 10 times higher than the nominal one (which induced nano-rings structures). Indeed, this nominal concentration (volume fraction = 7.8x10 -5 ) represents a threshold value to obtain ring-like structures.

Figure 2 . 2 . 2 . 7 :

 2227 Figure 2.2.2.7: Height AFM image of 25 nm diameter gold nanoparticles self-assembled into full-NPs diskstructures, due to an over crowding of the confined nanodroplets interface with NPs. Frame size: 3 µm.

Figure 2 . 2 . 2 . 8 :

 2228 Figure 2.2.2.8: Phase AFM images of gold nanorods self-assembled into ring-like structures after drying of confined nanodroplets embedded at a hydrophobic surface. (a) Random organization of Au nanorods nanorings structures, (b) zoom in on a Au nanorods assembled into a ring pattern. Frame sizes: 4 µm, 600 nm respectively.

Figure 2 . 2 . 2 . 9 :

 2229 Figure 2.2.2.9: TEM images of gold nanorods self-assembled into ring-like structures after drying of confined nanodroplets embedded at TEM grid interface. Scales a) 200 nm b) 300 nm.

Part 2 :

 2 Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 2: Nanobubbles and nanodroplets template growth of particles nanorings in drying nanofluids 123 c.3. Substrate effect The structure of a substrate represents a way to selectively organize the NPs nanorings onto the surface. We have proposed to use SAM patterned substrate obtained by microcontact printing technique (described in chapter 2 of part 1) to control the emergence of the NPs ring-like structures. The patterned substrates are made of hydrophilic domains surrounded by a hydrophobic continuum. The procedure to obtain ring-like structures on these prepatterned substrates is based on the condensation of ethanol vapor on the surface at 4 °C. This solvent deposition in the hydrophilic domains forms a discontinuous film bearing defect holes onto the substrate as sketched out in figure 2.2.2.10. The final step of the method consists on the deposition of a drop of hydrophobic coated NPs suspension in cyclohexane on the substrate, at 4 °C. Finally, the temperature of the support is slowly increased until room temperature (20 °C) to dry the solvent and form the NPs ring-like structures.

Figure 2 . 2 . 2 . 10 :

 22210 Figure 2.2.2.10: Sketch of the formation of ethanol discontinuous film bearing defect holes, after its condensation on prepatterned substrate.

Figure 2 . 2 . 2 .

 222 Figure 2.2.2.11 displays AFM images presenting the formation of NPs ring-like structures on hydrophilic domains of 4 µm size, after the evaporation/drying of the suspension drop.

Figure 2 . 2 . 2 . 11 :

 22211 Figure 2.2.2.11: Height AFM images of gold NPs self-assembled into ring-like structures after drying of confined droplets embedded at patterned surface (condensed ethanol). (a) Organization of Au NPs nanorings structures on the hydrophilic domains, (b) zoom in on Au NPs assembled into a ring pattern. Frame sizes: 20 µm, 8.4 µm, respectively. Inset 1.6 µm.

Figure 2 . 2 . 2 . 12 :

 22212 Figure 2.2.2.12: Height AFM image of gold nanoparticles self-assembled into ring-like structures after drying of confined nanodroplets embedded at patterned surface (condensed ethanol), the image shows a single big hydrophilic domain of 60 µm.

Figure 2 . 2 . 2 .

 222 Figure 2.2.2.12 : a) and c) AFM height images of respectively, randomly dispersed Au nanoparticles and random rings of nanoparticles on the surface; b) optical microscopy image of drying suspension drop and d) SERS spectra from NPs configurations a,b and c. C-H deformation vibration of CH3 aliphatic: 1465-1440 / of -(CH2) n-: 1445-1485 cm -1 . CH2 vibration of CH2-S-: 1305-1215 / C-C skeletal vibrations of -(CH2) n-: 1305-1295 cm -1 .

Part 2 :

 2 Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 2: Nanobubbles and nanodroplets template growth of particles nanorings in drying nanofluids 127 In the spectra of Figure 2.2.2.13 d the strong peak at 1460 cm -1 corresponds to the deformation vibration C-H of aliphatic CH3. A second strong peak at 1445 cm -1 thatinterferes with the first one in the zone between 1400 and 1600 cm -1 is assigned to the deformation vibration C-H of -(CH2) n-. And finally, the smaller peak at 1305 cm -1 corresponds to the CH2 vibration of CH2-S-and to the C-C skeletal vibrations of -(CH2) n-.

Figure 2 .

 2 Figure 2.2.2.13: (a) Horizontal cut of the near field distribution and field enhancement for a nanoring. The scale bar shows the field enhancement. (b) Vertical cross section of the same nanoring for y =0 nm. The polarization vector is indicated by arrows and the incident light is propagating downwards in (b).6

Part 2 : 3

 23 Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 3: Drying-mediated assembly structures of binary solutions of (NPs/biopolymer) mixtures 130 Chapter Drying-mediated assembly structures of binary solutions of (NPs/biopolymer) mixtures 2.3.0. Introduction Throughout nanoresearch fields, different techniques were developed for the design and the fabrication of structured materials, and particularly to organize NPs in 1, 2 and 3 D

  23 DNA can be found in the nucleus of every human cell. It determines all of the physical characteristics through genes. The monomers of DNA are called nucleotides. Each nucleotide consists of a 5-carbon sugar (deoxyribose), a base (either a purine or a pyramidine), and a phosphate. There are four bases: Adenine, Thymine, Cytosine, and Guanine [figure 2.3.0.1, referred as A, T, C and G].

Figure 2 .

 2 Figure 2.3.0.1: DNA structure.23

Figure 2 . 3 .0. 2 :

 232 Figure 2.3.0.2: Chair structure of the Mannuronic and Guluronic acid units constitutive of alginic acid. G: Guluronic and M: Mannuronic acid block.

Part 2 :

 2 Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 3: Drying-mediated assembly structures of binary solutions of (NPs/biopolymer) mixtures 138

Table 2 . 3 . 1 . 1 :

 2311 3.1.1]. The binary solutions of (NH3 + )-stabilized NPs and alginate were also prepared from the centrifuged SA stock solution by mixing 1v of SA1 with 100 v, and 1000 v of NPs solutions ("asprepared" and "dialyzed"), to obtain mixed solutions of nominal SA1 concentrations equal to those of the pure SA solutions at dilute concentrations (10 -6 and 10 -7 M). The drying patterns of the binary solutions can be compared with the reference patterns produced by the pure SA1 solutions of equivalent concentrations, on the one hand, and to those produced by the NPs solutions on the other hand. Physicochemical characteristics of a) the amine-stabilized gold NPs [(NH3 + )-stabilized NPs], and b) the pure the sodium alginate (SA) solutions and (SA/NPs) binary system (at different concentrations). Part 2: Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 3: Drying-mediated assembly structures of binary solutions of (NPs/biopolymer) mixtures 139

  of the single-(references) and the bi-component (SA/NPs) solutions, the conditions and the phenomenology of the occurrence of the drying patterns, their morphology as well as their composition. The formation of highly ramified fibril-like aggregation patterns assisted by the drop evaporation has also allowed the directed fabrication of nanocomposite microfibrils using the capillary suction of the mixed solution into patterned microgrooves. Finally, the induced nanoscopic structures prepared with ultra-low concentration of SA and particles were characterized by AFM in the aim to visualize individual component separately and to better understand the mesoscale and molecular structures of the (SA/residual ions/NPs) complexes.a. Structural characterisation of samplesThe main morphological features of the single-and bi-component solutions are captured with TEM. The images of a dried drop of the respective solution deposited on a TEM grid are shown in figure 2.3.2.1. Interestingly, the mixed solutions of SA1/asprepared NPs [figure 2.3.2.1c] reveal the presence of small NPs (~2 nm) which remain entrapped within the residual web-like network of the dried mixed-solution, compared to the dried solution of the as-prepared 25 nm NPs suspension. The concentration of these smaller particles appears to be much lower on the TEM image of the as-prepared NPs solution [figure 2.3.2.1a], although they were present at the same concentration in the dried drop. A possible hyspothesis explaining this difference might arise from the drying process. For the as-prepared NPs drop, most of these small NPs are sucked along the TEM grid "corners" or under larger 25 nm NPs where they are stuck, and thus hidden and less accessible during the imagery. This structural information is further supported by the characterization of a mixed solution of SA1/"dialyzed" NPs [figure 2.3.2.1d] after 3 days of dialysis through 30 Å membranes. Indeed, most of the small (~2 nm) NPs of a as-prepared NPs suspension have been extracted by dialysis, leading to TEM images which essentially show monodisperse 25 nm particles as displayed in figure 2.3.2.1a. However, these two figures [figures 2.3.2.1a and d] display clear distinctive features concerning the NPs aggregation morphology. Whereas the SA1/as-prepared NPs features are composed of NPs which are connected in chainlike, and more or less branched aggregates which suggest the presence of particles/particles "connecting" agent (SA1 chains), the as-prepared NPs solutions are mainly made of single or finite-size cluster [figure 2.3.2.1a]. Finally, the image in figure 2.3.2.1b which shows the dried single-component (pure) SA1 solution at 10 -6 M nominal concentration, is in good agrement with literature as it is highly reminiscent of TEM images of freestanding polymer-and biomolecule-based nanomembranes. 52

Figure 2 . 3 . 2 . 1 :

 2321 Figure 2.3.2.1: TEM images of a) the as-prepared (NH3 + )-stabilized NPs solution, b) the pure SA1 solution of 10 -6 M nominal concentration, and of the mixed solutions of c) (10 -6 M SA1/as-prepared NPs) and d) (10 -6 M SA1/dialyzed NPs) solutions, as observed from the dried drops on TEM grids.

b. The surface microscopic complex aggregation patterns b. 1 .

 1 figure 2.3.2.2a-f. As discussed in the first chapter of part 2, the as-prepared NPs solutions

  5x10 -4 mM for NaBH4 in the reference solution. As compared to pure 10 -6 M SA1 solutions [figure 2.3.2.2e-f], the drying of this reference drop [figure 2.3.2.2g-i] shows some distinctive features. The final drying spot that is confined within an area of ~400 m large, is mainly formed of thick dendrite structures that are reminiscent of rosette-like dandelion greens.

Figure 2 . 3 . 2 . 2 :

 2322 Figure 2.3.2.2: Optical microscopy images of the drying areas and structures of single-component, NPs and SA solution drops: a-b) as-prepared NPs solution, c-d) dialyzed NPs solution, e-f) 10 -6 M SA solution showing, respectively, the outer region (e) and the final spot (f) of the drying area. The images g)-h) and i) are intended to show the reference drying patterns of a mixed solution of SA and NaBH4, the reducing salt entering the preparation of the NH3 + stabilized Au NPs, and which remains as a synthesis residue in all the as-prepared solutions, the pure NPs as in a-b), and the (SA/NPs) mixtures, as we will see in the following: g) represents the outer region of the drying area, and f) and i) the final spot and associated drying structures.

Figure 2 . 3 . 2 . 3 :

 2323 Figure 2.3.2.3: Characteristic features, as seen by optical microscopy, of the drying patterns of (SA1/asprepared NPs) mixture drops, for nominal concentrations of SA1 of, a-b) 10 -6 M and, c-d-e)10 -7 M: a-b) represent the final drying spot where the highly ramified fibrillar pattern almost exclusively form at SA1 concentration of 10 -6 M, c-d) represent the border of the drying area where the ramified fibrillar pattern appears at the lower SA1 concentration of 10 -7 M, leaving in panel e) the centre of the drying area, either depleted or covered by a few aggregates.

