S Albert

Th Bauer

M Michl

G Biroli

J.-P Bouchaud

A Loidl

P Lunkenheimer

R Tourbot

C Wiertel-Gasquet

F Ladieu

Fifth-order susceptibility unveils growth of thermodynamic amorphous order in glass-formers

Glasses are ubiquitous in daily life and technology. However the microscopic mechanisms generating this state of matter remain subject to debate: Glasses are considered either as merely hyper-viscous liquids or as resulting from a genuine thermodynamic phase transition towards a rigid state. We show that third and fifth order susceptibilities provide a definite answer to this longstanding controversy. Performing the corresponding high-precision nonlinear dielectric experiments for supercooled glycerol and propylene carbonate, we find strong support for theories based upon thermodynamic amorphous order. Moreover, when lowering temperature, we find that the growing transient domains are compact -that is their fractal dimension d f = 3. The glass transition may thus represent a class of critical phenomena different from canonical second-order phase transitions for which d f < 3.

The glassy state of matter, despite is omnipresence in nature and technology [START_REF] Ediger | Perspective: Supercooled liquids and glasses[END_REF], continues to be one of the most puzzling riddles in condensed-matter physics [START_REF] Ediger | Perspective: Supercooled liquids and glasses[END_REF][START_REF] Berthier | Theoretical perspective on the glass transition and amorphous materials[END_REF]: For all practical purposes, glasses are rigid like crystals but they lack any long-range order. Some theories describe glasses as kinetically constrained liquids (3), becoming so viscous below the glass transition that they seem effectively rigid. By contrast, other theories [START_REF] Dzero | Structural glasses and supercooled Liquids: theory, experiment, and applications[END_REF][START_REF] Tarjus | The frustration-based approach of supercooled liquids and the glass transition: a review and critical assessment[END_REF] are built on the existence of an underlying thermodynamic phase transition to a state where the molecules are frozen in well defined, yet disordered positions. This so-called "amorphous order" cannot be revealed by canonical static correlation functions, but rather by new kinds of correlations [i.e. point-to-set correlations or other measures of local order [START_REF] Mossa | Locally preferred structure in simple atomic liquids[END_REF][START_REF] Biroli | Thermodynamic signature of growing amorphous order in glass-forming liquids[END_REF]] that have now been detected in recent numerical simulations [START_REF] Biroli | Thermodynamic signature of growing amorphous order in glass-forming liquids[END_REF][START_REF] Pinney | Recasting a model atomistic glassformer as a system of icosahedra[END_REF][START_REF] Berthier | Efficient measurement of point-to-set correlations and overlap fluctuations in glass-forming liquids[END_REF]. In these theories, thermodynamic correlations lock together the fluctuations and response of the molecules, which collectively rearrange over some length-scale , ultimately leading to rigidity. In this thermodynamic scenario, is proportional to a power of ln(τ α /τ 0 ) where τ α is the structural relaxation time and τ 0 is the microscopic time-scale, generally smaller than 1 arXiv:1606.04079v1 [cond-mat.dis-nn] 13 Jun 2016 1ps (4, 5). Because equilibrium measurements require a time larger than τ α , they cannot be performed in the range where is very large since this would require exponentially long times. This limitation is essentially why the true nature of glasses is still a matter of intense debate.