Figure 2 . 3 . 2 . 4 :

 2324 Figure 2.3.2.4: Drying of the mixed (SA/Dialysed-NPs) solution drops, characterized by either the absence of structure (SA concentration of 10 -7 M /panel A), or by the formation of low amount of small dendrite aggregates in the final spot (SA concentration of 10 -6 M / panel B).

Figure 2 . 3 . 2 .

 232 Figure 2.3.2.3 shows large size dendrite patterns that often comprise a single [figure 2.3.2.3a] or only a few fourfold dendrite aggregates (as shown later in figure 2.3.2.14). Interestingly, these dendrites are also characterized by a rather unusual and virtually infinite branching density [figure 2.3.2.3a], with all secondary branches growing parallel to each other [figure 2.3.2.3a-b, figure 2.3.2.14c-e], with nearly an angle of /2 with respect to their "root-branches". Furthermore, the pattern of figure 2.3.2.3a-b has the distinctive feature of being composed of short cylinder-shaped domains (segments) that result from the high growth density of secondary structure, and the merging of the lastorder growing branches in the increasingly confined space [figure 2.3.2.5].

Figure 2 . 3 . 2 . 5 :

 2325 Figure 2.3.2.5: Schematic sketch showing the nucleation of fourfold fractal aggregate, the highly ordered growth of secondary branches, and the merging of the last-order growing branches in the confined space.

Figure 2 . 3 . 2 . 6 :

 2326 Figure 2.3.2.6: Dynamic images of drying drop of (SA1 @ 10 -6 M/ as prepared NPs), showing the nucleation and the growth of high symmetrical ramified dendrite patterns (growth kinetics).

Figure 2 . 3 . 2 .Figure 2 . 3 . 2 . 7 :

 2322327 Figure 2.3.2.7a shows the graph corresponding to the growth kinetics of the ramified complex pattern. We present the variations of the occupied area by the dendrite branches Ad [figure 2.3.2.7b], normalised to the total area occupied by the whole pattern, AT, vs. time (t).

  in their relative orientation and in their orientation with respect to "root-branches". This is possibly due to the location of the structures as well as their high density, which result for the stronger shear deformation and orientational hindrance experienced by the branches during the depining and receding of the drop [figure 2.3.2.8]. The final drying area of the low SA1 concentration mixture [10 -7 M SA1/as-prepared NPs] coincides with the initial contact area of the drop. The first stage of the evaporation corresponds to a drying at constant area due to the pinning of the drop. This pinning stage is then followed by a brutal depinning of the residual film [figure 2.3.2.8.b and 2.3.2.9.b]. On the other hand, the drying of the higher SA1 concentration mixtures (10 -6 a b and 10 -5 M) shows a quite axi-symmetrical receding of the drop after a short time interval of pinning, accompanied by a certain "stick-slip" motion of receding contact line [figure 2.3.2.8.a and 2.3.2.9.a].

Figure 2 . 3 . 2 . 8 :

 2328 Figure 2.3.2.8: Drying dynamic drop of a) 10 -6 M SA1/as prepared amine coated NPs, and b) 10 -7 M SA1/ as prepared amine coated NPs. Contact angle and contact diameter, vs. time.

Figure 2 . 3 . 2 . 9 :

 2329 Figure 2.3.2.9: Sketch of two "evaporation/drying" regimes of sessile suspension droplets, and their associated localizations of the drying structures under partial wetting conditions: a) Depinning/recedingdominated evaporation/drying regime. Here, the evaporation leads to the 'early' depinning and receding of the drop, which now collects during its inward motion (shear-drainage) all the solutes that are loosely attached to the substrate. These solutes are then accumulated inside the final drying spot where the structures (when they form) appear essentially. b) Pinning-dominated evaporation/drying regime. Here, the drying results in an accumulation of solutes along the drop border, either due to a complete pinning or a pinning for a finite but sufficient time for evaporation-gradient to drive the outward particle transport. In the final stage, the residual fluid may either detach from the peripheral accumulated particles and recede, or dry homogeneously in its depleted central part, or dewet through heterogeneous nucleation (most probable).

eq 2 . 3 . 2 . 2

 2322 This represents the driving force for fluid outward flow, and related transport of particles, and their accumulation at the periphery of the drop. In this process of particles transport, the viscosity of the fluid η and the size of the particles for a given particle velocity v are the limiting factors, according to the Stokes law, Fd = -3πdηv, eq 3.3.2.3

- 6 M 2 . 3 . 2 . 8 .

 62328 SA/NPs solution, as shown in equation 4 for solution of individual solutes size (NPs, ions), u = (v/ Fd) ~1/ η eq 2.3.2.4In the late stage of the evaporation and as result of the less amount of peripheral particle aggregates, a depinning of the high SA1 concentration drop appears earlier ( within 13 minutes) than for the low SA1 concentration drop (after 23 minutes), as shown in figure On the contrary, the long pinning time of the low SA1 concentration drop generates an intense accumulation of particles at its periphery until the residual film breaks at its periphery, leading to the abrupt receding motion. Consequently, the receding contact angle θr of this residual film is lower than the one of the high SA1 concentration drop. At the opposite, the instantaneous velocity U of the abrupt contact line retraction Δr over the short timescale Δt between depinning and re-arrest is higher and of the order of U ~ 3.28x10 -1 m.s -1 for the low SA1 concentration, against an average receding velocity U ~ 5.93x10 -6 m.s -1 for the high SA1 concentration drop. Finally, the force (per unit length) experienced by the "NP/SA chains" complexes during the receding in the wedge can be expressed at first order as: 46 F UL/ r eq 2.3.2.5 where is the viscosity, U the instantaneous velocity and L a logarithmic factor of the order of 10 defined by L= ln[ (w/a)], where w is the lateral size of the wedge and a, a cut-off length which is of molecular size. This higher frictional force generated in the low SA1 concentration suspension, contributes through shear-induced alignment and structuration to the genesis of the complex structures at the periphery of the drop. The absence of structure in the middle of the drop can be explained by a depletion of NPs and residual ions in this area, although these NPs and residual ions reappear at higher concentration in the final spot, due to their drainage and accumulation in tiny area by the receding motion.

Figure 2 . 3 . 2 .

 232 Figure 2.3.2.10 shows EDX spectra on the structures in the final drying spot of SA1 at 10 - 6 M/ dialyzed NPs, and SA1 at 10 -6 M/ as-prepared NPs solutions. We can observe the presence of carbon (C), oxygen (O) (of SA) and gold (Au) for the dialyzed solution.

Figure 2 . 3 . 2 . 10 :

 23210 Figure 2.3.2.10: EDX spectra of the complex drying patterns of a) SA1 at 10 -6 M/ dialyzed NPs and, b) SA1 at 10 - 6 M/ as-prepared NPs solutions.

Figure 2 . 3 . 2 . 11 :

 23211 Figure 2.3.2.11: Raman spectrum realized on the complex structures obtained in the final drying spot of SA1 at 10 -6 M/ as-prepared NPs solution.

  figure 2.3.2.12 a Raman mapping of an area of the final drying spot containing structures. This Raman mapping is based on a local surface analysis realized point by point [figure 5.2.11a] on a chosen area on the surface. This mapping corresponds to the variation of intensity of one specific peak. Here, we have chosen the peak at 1480 cm -1 coresponding to the vibration of the end-group (NH3 + ) of the thiol molecule grafted onto Au NPs, or to the vibration of the (Au/SA) bond (NH3 + / COO -) (peak c in figure 2.3.2.11). This peak should have no specific contribution from the single SA chains and should reveal the presence of Au NPs [figure 2.3.2.10].

Figure 2 .

 2 Figure 2.3.2.12: a) Zoom out of a cliché of b) the analysed surface (optical image) corresponding point by point to the Raman mapping area. c) Raman mapping of the structures in the final spot exhibiting the variation of intensity of the peak (c) of the raman spectrum observed in figure 2.3.2.11.

Figure 2 . 3 . 2 .

 232 13 presents the evolution of the intensity of the peak (c) at different positions in the residual drying spot. The plotted results correspond to the averaged values measured at the different positions indicated in figure 2.3.2.12a.

Figure 2 . 3 . 2 .Part 2 :

 2322 Figure 2.3.2.13: a) Locations of the points where the intensity of the Raman peak c was measured, b) evolution of the intensity of Raman peak c (figure 2.3.2.11), at different positions inside the residual drying spot.

2. 3 . 2 .

 32 14 shows the structures emerging in the drying spot of SA @ 10 -6 M/ dialyzed NPs solution to which 0.06 M of NaCl was added. The concentration of NaCl was chosen to achieve the conductivity of 2 mS/cm, which is the equivalent conductivity of the SA1/ asprepared NPs solution.

Figure 2 . 3 . 2 . 14 :

 23214 Figure 2.3.2.14: Structures induced in the final drying spot of (SA1 @ 10 -6 M/dialyzed NPs + 0.06 M of NaCl) solutions.

2 .

 2 The larger 25 nm NPs mixtures drops display a different drying behavior. Here, the drops that are pinned only transiently proceeds through a receding motion which collects the solutes towards the final drying spot, where well-defined dendrites aggregates with much coarser branches are formed [figure 2.3.2.15c-f], compared to the dendrites issued from the 2 nm NPs [figure 2.3.2.15a, border].

Figure 2 . 3 . 2 . 15 :

 23215 Figure 2.3.2.15: NP size dependence of the drying patterns of mixed (SA1/as-prepared NPs) solution drops of identical SA1 concentration. In a-b), and the corresponding inset, the solution of 10 -6 M SA contains NPs of 2 nm, and the drying areas shown correspond to the border (a) and the centre (b) of the drop. In c-d), the solution of 10 -6 M SA1 contains NPs of 25 nm, and the structures form only in the final central drying spot. In ef), the solution contains NPs of 25 nm, with a higher SA1 concentration (10 -5 M), and the coarser fibrillar structures form only in the final drying spot.

(

  SA chains) in the drying drop, and thus in the final drying spot after the drainage of solutes by the receding drying drop. Furthermore, unlike single-component SA solution for which the increased flexibility of the chains upon counter-ions condensation was shown to increase their conformational accommodation [figure 2.3.2.16a], favoring their assembly, packing and ordering, 46 one may expect a priori the formation of (SA/NPs) complexes in the mixtures to increase the "chain" stiffness and thus impede their assembly, packing and ordering. But interestingly, our results rather show the opposite [figure 2.3.2.3a-to-d, and figure 2.3.2.15e-f].

Figure 2 . 3 . 2 . 16 :

 23216 Figure 2.3.2.16: Suggested schema of a) totally flexible SA chains presenting counter ions condensation along the chain, b) totally rigid complexe (NPs/SA) chain for a high (NPs/SA monomers) ratio, c) relatively rigid complexe (NPs/SA) chain for a low (NPs/SA monomers) ratio, d) totally rigid complexe NPs/SA chain for a high (NPs/SA monomers) ratio, when using relatively small NPs (2 nm) and e) quasi flexible complexe NPs/SA chain for a low (NPs/SA monomers) ratio, when using relatively small NPs (2 nm).

  based on the capillary suction through microscale groove template. The following paragraph describes these studies.