Here, we propose a pioneering strategy to unveil the existence of a thermodynamic length that grows upon cooling. Instead of only varying the temperature T , we also vary the non-linear order k of the response of supercooled liquids. This is motivated by a general, although rarely considered [START_REF] Kimura | Nonlinear dielectric relaxation spectroscopy of ferroelectric liquid crystals[END_REF], property of critical points: At a second order critical temperature T c , the linear susceptiblity χ 1 associated to the order parameter is not the only diverging response. As a function of temperature, all the higher order responses χ 2m+1 with m ≥ 1 diverge even faster than χ 1 itself. This comes from the fact that the divergencies of all the χ 2m+1 have the same origin, namely the divergence of the length . By using the appropriate scaling theory, it can be shown that the larger m, the stronger the divergence in temperature. As theoretically shown below, transposing this idea to glasses requires taking into account that the putative "amorphous" or hidden order in supercooled liquids [START_REF] Biroli | Thermodynamic signature of growing amorphous order in glass-forming liquids[END_REF][START_REF] Bouchaud | On the Adam-Gibbs-Kirkpatrick-Thirumalai-Wolynes scenario for the viscosity increase in glasses[END_REF] is not reflected in χ 1 itself, but only in higher-order response functions χ 2m+1 with m ≥ 1. This idea is indeed supported by previous measurements and analyses of the third order susceptibility χ 3 [START_REF] Crauste-Thibierge | Evidence of growing spatial correlations at the glass transition from nonlinear response experiments[END_REF][START_REF] Th | Cooperativity and the freezing of molecular motion at the glass transition[END_REF][START_REF] Brun | Evidence of growing spatial correlations during the aging of glassy glycerol[END_REF][START_REF] Buchenau | Probing cooperative liquid dynamics with the mean square displacement[END_REF][START_REF] Casalini | Dynamic correlation length scales under isochronal conditions[END_REF]. We report results on the fifth order susceptibility χ 5 (T ) and compare them to χ 3 (T ) in two canonical glass forming liquids, glycerol and propylene carbonate. If critical phenomena really play a key role for the glass transition, χ 5 should increase much faster than χ 3 as the liquid becomes more viscous.

This scenario can be understood by means of a theoretical argument based on previous work [START_REF] Bouchaud | Nonlinear susceptibility in glassy systems: A probe for cooperative dynamical length scales[END_REF] and further detailed in (18). Suppose that N corr = ( /a) d f molecules are amorphously ordered over the length-scale , where a is the molecular size and d f is the fractal dimension of the ordered clusters. This implies that their dipoles, oriented in apparently random positions, are essentially locked together during a time τ α . We expect that in the presence of an external electric field E oscillating at frequency ω ≥ τ -1 α , the dipolar degrees of freedom of these molecules contribute to the polarisation per unit volume as

p = µ dip ( /a) d f ( /a) d F µ dip E ( /a) d f kT (1)
where µ dip is an elementary dipole moment, F is a scaling function such that F (-x) = -F (x), and d = 3 the dimension of space. This states that randomly locked dipoles have an overall moment ∼ √ N corr , and that we should compare the energy of this "super-dipole" in a field to the thermal energy. Equation 1 is motivated by general arguments involving multi-point correlation functions through which d f can be given a precise meaning (18) and is fully justified when diverges, in particular in the vicinity of a critical point such as the Mode-Coupling transition or the spin-glass transition. In the latter case, Eq. 1 is in fact equivalent to the scaling arguments of [START_REF] Levy | Critical-dynamics of metallic spin glasses[END_REF], provided one performs the suitable mapping between the magnetic formalism of (19) and ours.

Expanding Eq. 1 in powers of E, we find the "glassy" contribution to p:

p µ dip = F (0) a d f -d µ dip E kT + 1 3! F (3) (0) a 2d f -d µ dip E kT 3 + + 1 5! F (5) (0) a 3d f -d µ dip E kT + . . . (2)
Because d f must be less or equal to d, we find that the first term, contributing to the usual linear dielectric constant χ 1 (ω), cannot grow as increases. This simple theoretical argument explains why we do not expect spatial glassy correlations to show up in χ 1 (ω). The second term, contributing to the third-order dielectric constant, does grow with provided d f > d/2. Although d f < d close to a standard second order critical point [START_REF] Coniglio | Encyclopedia of complexity and systems science[END_REF] such as the spinglass transition, several theories suggest (4, 5, 21, 22) that ordered domains are compact (d f = d), in which case a 2d f -d = a d = N corr , as assumed in our previous papers [START_REF] Bouchaud | Nonlinear susceptibility in glassy systems: A probe for cooperative dynamical length scales[END_REF][START_REF] Ladieu | Nonlinear dielectric susceptibilities in supercooled liquids: A toy model[END_REF]. The third term of Eq. 2 reveals that the fifth-order susceptibility χ 5 (ω) should diverge as 3d f -d . Therefore, the joint measurement of χ 3 (ω) and χ 5 (ω)