Figure 2 . 3 . 2 . 17 :

 23217 Figure 2.3.2.17: Microfabrication steps of the composite (SA/NPs) hydrogel microfibers showing in a), the capillary filling of the microgrooved PDMS support, in b) the optical microscopy images of the lifted microfibers, and in c) the TEM images showing embedded NPs. In a), the peaks of the grooves are the clear lines (3 µm large) that are separated by dark bands corresponding to the grooves width (6 µm), with a peakto-valley depth of 6 µm. The thick lines inside the grooves are (SA/NPs) fluid segments that have been, or are being sucked. The real-time growth of a fluid segment was captured in the circled zones (arrows). In c), the TEM images show two fibrils, one with no significant damage (c1), and the other with drastic dehydrationinduced morphological damage during TEM conditioning (c2).

Figure 2 . 3 . 2 .

 232 Figure 2.3.2.18 presents AFM images of dried suspension of dialyzed amine stabilized NPs solution on SiO2 substrate under ambient conditions (22 °c, 33 % RH). These AFM images in Tapping mode represent the references images for single NPs solution drying and aggregation morphology.

Figure 2 . 3 . 2 . 18 :

 23218 Figure 2.3.2.18: AFM phase images of dialyzed suspension of gold NPs deposited onto Silica surface Frame sizes: a) 323 nm and b) 183 nm.

Figure 2 . 3 . 2 . 19 :

 23219 Figure 2.3.2.19: AFM phase image of dried a) reference SA1 (10 -7 M) and, b) and c) binary SA1 (10 -7 M)/dialyzed NH3 + stabilized NPs, at middle distance between the edge of the drop and the final drying spot. Frame sizes: a) and b) 1µm and c) 500 nm.

Figure 2 . 3 . 2 .

 232 Figure 2.3.2.20 shows AFM and EFM images of reference SA2 of nominal concentration of 10 -7 M. Of particular interest, these images reveal the presence of segment-, cylindershape structures [figure 2.3.2.20a] located on the top of an interconnected sub-structure [figure 2.3.2.20c], which is similar to the one observed for the SA of smaller chain length (SA1). The EFM images [figure 2.3.2.20b-d] do not show any contrast, contrary to AFM images, indicating a too low electrostatic interactions between the conductive tip and the pure SA surface structures, and dearly attesting for the organic nature of the segmental structures of figure 2.3.2.20a.

Figure 2 . 3 . 2 . 20 :Figure 2 . 3 . 2 .

 23220232 Figure 2.3.2.20: AFM and corresponding EFM phase images of dried SA2 of nominal concentration of 10 -7 M. a) AFM phase image of the fibrillar structure, and b) corresponding EFM phase image of a). c) AFM phase image of the interconnected sub-structure, and d) corresponding EFM phase image of c).

Figure 2 . 3 . 2 . 21 :

 23221 Figure 2.3.2.21: AFM and EFM images of the drying structures of binary (SA2 at 10 -7 M/ NPs) solution drops. a), b) and c) AFM phase image of the segmental aggregates of (SA chains/NPs) complexes and, d) corresponding EFM phase image of c). e) and f) AFM phase image of the interconnected sub-structure of the binary system and, g) corresponding EFM phase image of f).

  from both the intrinsic chain backbone rigidity Lb and the electrostatic persistence length Le, Lp= Lb+ Le. The latter arising from the repulsion of the polyion charges is related to the ions concentration Cion, given at first order by Le~(LB/Cion) where LB is the Bjerrum length. As a result Le, and thus Lp decreases at higher ions condensations allowing higher chain flexibility. The condensation of counterions along the biopolymer chain thus allows additional conformational fluctuations generating new possible interconnection with other chains to form aggregates [figure 2.3.2.22]. These phenomena thus depend on the chain length as well as on the strength of the charge interacting with the chain regarding to his length. Hence, longer chains (SA2 comparing to SA1) can create globular aggregates [figure 2.3.2.20a/ SA2] in addition to the surface interconnected aggregation structures [figure 2.3.2.19a/ SA1]. As also expected from the ions concentration in the solutions, we observe a regular increase in the size and the compactness of the aggregate with ions concentrations [figure 2.3.2.2f/low ions concentration and 2.3.2.2h/high ions concentration]. Indeed, the condensation of Na + counterions strongly lowers the electrostatic inter-chains repulsion, making predominant the attractive VdW force between chains. In concentrated chains (late stage of drying, final spot), this attractive VdW force drives the self-assembly of the SA chains into interconnected aggregations structures [figure 2.3.2.22].

Figure 2 . 3 . 2 .

 232 Figure 2.3.2.22: a) and a') AFM phase images of aggregation structures formed by drying SA2 solution drops and, b) sketch of SA chains in the solution containing salt cations.

3. 1 . 1 .

 11 Aging of complex structures induced by drying of colloidal NPs sessile drop Most works dealing with the stability and structures reconstruction concerns metallic thin films. This research activity mainly focuses on the way to create and control the film morphologies arising from these instabilitties. For instance, combined meltingdewetting-reorganisation, either by plasma, ion-or laser beam bombardment are used to pattern metallic nanostructures. Dewetting of Co films under energetic ion-beam bombardment and Rayleigh instability enabled creation of templates of controlled morphology (size and shape).

  Figure 3.1.1.1 displays a "phase" diagram of the images depicting the progression of the aging alteration for dendrites structures formed by 25 nm NPs, vs. the time, and the relative humidity.

Figure 3 . 1 . 1 . 1 :

 3111 Figure 3.1.1.1: Diagram of the aging of the complex patterns, vs. time and relative humidity, for the 25 nm NPs complex patterns.

Figure 3 . 1 . 1 . 2 :

 3112 Figure 3.1.1.2: Diagram of the aging of the complex patterns vs. time and RH, for the 15 nm NPs complex patterns.

Finally, Figure 3

 3 .1.1.3 shows the "phase" diagram of the images depicting the progression of the aging alteration for dendrite structures formed by 3nm NPs, vs. the time RH.

Figure 3 . 1 . 1 . 3 :of

 3113 Figure 3.1.1.3: Diagram of the aging of the complex patterns, vs. time and RH, for the 3 nm NPs complex patterns.

Figure 3 . 1 . 1 .

 311 Figure 3.1.1.4 represents a "zoom in" on a branch of the complex pattern image whichshows the clusters in the 1D-NPs aggregates are bridged, probably with residual salts and condensed water. Indeed, the branches are not formed of a homogeneous and compact aggregate; they are formed of quasi-discrete NP clusters interconnected with these residue bridges. After several hours of storage in a controlled environmental chamber, the aggregates start to disconnect. As a high relative humidity (above 11%) favors the disassembly of the cluster units constituting the aggregate ramification, one can assume that the condensed water film at the surface will play a role in the lubrication during the aggregates migration.

Figure 3 . 1 . 1 . 4 :

 3114 Figure 3.1.1.4: Aging of aggregate branch showing fluctuations and the dislocation into cluster units, vs. time.

Figure 3

 3 Figure 3.1.1.5: a) Plot of the mean square of the migration distance x 2 vs. time t of a cluster taken in the principal branch of a dendrite structure. The squares correspond to the experimental data, and the red line represents the simulated fit. b) Logarithm of x vs. that of t.

Figure 3 . 1 . 1 . 6 :

 3116 Figure 3.1.1.6: Binarized images of the studied cluster migrating from the principal branch of the dendrite structure toward free surrounding place.

  surfaces (clusters and substrate wall) is given by , where µ is the friction coefficient in the contact, Fext the applied external load (cluster weight), and Fadh the intermolecular adhesion force. Obviously, the µ determined under the action of the sole intermolecular adhesive forces may differ, more or less, from that determined under the combined effect of Fext+Fadh above a certain value of external force Fext.

Figure 3 .

 3 Figure 3.1.2.1 displays the evolution of (SA/NPs) branches of a ramified structure. In particular, the degeneration of the structure starts with the emergence of instabilities

Figure 3 . 1 . 2 . 1 :

 3121 Figure 3.1.2.1: Complex aggregation patterns obtained after drying a bi-component (SA/NPs) mixture. a) At their initial state, and b) after 1 day (fluctuations along the branches). c) Representative scheme of Rayleigh instabilities for a cylinder struture.

  The degenerating structure of this branch can then be envisaged as a row of droplets of radius b [fig 3.1.2.1c], if the destabilization of the cylinder is driven by a capillary fluctuation of the surface, with a characteristic wavelength λ [figure 3.1.2.1c]. The volume per wavelength of the cylinder equals the volume of each resulting droplet after the breakup of the cylinder. This assumption then leads to say that the droplet radius is:

Figure 3 .

 3 Figure 3.1.2.2 shows the images of a ramified pattern formed in the final drying spot, before, and after addition of CaCl2 solution drop.

Figure 3 . 1 . 2 . 2 :

 3122 Figure 3.1.2.2: Optical Images of the pattern in the final drying spot a,e) before and b,f) after the ddition of CaCl2 solution drop. c,d) AFM images on one branch before and after gelling.

Figure 3 . 1 . 2 . 3 :

 3123 Figure 3.1.2.3: optical microscopy images of the evolution of the patterns of composite (SA/NPs) without gelling stabilization. a) Freshly formed pattern (initial state) and b) after 8 months of storage at 23°C and 33% of RH.

  of NPs-based complex structures formed at solid surfaces was investigated along this chapter, focusing on the role of the environmental parameters (water vapor/ RH) and NP size. The results indicate that a threshold value of relative humidity exists which determines the domain of stability of these aggregation structures. The mechanism underlying the degeneration of the patterns is mainly related to the aggregates surface diffusion. In addition, the stability of the ramified patterns was significantly enhanced by decreasing the size of the Au NPs building units, bringing a clear evidence of size effects in the aging of nanostructured materials.

Chapter 2 AFM

 2 Manipulation of NPs on Model Surfaces-a tentative account of the surface mobility and dislocation of aging NPs structures 3.2.0. Introduction To better understand the NPs mobility evoked in the previous chapter, and the related physical parameters (friction coefficient of the NPs, interactions playing between NPs and their environment), we develop in this chapter an approach based on the manipulation of single NPs using atomic force microscopy. These experiments are aimed at understanding the correlation that might exist between these single NPs manipulation and motion under an AFM tip on a substrate, and the previous NPs cluster mobility in the dislocating aggregates of the complex NP-based structures issued from drying NPs suspension. Nanomanipulation is a complex 3D-problem. Because mechanical and chemical properties of substrates, probing tools and nano-objects (especially 'particles') are combined, different results are expected depending on the environmental and operating conditions.

  and V from Veeco (Bruker), Enviroscope: Nanoscope III from Veeco and Mobile S from Nanosurf). Rectangular silicon cantilevers with resonance frequencies f0 around 120 kHz and 190 kHz, quality factors around 800 and 600, and nominal spring constants of 5 and 48 N/m (respectively, MPP12100 from Veeco and PPP-NCLR from Nanosensors) were used. During manipulation, the oscillation amplitude of the tip, ~ Aset, was kept constant by a feedback loop. In such case, the power dissipation accompanying the tip-sample interaction can be determined using the formula:21

Figure 3 . 2 . 2 . 1 :

 3221 Figure 3.2.2.1: Evolution of the logarithm of the dissipated power normalized by the radius (R) of a) assynthesized spherical Au NPs on bare silicon wafer versus the radius R  experimental data ─ theoretical data corresponding to a pure sliding model of a NP, after the tap of a tip in a typical AFM Tapping mode manipulation as described by Sitti 17, 22, 23 and b) spherical Au NPs on silicon wafer coated with -CH3 terminated groups (hydrophobic coating) versus the radius R  experimental data ─ theoretical data corresponding to a pure rotation model of the NP, after the tap of a tip in a typical AFM Tapping mode manipulation as described by Sitti.

Figure 3 . 2 . 2 . 2 :

 3222 Figure 3.2.2.2: Scheme presenting the different forces interacting between tip/particle and particle/substrate and the angles α and β.

24

 24

  24 A. Rao, E. Gnecco, D. Marchetto, K. Mougin, M. Schoenenberger, S. Valeri, E. Meyer,Nanotechnology, 2009, 20, 115706.

Figure 3 . 2 . 2 . 3 :

 3223 Figure 3.2.2.3: Typical trajectories of bare gold NPs (20 nm diameter) on silicon substrate when the probing tip moves along a zigzag path: a. low drive amplitude, b. high drive amplitude; scan size: 5µm. Slow scan axis: down.

Figure 3 . 2 . 2 . 4 :

 3224 Figure 3.2.2.4: Typical Scan patterns adopted in AFM: a. raster scan path used by Nanosurf b. zigzag scan path used by Veeco. Top view: the grey disk corresponds to the position of the tip on the surface and the yellow, blue and red ones are the positions of spherical particles pushed by the tip along its scan path.

Figure 3 . 2 . 2 . 5 :

 3225 Figure 3.2.2.5: AFM images of nanocluster movement during their manipulation a. gold nanorods deposited onto silicon wafer, scan size: 12µm, b. antimony islands on HOPG, scan size: 1,5µm. c. Au nanotriangles on silicon wafer. Middle triangles have been voluntary colored in violet to precise the trajectory of the Au NPs during manipulation, scan size: 5µm

  of the chemistry of the particles on a flat substrateBecause real surfaces are often heterogeneous in their chemical composition, functionalized NPs provide good model systems to study and tune the mobility of nanoobjects on these substrates.As a next step, the role of the hydrohilicity and hydrophobicity of the the functional grafting on spherical Au NPs is illustrated in figure 3.2.2.6. These series of experiments were performed on a Veeco AFM whose tip follows a zigzag scan path (contrary to a Nanosurf AFM which uses a raster scan path).

Figure 3 .

 3 Figure 3.2.2.6: a. Average power dissipation accompanying the onset of motion of as-synthesized and coated NPs on silicon in air, versus temperature: black column: as-synthesized NPs that are uniformly distributed on the substrate, dark gray column: CH3 coated NPs, light gray column: as-synthesized NPs that are randomly distributed on the substrate. b. Logarithm of the dissipated power in moving as-synthesized and coated NPs on silicon wafer, versus the inverse of temperature for:  as-synthesized NPs,  as-synthesized NPs ordered organized, □ CH3 coated NPs, ▲OH coated NPs.

Figure 3 .

 3 Figure 3.2.2.6 represents a histogram of the raw values of the power dissipation, versus the temperature, for temperatures ranging from 20 to 150 °C. These results clearly showthat the power dissipation involved in the motion decreases with the temperature. This effect appears to be stronger on hydrophilic particles. Intuitively, one could expect this result since the temperature (thermal energy kT) acts as an obstacle in forming stable intermolecular bonds and water bridges between particles and substrate, reducing the adhesion between them. Similar thermal effects have been recognized in friction on hydrophilic surfaces measured with different scan velocities.27 It is worth noting that during this temperature dependent manipulation, no evident damage was observed on working areas.

Figure 3 . 2 . 2 .

 322 Figure 3.2.2.6b corresponds to a logarithm plot of the dissipated power as a function of the inverse of temperature (1/T). These experimental data display a good linear fit (r² >0.90) for all NPs/substrate couples, except for as-synthesized NPs for which r² is ~0.78. This linear behavior of [log (dissipated power)], versus (1/T), actually corresponds to an

Figure 3 . 2 . 2 . 7 :

 3227 Figure 3.2.2.7: AFM images of 25 nm diameter gold NPs deposited onto a silicon wafer. (a) Ordered organization as described in the text, (b) Random distribution. Frame sizes: 3 µm and 1µm respectively.

(

  10 to 90% at 25 °C). These models are referred to as: hydrophilic NPs (citrate coated) on partially hydrophilic substrate (model 1), hydrophilic NPs on hydrophobic substrate (model 2) and hydrophobic NPs (CH3-coated) on partially hydrophilic substrate (model 3). 29 J. Israelachvili, Intermolecular & Surface Forces, Academic Press, San Diego, CA, 1992.

e. 1 .

 1 Model 1(hydrophilic NP/partially hydrophilic substrate) The results of the model 1 are displayed in figure 3.2.2.8. The graph presents the threshold energy dissipation (eV) of the Tapping tip to move the NP, vs. the RH.

Figure 3 . 2 . 2 . 8 :

 3228 Figure 3.2.2.8: Evolution of the threshold energy dissipation (eV) to move citrate coated NPs (hydrophilic) on SiO2 (partially hydrophilic), vs. the relative humidity. At 2 % of RH the pressure was 10 mbar, and this state represents the reference of "quasi-dry" environment for the motion of the NPs on the substrate.

Figure 3 .

 3 Figure 3.2.2.8 shows the evolution of the threshold energy to move hydrophilic NPs onpartially hydrophilic substrates. At 2% of RH the air pressure was 10 mbar. This point is considered as the reference value of energy to move NPs with the lowest contribution of water vapor or air for this serie of measurements ("quasi-dry" atmosphere). The graph shows an increase of the dissipated energy to move NPs with the relative humidity. That increase of the dissipated energy already seems to indicate that a part at least of this energy might be dissipated in the condensed water film (bridges) that are formed between both interfaces: (surface/NP), and (tip/NP).

  and referred to as E0 [figure3.2.2.9a]. Increasing the relative humidity to 10 % (and the pressure to 10 3 mbar), also leads to an increase of the energy dissipation. Going from 10 % to 40 % of RH, the energy dissipation increases only slightly. The energy dissipations to move the particle are now E1(10), E1(20) and E1 (40). The subtraction between E1 and E0 corresponds to the additional dissipated energy in the condensed water layers of different possible configurations and thicknesses, going from 10 to 40 % of RH. We will consider E1 as the energy to move NPs in the presence of water layers [figure 3.2.2.9b], or more simply in water at the substrate surface. If we increase the RH to 80 %, a much larger increase of the energy dissipation to move NPs is required. Indeed, at 80 % of RH, the NPs are immersed in the condensed water film. The energy to move NPs is now E2, and the subtraction between this energy and the reference energy E0 is considered (approx) as the sum of the energy to move NPs in the presence of water layers E1 (40), and the dissipated energy of the tip in the water film Ex [figure 3.2.2.9c].

Figure 3 . 2 . 2 . 9 :

 3229 Figure 3.2.2.9: Schemes of the system configuration (hydrophilic particle/ partially hydrophilic substrate/ partially hydrophilic tip), at different RH values. a) RH of (2 % /P=10 mbar), b) RH of (10 to 40 % /P= 10 3 mbar) and c) RH of (80 % /P= 10 3 mbar).

Figure 3 . 2 . 2 . 10 :

 32210 Figure 3.2.2.10: Evolution of the threshold energy dissipation (eV) to move citrate coated NPs (hydrophilic) on silicon wafer coated with -CH3 terminated groups (hydrophobic coating) vs. the relative humidity of the manipulation chamber.

Figure 3 . 2 . 2 . 11 :

 32211 Figure 3.2.2.11: Schemes of the system configuration (hydrophilic particle/ hydrophobic substrate/ partially hydrophilic tip), at different RH values. a) RH of (2 %/P=10 mbar), b) RH of (10 to 80 %/P= 10 3 mbar) and c) AFM phase image in Tapping mode, during the manipulation of NP; the black line corresponds to the trajectory of the NP (slow scan axis down).

e. 3 .

 3 Model 3(hydrophobic NP/partially hydrophilic substrate)The results of the model 3 are displayed in figure3.2.2.12. The graph still presents the threshold energy dissipation (eV) of the Tapping tip to move the NP, vs. the RH.

Figure 3 . 2 . 2 . 12 :

 32212 Figure 3.2.2.12: Evolution of the threshold energy dissipation (eV) to move CH3-coated NPs (hydrophobic) on silicon wafer (partially hydrophilic), vs. relative humidity.

Figure 3 . 2 . 2 . 13 :

 32213 Figure 3.2.2.13: Schemes of the system configuration (hydrophobic particle/ partially hydrophilic substrate/ partially hydrophilic tip), at different RH values. a) RH of (2 % /P=10 mbar), b) RH of (10 to 40 %/P= 10 3 mbar) and c) RH of (80 % /P= 10 3 mbar).

Figure 3 . 2 . 2 . 14 :

 32214 Figure 3.2.2.14: AFM image of nanopatterned surface presenting some Si-pits: frame size: 3µm.

  Manipulation experiments were repeated to check the influence of the deep grooves (either Si wafer or HOPG) on the trajectory of the moving particles. It was found that the deep grooves slightly influence the direction of the particles movement as particles tend to follow their preferential angle during movement.

Figure 3 . 2 . 2 . 15 :

 32215 Figure 3.2.2.15: Manipulation of as-synthsized Au NPs on a.a flat silicon wafer with a spacing of 9.7nm, b. a nanopatterned one with a spacing 16nm and c. a patterned with a spacing of 3.9nm.