provides a direct way to estimate d f experimentally, through the following relation:

|χ 5 | ∝ |χ 3 | µ(d f ) ; µ(d f ) = 3d f -d 2d f -d ; d f (µ) = d µ -1 2µ -3 (3)
where the exponent µ(d f ) is equal to 2 when the dynamically correlated regions are compact (d f = d), and is higher otherwise. We predict two key results that can obtained from χ 5 and χ 3 susceptibility measurements. First, if amorphous order increases approaching the transition, the frequency dependence should be more anomalous [i.e. more humped (18)] for χ 5 (ω) than for χ 3 (ω). Second, the growth of χ 5 should be much stronger than that of χ 3 when lowering the temperature, following χ 5 ∼ χ 2 3 if we assume compact amorphous domains. Our work provides experimental evidence that these predictions indeed hold and suggests that the glass transition represents a new type of critical phenomenon with growing length and time scales but with d f = d, in contrast to the spin-glass transition that instead displays (19) canonical critical behavior with d f ≈ 2.35.

We measured χ 5 (ω) in two canonical glass formers, glycerol and propylene carbonate, by applying a field of amplitude E and of frequency f = ω/(2π), see (18). The fifth-order response is ∝ χ 5 E 5 , and orders of magnitude smaller than the cubic and linear ones, given by ∝ χ 3 E 3 and ∝ χ 1 E respectively. We avoided any contributions of χ 3 and of χ 1 by measuring the signal at 5ω, which only contains the component χ (5) 5 of the fifth order susceptibility (18). We measured χ (5) 5 with two independent setups due to the very small amplitude, optimized along complementary strategies. One setup (in Augsburg) was designed to achieve the highest possible field (reaching 78 MV/m). We optimized sensitivity with a differential technique using two samples of different thicknesses in the other setup (Saclay, see Fig. S1 of ( 18)), which required lower fields (up to 26 MV/m).

We have obtained the values of |χ

5 (ω)| for glycerol at various frequencies and temperatures by using the two aforementioned techniques (Fig. 1A). A clear peak arises for a given T in |χ [START_REF] Tarjus | The frustration-based approach of supercooled liquids and the glass transition: a review and critical assessment[END_REF] 5 (ω)| for a frequency f peak 0.22f α where the α-relaxation frequency f α , defined by the peak of the out-of-phase linear susceptibility, is indicated by arrows in Fig. 1A. Even though the data were determined by two independent setups, the overall agreement is remarkable (Fig. 1B). The most accurate comparison is possible at 204K where f peak is well inside the frequency range accessible by the two setups. The two spectra at 204K coincide on the low frequency side of the peak (18). On the other side of the peak, a discrepancy between the two sets of data progressively increases with frequency, reaching a constant factor of 4 at the highest frequencies (Fig. 1B). Apart from the value of the electric field, the main difference between the two experiments is the number of applied field cycles n. The Saclay setup measured the stationary responses (n → ∞), whereas n remained finite in the Augsburg setup [similarly to [START_REF] Richert | Nonlinear dielectric response and thermodynamic heterogeneity in liquids[END_REF]], ranging from n = 2 at the lowest frequencies to n ∝ f at the highest frequencies. The two setups give the same results for χ [START_REF] Tarjus | The frustration-based approach of supercooled liquids and the glass transition: a review and critical assessment[END_REF] 5 because at sufficiently low values of f /f α , the response of the supercooled liquid is likely to instantaneously follow the field. By contrast, at higher frequencies ω ≥ τ -1 α the finite cycle number may play a role, making a quantitative treatment of this effect difficult (18). Our further analysis relies on the behavior of the peaks of χ (5) 5 , and more precisely on their relative evolution with temperature, which reasonably agrees in the two setups (see below).