Figure 3 . 2 . 2 . 16 :

 32216 Figure 3.2.2.16 : Logarithm of the dissipated power in moving as-synthesized NPs on silicon wafer, versus the tip scan speed on  SiO2 silicon wafer  NH2 amine coated silicon wafer (hydrophilic substrate)  CH3 methyl coated silicon wafer (hydrophobic substrate). a. 35nm diameter gold NPs, b. 60nm diameter gold NPs.

  mediated assembly in either original or functional mesoscale aggregation patterns, on model solid substrates. The maion objective of this work was to unserstand the mechanism and describe the key parameters controlling the morphogenesis of such drying structures and patterns from NPs-based complex fluids.Besides the formation of these structures from both single component NPs, and mixed binary (NP/biopolymer) solutions, their aging and disaggregation mechanism was investigated, highlighting the size effect of the NPs building units on the cohesion and stability of these structures. Finally, we have shown that the above fundamental studies and understanding could be usefully tuned toward the fabrication of effective wettingand drying-mediated nanostructures (nanorings) and nanomaterials ("NPs/sodium alginate" hydrogel microfibers). The following summarizes briefly the main steps of this work, highlighting the corpus issues that have been addressed and the significant findings.The first part of this thesis has focused on the synthesis of nanomaterials such as gold colloidal nanoparticles and self-assembled homogenaous and heterogeneous monolayers. First, spherical Au NPs were synthesized from few nanometers up one hundred nanometers diameters. The precise control of operating conditions such as temperature, nature and amount of surfactants or reducing agent, has allowed to tune accurately the Au NPs chemical and structural parameters. Asymmetrical Au NPs such as elongated ones (rods) have also been synthesized using a seed mediated approach to provide rods with aspect ratios varying from 2 to 15. Nevertheless, the stability of the whole NPs suspensions strongly depends on the functionalization of the NPs and the solvent medium. The studied spherical nanoparticles were either coated and stabilized with amine, citrate or methyl terminiated functional molecules. The control of the structural and chemical modification of Au NPs have a strong impact on the character and performance of NPs assembly. Finally, the morphological and crystallographic parameters of Au NPs as well as NPs suspension stability have been carried out by TEM and UV-VIS spectroscopy measurements. Secondly, we focused on the elaboration of either homogeneous or heterogenous self-assembled organosilanes monolayers on oxidized silicon substrate, as model substrates for the drying and the adsorbion of NPs. These surfaces were characterized by contact angle measurements and ellipsometry to verify their chemical properties (hydrophobic or hydrophilic) as well as their compactness of the molecualr film. Then, microheterogeneous molecular binary surfaces presenting geometrical controlled domains distribution were realized by microprinting techniques. These nanopatterned surfaces have provided a model system (such like a controlled and tunable playground) to study the organization of Au NPs toward a better understanding of the interplay between 2-D nanostructuration and the control of interfacial phenomena.

  understanding and confirming the major experimental findings of this Ph-D work.Moreover, beyond these specific investigations, the size-scaling effect might represent a more universal criterion, which accounts for the influence of nanoscale effects in aggregation phenomena at specific surfaces. In this sense, these results may also provide a new picture toward the complete understanding of the 2-D self-organization and complex pattern formation in both living and nonliving systems, as they open an attractive route for the controlled growth of 2-D networks for nanophysics and biology. For instance, the co-encapsulation of metal NPs and oxidase within gel matrix (alginate, chitosan) should provide a simple route for the fabrication of optical biosensor. In all these NPs-based assemblies, if we exchanged Au NPs with Co or Ni ones, each of aggregation structures, may serve as a potential model in studying the dependence of the electromagnetic properties of an object (1-, 2-or 3-D network) on its intrinsic topological feature. To conclude, the development of a new generation of thin coating based on (NPs/polyme)r nanocomposites will open potential and specific optical, biological, regenerative medecine, and sensing applications related to nano-objects. A4 combination of two alternating and distinct interactions. Basically, an electrostatic interaction was used to bind the charge stabilized (citrates) colloidal gold NPs, to the terminal amine of an alkylthiol linker. The second binding is a covalent one (Au/S) that attaches the second layer of Au particles to the terminal sulfur (S) of the alkylthiol linker, as shown on Figure 1.

Figure 1 :Figure 2 :

 12 Figure 1: Schematic representation of the combined electrostatic-covalent layer-by-layer (LbL) formation of gold NPs multilayers (relative size of linker and NPs are not at scale).

Figure 3

 3 Figure 3 presents the organization of NPs, layer after layer on the same sample (step by step adsorption) for both particle sizes, 15 and 5 nm.

Figure 3 :

 3 Figure 3: AFM pictures in Tapping Mode of the last NPs layer at the different (successive) steps of the formation of the complete multilayer structure on the substrate. From a to c, the images correspond to the 15 nm sized NPs, and from d to f, to the 5 nm NPs. 15 nm NPs: a. first layer, b. second layer, c. fourth layer; the scale is (1x1 µm), a zoom in. AFM phase contrast image of a zoom in of the 2D-assembly of the NPs; the scale is (500x500 nm). 5 nm NPs: d. first layer, e. second layer, f. fourth layer; the scale is (1x1 µm), d zoom in. AFM phase contrast image of a zoom in of the 2D-assembly of the NPs.

Figure 4 :

 4 Figure 4: AFM pictures in Tapping Mode of the fourth layer of the multilayer structure before and after sonication in water for 20 minutes. a and b correspond to the AFM images of the 15 nm sized nanopoarticles, and c and d, to the 5 nm Au NPs. 15 nm Au NPs: a. before sonication (1x1 µm), b. after sonication (5x5 µm). 5 nm Au NPs: c. before sonication (1x1 µm), d. after sonication (1x1 µm).

Figure 5 :

 5 Figure 5: a.SERS spectra of 15 nm Au NPs multilayer structure and thermally evaporated Au film: 1.(blue curve) a standard Au thermally evaporated film of 30nm, 2. (violet curve) one monolayer of gold NPs deposited onto a SAMs coated silicon wafer, 3. (red curve) three layers of NPs hybrid architecture 4. (dark green curve) five layers of NPs hybrid architecture. b. SERS spectra of 5nm Au NPs multilayer structure: 1.(green curve), one monolayer of gold NPs deposited onto a SAMs coated silicon wafer, 2. (violet curve) two layers of NPs hybrid architecture 3. (blue curve) three layers of NPs hybrid architecture 4. (orange curve) four layers of NPs hybrid architecture.

Figure 6 :

 6 Figure 6: SERS spectra of Methylene Blue adsorbed on a 15 nm sized NPs multilayer structure and a thermally evaporated Au film; A. (violet curve) thermally evaporated Au film, B. (green curve) five layers of gold NPs multilayer architecture.

Figure 7 :

 7 Figure 7: a. Zoom in on the main MB peak at 1623cm -1 of Methylene Blue adsorbed on a 15nm diameter NPs multilayer structure and Au thermal evaporated film obtained by SERS: a. (blue curve) Au evaporated thermally evaporated film, B. (violet curve) three layers of NPs hybrid architecture C. (black curve) five layers of gold NPs hybrid architecture. b. Evolution of the intensity of the main MB peak at 1623 cm -1 of Methylene Blue adsorbed NPs multilayer structure vs the number of layers.

Figure 8 :

 8 Figure 8: Representative scheme of A. 5 layers of 5 nm diameter Au gold NPs, B. 2 layers of 15 nm diameters gold NPs (relative size of linker and NPs are not at scale).

Figure 9 :

 9 Figure 9: SERS spectra of Methylene Blue adsorbed 15 nm and 5 nm sized Au NPs multilayer structure A. (black curve) 3 layers of 5 nm sized gold NPs hybrid architecture, B. (red curve) monolayer of 15nm sized gold NPs hybrid architecture.

  M.D. Porter, T.B. Bright, D.L. Allara, C.E.D. Chidsey, J. Am. Chem. Soc., 1987, 109, 3559.

23

G.K. Jennings, P.E. Laibnis, Langmuir, 1996, 12, 6173. 24 K.R. Stewart, G.M. Whitesides, H.P. Godfried, Surf. Sci., 1988, 57, 1381.

25 A.R. Bishop, R.G. Nuzzo, Current Opinion in Colloid and Interface Science, 1996, 1, 127.

26 J.C. Love, L.A. Estroff, J.K. Kriebel, R.G. Nuzzo, G.M. Whitesides, Chem. Rev., 2005, 105, 1103.

  Brust et al. reported a convenient two-phase synthesis of isolable and soluble alkanethiolate protected Au NPs in 1994.28 His one-step method had a huge impact on the nanoparticle research. Afterwards, Hostetler et al. prepared 1-Decanethiol protected gold nanoparticles according to a modified Brust-Schiffrin reaction.38 They showed how the mean size of the gold core in the synthesis of

dodecanethiolate-stabilized Au cluster compounds can be finely adjusted by choice of the Au:dodecanethiolate ratio, the temperature and rate at which the reduction is conducted. Niidome et al. reported the synthesis of cationic NPs prepared by reducing HAuCL4 with NaBH4 in the presence of 2-aminoethanethiol, and they used it to form complex with plasmid DNA that can be transferred into cultivated cells.

39

  . Lin et al.41 proposed a two-step approach to functionalize gold NPs prepared by reducing tetrachloroauric acid by trisodium citrate in water. The chloride and citrate physisorbed on the gold NPs are displaced by thioctic acid (TA), which was then exchanged by thiols containing the desired functionality in the second step method.

Badin, Self-Assembled Monolayers on Gold Substrates: Structure and Characterization, VDM Verlag Dr. Mueller e.k., 4 avril 2008.

37 M. Giersig, P. Mulvaney, Langmuir, 1993, 9, 3408. 38 M.J. Hostetler, J.E. Wingate, C.J. Zhong, J.E. Harris, R.W. Vachet, M.R. Clark, J.D. Londono, S.J. Green, J.J. Stokes, G.D. Wignall, G.L. Glish, M.D. Porter, N.D. Evans, R.W. Murray, Langmuir, 1998, 14, 17.

39 T. Niidome, K. Nakashima, H. Takahashi, Y. Niidome, ChemCom, 2004, 1978.

40 A. Manna, T. Imae, K. Aoi, M. Okazaki, Molecular Simulation, 2003, 29, 661.

size

Table 1 .

 1 is heated up to 70 ° C or 90° C depending on the requested size of NPs as displayed in table 1.1.1. Then, different amounts of solution 2 are added under stirring during half hour. After addition of the reducing agent, temperature is kept constant for 10 minutes at 70 or 90°C and then the heating was stopped [table 1.1.1.1].

	The suspensions are finally stored at 4 ° C.
	Suspension	Temperature (° C)	Amount of solution 2	Diameter (nm  5)
			(mL)
	A	70	0.15	35
	B	70	0.5	25
	C	70	1	15
	A'	90	0.15	50
	B'	90	0.5	30

(NaBH4) for 5nm diameter NPs or Tetrakis Hydroxymethyl Phosphoniumchloride [THPC], 45 for smaller ones (1-3nm diameter). a.1. Procedure to obtain 50, 35, 30, 25 or 15 nm diameter gold nanospheres: Gold nanospheres of 50, 35, 30, 25 and 15 nm diameter are prepared by mixing the two freshly prepared aqueous solutions: -Solution 1: HAuCl4 (0.01 % by weight) -Solution 2: Na3-citrate (1 % by weight). 41 S.Y. Lin, Y.T. Tsai, C.C. Chen, C.M. Lin, C.H. Chen, J. Phys. Chem. B, 2004, 108, 2134. 42 T.K. Sau, C.J. Murphy, Langmuir, 2004, 20, 6414. 43 S. Bharathi, M. Nogami, S. Ikeda, Langmuir, 2001, 17, 1. 44 T. Pham, J. B. Jackson, N. J. Halas, T.R. Lee, Langmuir, 2002, 18, 4912. 50 mL of solution 1 1.1.1: Experimental data on the preparation of gold nanospheres.

Table 1 .

 1

	Suspensions	Concentration in	Volume fraction	Particles number	Average
		weight		in 20µL	diameter (nm)
	A	0.00508 %	2.582  10 -4	2.3  10 11	35
	B	0.00515 %	2.589  10 -4	6.3  10 11	25
	C	0.00493 %	2.562  10 -4	2.9  10 12	15
	D	0.00508 %	2.545  10 -4	3.6  10 14	3 to 5
	E	0.00485 %	2.585  10 -4	7.9  10 13	3 to 5

These determined values for A, B, C, D and E suspensions are presented in table 1.1.1.2. 1.1.2: Different concentrations calculation of A, B, C, D and E.

  51,52 By UV-irradiation, gold nanorods having aspect ratio (length/ cross-

50 K. Torigoe, K. Esumi, Langmuir, 1992, 8, 59. 51 K. Esumi, K. Matsuhisa, K. Torigoe, Langmuir, 1995, 11, 3285. 52 K. Esumi, H. Junko, A. Nariaki, K. Usui, K. Torigoe, Journal of Colloid and Interface Science, 1998, 208, 578.

  69,70

67 J. Fink, C. J. Kiely, D. Bethell, D.J. Schiffrin, Chem. Mater., 1998, 10, 922. 68 N.R. Jana, L.A. Gearheart, S.O. Obare, C.J. Johnson, K.J. Edler, S. Mann, C. J. Murphy, J. Mater. Chem., 2002, 12, 2909. 69 N.R. Jana, Angew. Chem., Int. Ed., 2004, 43, 1536.

  Huang, I.H. El-Sayed, W. Qian, M.A. El-Sayed, J. Am. Chem. Soc., 2006, 128, 2115. ......................................................................................................Annexe

	Au NPs of various sizes, shapes and morphologies, and finally the specific wet chemical
	method we have used and improved in this work. The morphological and
	crystallographical characterization of Au NPs has been carried out by TEM. In particular,
	a high resolution TEM study has enabled to follow the removal of the NPs coating, in the
	aim to exchange this "native" coating with new functional ones, like thiols. The
	morphological and chemical stability of the suspensions have been studied by UV-vis spectroscopy. Absorbance (a.u) The following Chapter will highlight the elaboration and characterization of
	homogenous and heterogeneous self-assembled monolayers coated onto silicon
	400 substrate. These surfaces will be used as model supports for the adsorption and drying-500 600 700 800 900 1000 1100 Wavelength (nm)
	mediated structure formation introducing the synthesized NPs suspensions.
	Spherical and asymetrical Au NPs were synthesized using wet-chemical methods. This
	annexe first describes the synthesis of 65 nm diameter gold nanospheres (biggest
	spherical NPs size used in our work). Then, we will describe other shaped Au NPs, such
	as octahedron and net-like morphology.
	78 J. Pérez-Juste, I. Pastoriza-Santos, L. M. Liz-Marzán, P. Mulvaney, Coord. Chem. Rev., 2005, 259, 1870.
	79 A. Brioude, X.C. Jiang, M.P. Pileni, J. Phys. Chem. B 2005, 109, 13138.
	80 K. Sokolov, M. Follen, J. Aaron, I. Pavlova, A. Malpica, R. Lotan, R. Richards-Kortum, Cancer Res., 2003, 63,
	1999.

81 H. Wang, T.B. Huff, D.A. Zweifel, W. He, P.S. Low, A. Wei, J. X. Cheng, Proc. Natl. Acad. Sci. U.S.A., 2005, 102, 15752.

.

  The substrate used is an activated silicon wafer. The preparation can be carried out in two main phases as for hydrophobic coated surfaces. The main difference being the nature of the solvent used in solution phase, as in this case, the more appropriate solvent is ethanol. The rest of the procedure is similar to the previous one.

	a.3. Grafting Mechanism of organosilanes onto silicon wafers
	Independently of the reactive group the basic physico-chemical processes of
	organosilanes grafting are roughly similar.
	We therefore have considered the specific case of HTS. The HTS molecules contain
	chlorine tail groups. From a common point of view, the grafting of the organosilanes
	involves the hydrolysis of the chloro (or alkyloxysilyl headgroups in general) with the
	residual molecular film of water strongly adsorbed onto the silicon substrate. The
	reactions involved in the grafting process are represented in figure 1.2.2.3. The silanols
	groups issued from this reaction can form a covalent bond with the silanol group arising
	from the silicon surface (Si-O-Si) as Ulman, Azzopari and Arribart asssume 9 [figure
	1.2.2.3b1]. The stable linkage of the SAMs to the subtrate is provided by a crosslinking
	process of the silanol groups to form a siloxane network on the extreme layer of the
	substrate [figure 1.2.2.3c1]. However, Yoon, 10 Sillberzan, 11 or Tripp and Hair 12 propose
	a second mechanism involving a grafting of the silane chains through hydrogen bonds
	with the physisorbed water on the surface [figure 1.2.2.3a2, b2, c2].
	9 M.J. Azzopardi, H. Arribart, J. of adhesion, 1994, 46, 103.
	10 D.H. Finn, R.H. Yoon, D.A. Guzonas, Colloid Surf. A, 1994, 87, 163.
	11 P. Silberzan, L. Léger, D. Ausserré, J.J. Benattar, Langmuir, 1991, 7, 1647.

Table 1 .2.2.1: Wetting properties of model molecular surfaces.

 1

	grafting	Crosslinking at the surface

Table 1 .

 1 2.2.2 displays the results of thickness measurements of the grafted molecular films on oxidized silicon (HTS, OTS and NH2). The measurements are carried out on dozen of samples, at 22 °C and 33% relative humidity.

	SAMs

Total Thickness (A°) ± 2 Thickness of SiO2 (A°) ± 4 Thickness of monolayer (A°) HTS 58 36 22 OTS 61 36 25 NH2 44 36 8 Table 1.2.2.2: Ellipsometric measurements of the thikness of the elaborated self-assembled monolayers.

  Part 2: Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 1: Complex aggregation patterns issued from drying nanocolloidal suspensions 85 early stage thinning that further confines the drop, before it dries completely at constant diameter (complete pinning), or starts to recede slowly toward complete drying at a finite contact area. In both cases, the hydrodynamic flow involved in the drying process is rather mild, preventing, in conjunction with the interface adhesion, a flow-induced dislocation of the aggregates, at the difference of the non-wetted HTS and partially-

	wetted SiO2 surfaces especially in cases where the structures do not form. Figures
	2.1.2.5a and 2.1.2.5b illustrate these substrate dependent dynamic and hydrodynamic
	events, while providing elements to assess the relative impact of these effects on the
	stability of the aggregates. Indeed, the strong instabilities on SiO2 [figure 2.1.2.5a]
	related to high amplitude pinning and depinning (retraction) events of the drop can be
	3,10 These
	NH2/particle bonds ensure a stronger attachment and stability of the aggregates at
	interface, versus convective flow and contact line motion during the drying, at the

difference of the HTS and solvent cleaned SiO2 surfaces which mainly attach the particles through van der Waals forces. In addition, the drying nanofluids on NH2 surfaces, which have low receding contact angle (CA) ( r ~ 0) and hysteresis (< 15°) rather proceed by a quantified by the magnitude of the associated abrupt displacement D along the drop diameter. At those instabilities which are located in the last half time of the drying, the concentration of the residual drop which has significantly increased compared to the starting nominal one, is such as seed-aggregates (mostly wormlike ones) already exist in the drop.

3,10

At the first and stronger instability, the instantaneous velocity U of the abrupt contact line retraction D, over the short timescale t between depinning and rearrest of the contact line is, USiO2 = (D/t)  3.6x10 -2 ms -1 [figure 2.1.2.5a]. In comparison, the highest velocity measurable in the same last half-time on NH2 [figure

2

.1.2.5b] is, UNH2  5x10 -4 ms

-1

, with an averaged value of ~ 10 -4 ms -1 . If  is the viscosity of the concentrated residual drop at that instability, these dynamic instabilities produce an interface shear force (per unit length) F  in the wedge of the drying drop which is given by, F  ULn/r, eq 2.1.2.1

Table 2 .1.3.1: Conductivity and pH measurments of citrate stabilized and amine functionalized NPs suspensions, before and after dialysis.

 2

	4 hours at 60 °C in a 2% solution of

The results show that the suspension conductivity decreases from a high value before dialysis down to that of the pure water after dialysis, indicating an almost complete elimination of residual ions, and surfactants of synthesis [table

2

.1.3.1]. The volume fraction of the NPs in the suspension also decreases by 100 times after dialysis as displayed in table 2.1.3.2.

Table 2 .1.3.2: Volume fraction of particles in raw and dialyzed citrate stabilized and amine functionalized suspensions.

 2

Table 2 .

 2

	NPs	Conductivity (µs/cm) ± 1	Debye length	(nm)
	Water	2	-
	Citrate stabilized NPs	144	12.5
	Dialysed citrate
	stabilized NPs

1.3.3 displays the Debye length for the various NPs suspensions.

Table 2 .1.3.3: Conductivity of NPs suspension and equivalent Debye lengths for raw and dialyzed, citrate stabilized and amine functionalized Au NPs.

 2

  Y. Liu, T. Murao, Y. Nakano, M. Naito, M. Fujiki, Softmatter, 2008, 4, 2396. F. Q. Zhu, G. W. Chern, O. Tchernyshyov, X. C. Zhu, J. G. Zhu, C. L. Chien, Phys.Rev.Lett., 2006, 96, 27205.

	3 Z.L. Wangn, Materials Today, 2004, 26.
	4 F. Q. Zhu, D. L. Fan, X. C. Zhu, J. G. Zhu, R. C. Cammarata, C. L. Chien, Advanced Materials, 2004, 16, 2155.

Since this work that described some of the underlying mechanisms of the spontaneous self-assembly and growth of particles nanorings, other techniques have been developed based on different processes, especially on template-assisted techniques and nanolithography . For instance, Zhu et al. have proposed a method, referred to as "natural lithography", which uses nanospheres as template to create nanoring patterns. The diameter, area, density, thickness and composition of nanorings can be easily controlled by this method. The symmetry of nanorings can also be engineered to obtain asymmetric nanorings.

4,5

In a similar way, Aizpurua et al. have prepared ring-shaped gold nanoparticles using colloidal lithography.

6

A while ago, Bayati et al. have described an in-situ approach to the fabrication of metal nanoring array using an assembly of microbeads as template.

7

This method differs essentially from the other microbeads template-based techniques in that it relies on the in-situ synthesis of the nanoparticles, whereas the others use nanoparticles suspensions. Tripp et al.

8

have found a way to create assembly of Co 1 J.J. Miao, R.L. Fu, J.M. Zhu, K. Xu, J.J. Zhu, H.Y. Chen, Chem. Commun., 2006, 3013. 2 5 6 J. Aizpurua, P. Hanarp, D.S. Sutherland, M. Ka¨ ll, W. Bryant, F.J. Garcı´a de Abajo, Phys. Rev. Let., 2003, 90, 57401.

7 M. Bayati, P. Patoka, M. Giersig, E.R Savinova, Langmuir, 2010, 26, 3549.

  .2.0.1 which shows the spontaneous nucleation of nanohole defects,

	observed by Atomic Force Microscopy in a thin wetting film of sodium alginate solution
	(0.2 wt% in water ~19.2 μmol/L) deposited by drop-casting and dried on a cleaned
	21 W.S. Chang, L. S. Slaugther, B. P. Khanal, E. R. Zubarev, S. Link, NanoLett., 2009, 9, 1152.

22 B. P. Khanal, E. R. Zubarev, Angewandte Chemie, 2007, 46, 2195. 23 S. Stannard, H. Alhummiany, E. Pauliac-Vaujour, J.S. Sharp, P. Moriarty, Langmuir, 2010, 26, 13892. 24 K. Werner, B. Sto¨ckelhuber, A. Radoev, Wenger, H.J. Schulze, Langmuir, 2004, 26, 164. Part 2: Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 2: Nanobubbles and nanodroplets template growth of particles nanorings in drying nanofluids 110

  Part 2: Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 2: Nanobubbles and nanodroplets template growth of particles nanorings in drying nanofluids 113 timescale before contact line retraction reduces the density of sedimented nanodroplets/nanobubbles, preventing their collapse under the shear pressure.It is worth nothing here that an additional requirement for these experiments is related to the contact angle and the profile of the confined nanodroplets and nanobubbles. As depicted in figure 2.2.1.1, this should ensure their stability versus perturbations and contact line drainage, as well as the proper condition of confinement. Indeed, a too low contact angle (CA) θ would lead to a too thin spreading film which will be simply sheared with its NPs coating by the confined edge of the drying suspension drop. On the other hand, a too high CA would lead to non attached rolling nanodroplets which will be completely entrained and collected by the evaporating/receding suspension drop. Therefore, the additional requirement would be satisfied by a low, but

	Confined droplets	Contact angle on HTS in suspension (cyclohexane + NPs)
	Water	170 °
	Water/ Ethanol: (volume	140 °
	fraction: 1/4)
	Air (bubble)	140 ° (THF)

finite adhesion of the nanodroplet/bubbles, i.e., typically for θ > 90° and a wetting energy (adhesion),

W=γinterf (1 + cos θ) > 0 eq 2.2.2.1

As shown in table 2.2.2.1, the nanodroplets of (water/ethanol) mixture at (1V/4V) (and the air bubbles) satisfy this requirement, with a reasonably high nanodroplet/nanobubble height and a low, but finite attachment.

Table 2 .2.2.1: Contact angle measurements (at the equilibrium) of microdroplets of water and a mixed water/ethanol deposited on HTS in cyclohexane (+NPs) and of air bubble on HTS in THF.

 2

Table 2 .2.2.2: Assignment of the main peaks of the SERS spectra of alkane thiols grafted on Au NPs.

 2

  of metal NPs represent potential conductive nanowires. Gourishankar et al.27 have used oligonucleotides and their analogues such as phosphorothioates and peptide nucleic acids to electrostatically encapsulate cationic-capped gold NPs. They showed that DNA can act as a template for organizing lysine-capped cationic gold NPs into linear circulation time and to target specific tumoral tissues.36 Yet, an interesting investigation has been performed by Wu et al.37 reported on a pH-responsive aminopolysaccharide chitosan mediating the electrodeposition of model NPs. Chitosan, which is known to electrodeposit at the cathode surface in response to a high localized pH, is able to simultaneously drive the spatial and selective organization of NPs. These first results show that polysaccharides represent potential template for NPs assembly.

	superstructures by simple drop casting process. Single stranded phosphorothioate DNAs
	can act as connectors between gold NPs to generate superstructures and stabilize the
	hybrid system. In particular, alginic acid which, is a biodegradable, biocompatible, non-toxic, and low
	The above assemblies involve complementary electrostatic interactions between cost polymer, shows interesting physicochemical properties, such as wound healing, ion-
	polymer and metal NPs. However, assembly of DNA and anionic NPs has also been
	reported.	Harnack	et	al. 28	found	that	negatively	charged
	29 S.Y. Lim, J.S. Lee, C.B. Park, Biotechnology and Bioengineering, 2010, 105, 210.
	30 K.J. Sreeram, M. Nidhin, B.U. Nair, Colloids and Surfaces B: Biointerfaces, 2009, 71, 260.
	31 H. Huang, Q. Yuan, X. Yang, Colloids Surf., B, 2004, 39, 31.
	H. Nakao, H. Shiigi, Y. Yamamoto, S. Tokonami, T. Nagaoka, S. Sugiyama, T. Ohtani, Nano Lett., 2003, 3, 32 D.S. dos Santos, P.J.G. Goulet, N.P.W. Pieczonka, O.N. Oliveira, R.F. Aroca, Langmuir, 2004, 20, 10273.
	1391.

25

S. A. Maier, P. G. Kik, H. A. Atwater, S. Meltzer, E. Harel, B. Koel, A. G. Requicha, Nature Mater. , 2003, 2, 229.

26

G. Wang, R.W. Murray, Nano

Lett., 2004, 4, 95.

chains "tris(hydroxymethyl)phosphine"-capped gold NPs are able to bind to DNA and undergo electroless plating after adsorption to calf thymus. Hydrogen-bonding interactions (with DNA amines) were proposed as the driving forces for the assembly formation.

Finally, this latter issue of non-organic NPs assembly via polyelectrolytes adsorption was densely investigated with DNA molecules but sparsely with polysaccharides.

Indeed, various studies focusing on polysaccharides adsorption on NPs were done in the aim to stabilize or synthesize them, but not to generate 2D nanoscale structures.

29,30,31,32,33,34,35

Travan et al.

34

reported the formation and stabilization of silver NPs in a bioactive chitosan-derived polysaccharide solution, and showed their antimicrobial properties, either in solution or in 3D hydrogel structures. In addition, the medical applications and drug delivery (for example in cancer imaging) of polysaccharide-coated NPs were also expressed including their abilities to increase the 27 A. Gourishankar, S. Shukla, R. Pasricha, M. Sastry, K.N. Ganesh, Current Applied Physics, 2005, 5, 102. 28 O. Harnack, W.E. Ford, A. Yasuda, J.M. Wessels, Nano Lett., 2002, 2, 919. 33 Y. Yi, Y. Wang, H. Liu, Carbohydr. Polym. , 2003, 53, 425.

34 A. Travan, C. Pelillo, I. Donati, E. Marsich, M. Benincasa, T. Scarpa, S. Semeraro, G. Turco, R. Gennaro, S. Paoletti, Biomacromolecules, 2009, 10, 1429. 35 M. Lv, S. Su, Y. He, Q. Huang, W. Hu, D. Li, C. Fan, S.T. Lee, Advanced Materials, 2010, 22, 5463.

blood exchange ability, and absorption of metal ion.

38,39,40,41,42

This natural polysaccharide containing linear chains of β-D-mannuronic and α-L-guluronic acid [figure

2

.3.0.2], has found direct and strong applications in food and pharmaceutical industries,

38,39,40,43,44

environmental-materials 41,42 and electrical equipments.

45

  2.3.2.6. In the late stage of the drop evaporation, a fourfold fractal aggregate is nucleated [figure 2.3.2.6d], the main branches of which extend simultaneously to the growth of perpendicular side branches [figure 2.3.2.6e]. The side branches keep growing while additional new side branches to those first ones develop. This highly ordered structure keep growing, until the confinement of the branches in the structure, as shown in figures 2.3.2.3a and 2.3.2.6, and depicted schematically in figure 2.3.2.5.

  -5 M), none of the (SA1/dialyzed NPs) solutions has led to aggregation structures with morphological features that were distinctly or qualitatively different from those produced by the corresponding pure SA1 or NPs solutions [figure 2.3.2.4], unlike to the SA1/as-prepared NPs solutions. Two main differences between the dialyzed and the asprepared NPs solutions exist. First the salts in the form of reducing agents are removed after dialysis. Second, the dialyzed NPs solution is depleted in small NPs of ~ 2nm [figure 2.3.2.1d]. Therefore, the absence of the highly ramified complex drying patterns in SA/dialyzed NPs drops can arise either from the absence of salts (synthesis residues), or from small NPs and their possible interactions with alginate chains.

  These globules may thus either represent globular assemblies of SA2 chains, or for stronger signal, SA2 globules encapsulating NPs, as indicated by EFM contrast [figure 2.3.2.21f-g]. Indeed, the specific globular conformation in SA can be explained by the (SA chains/counter ions/NPs) interactions as discussed below.

SA chains/counter ions/NPs interactions (via SA chain length effect)

Pure single component SA solution (SA chains/ counter ions interaction)

  K. Mougin, Z. Zheng, N. Piazzon, E. Gnecco, H. Haidaraa, J. Colloid and Interface Science, 2009, 333, 719.

	1 J. Lian, L. Wang, X. Sun, Q. Yu, R. C. Ewing, Nano Lett., 2006, 6,1047.
	2 H.C. Kim, N.D. Theodore, T.L. Alford, J. Appl. Phys., 2004, 95, 5180.

3 G.C. Han, Y.H. Wu, P. Luo, J.J. Qiu, T.C. Chong, Solid State Commun., 2000, 126, 479.

4 5 A. El-Azab, S. Gan, Y. Liang, Surf. Sci., 2002, 506, 93. 6 H. C. Kim, T. L. Alford, D. R. Alle, Appl. Phys. Lett., 2002, 81, 4287.

  Part 3: Aging of the aggregation structures vs. NPs mobility_Chapter 2: AFM Manipulation of NPs on model surfaces-A tentative account of the surface mobility and dislocation of aging NPs structures 205

	3.2.2. Results and discussion
	19 T.F. Jaramillo, S.H. Baeck, B.R. Cuena, E.W. Mc Farland, J. Am. Chem. Soc., 2003, 125, 7148.

20

B.R. Cuena, S.H. Baeck, T.F. Jaramillo, E.W. Mc Farland, J. Am. Chem. Soc. 2003, 125, 12298. 21 B. Anczykowski, B. Gotsmann, H. Fuchs, J.P. Cleveland, V.B. Elings, Applied Surface Science, 1999, 140, 376.

  , or the rolling of the NP to occur. In these expressions, µ is a friction coefficient, is the shear strength, C a contact area, and and the angles which are defined in figure3.2.2.2. (tp) and (ps) as subscripts of C and µ represent respectively the (tip/particle) and (particle / substrate) contacts.

	sin	cos ps ps ps C		and						eq 3.2.2.1
	R	(sin	cos	ps	) C	µ ps	tp	sin tp C	tp	ps	cos	,	eq 3.2.2.2
	for the sliding

Tafazzoli, M. Sitti, Proceedings of IMECE'04 2004 ASME International Mechanical Engineering Congress Anaheim, CA, November 13-19, 2004.

  .2.2.13a] of environment (quasi-dry atmosphere).First, these results show that the energy dissipation values are intrinsically much lower for these interfaces. Unlike all the previous results [figures 3.2.2.8, 3.2.2.10], the graph here displays a decrease of the energy dissipation vs. RH. This quite unexpected result can be accounted for by the hydrophobic nature of the NPs which drives a quite spontaneous expulsion of this NP from the confined hydrophobic (tip/surface) interface toward the more hydrophobic "air" environment. This expulsion is even more triggered at higher RH (> 40 % RH) where water condensation at both the substrate and the tip makes the confined (tip/NP/substrate) interface more hydrophilic. As a result, the NP is more easily

(less energy cost) expelled toward the ahead in the non-confined and more hydrophobic (substrate/air) interface. These different situations and configurations are schematically depicted in figure

3

.2.2.13b and 3.2.2.13c.

Table 1 : Evaluation of the complex refractive index (n, k) of a NPs multilayer structure and a thermally evaporated Au film by Ellipsometry.

 1 General Annexe: Combined electrostatic-covalent building of Au NPs multilayers, and their size enhanced cohesive and SERS properties

	5 nm Au colloidal 1 layer equivalent to 5 nm	3.814	-0.896
	5 nm Au colloidal 4 layers equivalent to 20 nm	3.014	-1.664
	15nm Au colloidal 4 layers equivalent to 60 nm	3.045	-1.522

A.R. Bishop, R.G. Nuzzo, Current Opinion in Colloid and Interface Science, 1996, 1, 127.

A. Ulman, An introduction to Ultrathin Organic Films: from Langumir-Blodgett to self assembly, Academic press: San Diego, 1991.

C. R. Kessel, S. Granick, Langmuir, 1991, 7, 532.

A. G. Carson, S. Granick, J.Mat. Res., 1990,

5, 1745.

R. Maoz, J. Sagiv, J. Col. Interf. Sci., 1984, 100, 465.

D. K. Schwartz, S. Stienberg, J. Israelchvili, J. Azasadzinski, Phys.Rev. Lett., 1992, 69, 3354.

J. V. Davidovits, V. Pho, P. Silberzan, M. Goldman, Surf. Sci., 1996, 369, 352.

J. Wagner, T. Kirner, G. Mayer, J. Albert, J.M. Köhler, Chemical Engineering Journal, 2004, 101, 251.

R.D. Deegan, O. Bakajin, T.F. Dupont, G. Huber, S.R. Nagel, T.A. Witten, Nature, 1997, 389, 827.

H.Haidara, K. Mougin, Dekker encyclopedia of nanoscience and nanotechnology, 2004, 761.

J.Feder, PlenumPress: NewYork,USA, 1988, 11.

R. D. Deegan, O. Bakajin, T.F. Dupont, G. Huber, S.R. Nagel, T.A. Witten, Nature, 1997, 389, 827.

J. Israelachvili, Intermolecular & Surface Forces (Academic Press, San Diego, CA, 1992).

Part 2: Drying-mediated assembly of Au NPs in mesoscale structures on model solid surfaces _ Chapter 3: Drying-mediated assembly structures of binary solutions of (NPs/biopolymer) mixtures

Handbook of chemistry and physics, CRRC press, Inc., 74 th edition, 1993-1994.

Part 1

Presentation of the nanomaterials:

Suspension of nanoparticles Self-Assembled Monolayers Chapter 2

Self-Assembled Monolayers (SAMs)

Part 2

Drying-mediated assembly of gold nanoparticles in mesoscale structures on model solid surfaces

Binary SA/NPs solution (SA chains/ NPs interaction)

The neutralization of SA negative charge (COO-) in solution can be mediated by charged NPs. These charged NPs are cationic NH3 + stabilized Au spherical NPs in our work. In this case, the interaction between NPs and SA is of electrostatic nature and can be described as the adsorption of such polycationic particles on the polyanionic SA chain, when the NPs diameter is smaller than SA persistence length. The physicochemical properties of the system (SA persistence length, NPs size and charge, ions concentration…) determine the structure of the final complexes and thus the drying structures on the rigid substrates. Hereafter we will deal with two different SA chain lengths (SA1 and SA2 as notified previously), maintaining the same NPs size (25 nm in diameter) and ions concentration in the two studied complexes (SA1/ dialyzed NH3 + NPs) and (SA2/ dialyzed NH3 + NPs).

The drying structures of binary (SA1/NPs) solutions (shorter SA chains) rather display well-defined structures compared to that of single component SA solutions. The (NP/SA) complexes assemble into "beads-on-a-string" structures in the solution, and result in

vs. NPs mobility (AFM nanomanipulation)

Chapter 1

Aging of complex nanoparticle-based structures

stable at 33 % RH, even after 9 days of storage. However, the deterioration of the structure is achieved at 75 % RH, after 9 days of storage.

Comparison of the degeneration behaviour for the 3 different sizes of NPs

The first important remark concerns the high stability of all the aggregation structures

Role of the water condensate

The proposed mechanism to explain this degeneration and the reorganization of the complex structure is based on the adsorption of water on the substrate, and the formation of an ultrathin condensate film surrounding the particles aggregates. The presence of such condensate film to the wall promotes desorption and lateral diffusion of NPs and small clusters away from the structures. Possible concerted mechanism 10,11 11 Dislocation diffusion occurs when adjacent sub-units of a cluster move in a row-by-row fashion through displacement of a dislocation. The process begins with nucleation of the dislocation followed by what is essentially sequential displacement on a concerted basis. Glide diffusion refers to the concerted process cannot be estimated with this technique. Recently, it has been shown that another scanning probe technique, the atomic force microscope (AFM), is capable of positioning single atoms or clusters even at room temperature, that's why it has become popular as a simple manipulation tool. 6,7 Changing its function from only imaging to both imaging and manipulation, new challenging problems are introduced. In Atomic force Microscopy, three main modes were used: either non-contact (NC) mode or contact (C) mode or intermittent one (Tapping).

The first mode which was developed in AFM was contact mode. Manipulation of large C60 islands on NaCl was performed by Lüthi et al. using contact AFM. 8 Even if the shear between islands and crystal surface can be derived from the frictional forces experienced by the AFM tip while scanning, the applicability of contact AFM to nanomanipulation was limited to relatively large objects (tens of nanometers in size).

The last results obtained by Custance et al shows that it is now possible to manipulate single atoms using NC-AFM. 9 Byungsoo Kim et al have also proposed a new explanation of extraction and deposition of atoms using AFM. 10 In contact mode, different strategies (pushing, pulling…) have also been used to manipulate nanoclusters (NPs).The tip can be first used for positioning particles on a substrate by pushing or pulling operations. Based on the finding that a similar drying dynamics could lead to the formation of selfassembly aggregation structures in pure polysaccharide alginate solutions, we were interested in the mixture of (NPs/ biopolymer solutions), both for its fundamental and functional interest. On a fundamental viewpoint, the problem was to understand the relationship between the drying patterns of single-component solution drops (NPs and alginate), and those emerging from the compounding of two such pure components, for similar drying conditions. The issue of drying-mediated co-assembly and complex pattern formation in such binary systems, using anionic sodium alginate (SA) and amine

General Annexe

Combined electrostatic-covalent building of Au NPs multilayers, and their size enhanced cohesive and

SERS properties

General Annexe: Combined electrostatic-covalent building of Au NPs multilayers, and their size enhanced cohesive and SERS properties A2 1.0. Introduction

In recent years, considerable effort has been devoted to the design and fabrication of structured materials with functional properties. The long-range and large scale arrangement of NPs is an important issue in the development of nanostructured materials with new electronic, magnetic and photonic properties. 1 The two (2D) and three dimensional (3D) arrangements of NPs still remain difficult for certain particles shapes (anisotropic rods, ellipsoidal, stars etc…). Different top-down techniques like photolithography 2 and microcontact printing 3 have been developed to organize NPs on substrates.

In the filed, noble metal NPs, and especially gold NPs have attracted a great deal of interest. In particular, supported nanostructured films of gold NPs have appeared as promising functional structures for applications as diverse as optical field enhancement 4,5 and catalysis. 6,7,8 Indeed, metal particles of size smaller than the wavelength of light exhibit specific optical properties due to the resonant excitation of coherent electron oscillations, a phenomenon known as localized surface plasmons.

When used to enhance the optical susceptibility of molecules that are embedded in a nanoparticulate surface which is irradiated by an electromagnetic field (light), this optical property (surface plasmons) can be used as a powerful spectroscopic tool, also known as Surface-Enhanced Raman Spectroscopy (SERS).

However, the cooperative effect of these surface plasmons as well as the robustness of the multilayer structure will strongly depend on the interactions between the different building blocks (nanoparticle/nanoparticle, nanoparticle/linker) which determine the overall organization of the network.

A3

For the elaboration of such nanoparticulate multilayers, there two main approaches: a chemical one via colloids synthesis and assembly, and a more conventional one based on chemical vapor deposition (CVD) procedure. One of the advantages of colloidal assembly is the way the particle size, shape and chemistry can be easily adjusted. For instance, nanocolloidal gold particles can be prepared with diameters ranging from 1 to 120 nm with a relatively high monodispersity. As a result, surfaces made from colloidal Au NPs have a tunable nanometer-scale roughness determined solely by the particle diameter and packing. The ultimate surface and bulk properties of these nanoparticulate surfaces will be directly correlated to these intrinsic parameters of the individual NPs (nature, size, shape, functionalization).

In this work, the nanoparticulate multilayer superlattice was prepared using the principle of alternating adsorption (layer by layer procedure) which was introduced in 1966 by Iler from colloidal particles of opposite charges. 9 This method known as layerby-layer (LbL) deposition is based on electrostatic interactions between polyanions and polycations. Although Iler's work did not attract much attention at the time, it was one of the first studies that successfully demonstrate that thin films of NPs could be readily assembled on rigid supports. Twenty five years after Iler's discovery, Decher and coworkers utilized LbL technique to fabricate multilayer thin films from oppositely charged polyelectrolytes. 10 Hu and coworkers have also developed a facile approach for the preparation of multilayered nanostructure of gold nanorods using a linear polyethylenimine as a polymeric adhesive layer. 11 This LbL procedure has therefore inspired our work, although we have developed here a less conventional approach based on the use of two alternating and distinct bonds between the consecutive layers to assemble the Au particles in the multilayer. Two sizes of spherical NPs were used (5 and 15 nm diameter) to build two different multilayer systems, and to find out the size effect inside these structures on the optical and mechanical (cohesion) properties. The particles were transferred from the nanocolloidal solution, onto self-assembled monolayers (SAMs) coated silicon wafers, using dipcoating process. Two consecutive NPs layers were tightly bonded was insured by the The principle of the elaboration of the NPs multilayers is based on a Layer-by-Layer (LbL) deposition technique that consists essentially in the following steps:

The substrate, a silicon (Si) wafer bearing its native silica (SiO2) layer of ~2 nm was coated with a self-assembled monolayer (SAM) of a NH2-terminated silane molecule, as described in part 1.

a-Formation of the first layer of gold NPs

The sample was immersed in the solution of gold NPs of either 15 nm or 5 nm diameter for 15 to 20 minutes (optimal time to reach a compact layer of NPs). Then, it was rinsed and sonicated in water for about 1 minute in an ultrasonic bath.

Results and discussion

The gold NPs multilayers were characterized by AFM and ellipsometry to confirm the formation of the layered structures, their compactness and the spatial organization of the NPs.

a-Ellipsometry

For both multilayer systems made respectively of 15 and 5 nm diameter particles, the thickness of each NPs layer has been measured, using a Null-Ellipsometer (Multiskop, Optrel, Germany), working at 532 nm (Nd-YAG laser). For the ellipsometric modeling, each layer is represented by a monolayer of Au NPs with its tethered thiolate molecular film (linker). The thickness (t) of the nanoparticulate film at the different layering steps and the corresponding complex refractive index (n, k) were determined from the measured ellipsometric angles, using the resident Elli software.

The thickness (t) and refractive index (n, k) of the first layer were first determined. And for each additional layer, the refractive index of the new multilayer system was recalculated. It should also be mentioned here that the convergence of the layer model defined in the Elli software reaches its limit over three interfaces. In addition, the measurements of the refractive index of the Au NPs multilayers show that they do not display a bulk feature (n= 0.43; k=-2.455 for a laser=532 nm). For the 5 nm NPs, the average refractive index for the first layer was n= 3.5; k= -1.0 as displayed in table 1. For the first layer of the 15 nm and 5 nm r Au NPs, we obtained an average thickness of respectively 19.0±0.5 nm and 6.0±0.5 nm, using an approximate value of the film refractive index of 3 and an extinction coefficient of -1 [figure 2]. Those results of optical constants are very different from the Au bulk parameters reported in the literature. 13

List of Publications