The qualitative features of |χ [START_REF] Crauste-Thibierge | Evidence of growing spatial correlations at the glass transition from nonlinear response experiments[END_REF][START_REF] Th | Cooperativity and the freezing of molecular motion at the glass transition[END_REF]. Both quantities exhibit a humped shape, with a peak located at the same frequency f peak ≈ 0.22f α , as well as a strong increase of the height of the peak as the temperature is decreased. These two distinctive features are important since they are specific signatures of glassy dynamical correlations [START_REF] Bouchaud | Nonlinear susceptibility in glassy systems: A probe for cooperative dynamical length scales[END_REF], in contrast to trivial systems without correlations [START_REF] Coffey | Dielectric and Kerr effect relaxation in alternating electric fields[END_REF]. In this case, the modulus of all higher-order non linear susceptibilities monotonously decreases with frequency (18, 25).

To quantitatively compare the frequency dependency of the susceptibilities χ 1 is the linear susceptibility noted χ 1 above) (Fig. 1C). The peak amplitude for k = 5 is strongly enhanced compared to k = 3 -that is the higher the nonlinear order k, the more anomalous the frequency dependence (Fig. 1C and Figs. S2-S3 of (18)). This behavior is a decisive result and fully consistent with our scaling analysis. For archetypical glass formers, we can always fit the linear susceptibility by assuming a sum of Debye relaxations where χ 1, Debye ∝ 1/(1 -iωτ ). We do this by choosing than in glycerol (Fig. 3A). This suggests that the larger the fragility, the stronger the temperature dependence of the thermodynamic length . This is easily understood in the scenario of (4) where the critical point is the Vogel-Fulcher temperature T 0 : In this case, equilibrium measurements can be made closer to the critical point for more fragile liquids, because the larger the fragility, the smaller the difference between T g and T 0 .

Our experimental results are therefore consistent with the general predictions of theories -such as the Random First Order Transition or Frustration Limited Domains (4, 5) -where the physical mechanism driving the glass transition is of thermodynamic origin and where some non trivial (albeit random) long-range correlations build up between molecules. Only in this case (18) can one have N corr dipolar degrees of freedom collectively responding over some length-scale and on time-scales of the order of τ α . If instead the glass transition is regarded as a purely dynamical phenomenon, there would not be any anomalous increase of the normalized peak value of the higher-order susceptibilities at all (18). Our results therefore severely challenge theories advocating against any thermodynamic signature and favoring purely dynamic scenarios. Moreover, from a comparison of the higherorder susceptibilities, our results are consistent with χ 5 ∝ χ 2 3 . This constitutes evidence for compact amorphously ordered domains, i.e. d f = d, pointing towards a non-standard nature of the glass transition, in contrast to canonical second order phase transitions for which d f < d.

  )| (Fig.1A-B) are reminiscent of those of the third harmonic cubic susceptibility |χ

k

  of order k, we plotted |χ

k

  (f /f α )/χ (k)k (0)| of glycerol for k = 5, 3, and 1 (χ[START_REF] Ediger | Perspective: Supercooled liquids and glasses[END_REF]

ACKNOWLEDGMENTS

We thank C. Alba-Simionesco, A. Coniglio, P.-M. Déjardin, G. Tarjus, and M. Tarzia for interesting discussions. This work in Saclay has been supported in part by ERC grant NPRGLASS, by the Labex RTRA grant Aricover and by the Institut des Systèmes Complexes ISC-PIF. The work in Augsburg was supported by the Deutsche Forschungsgemeinschaft via Research Unit FOR1394. S.A., R.T., C.W-G. and F.L. developed the Saclay's experimental setup. Th.B. and P.L. developed the experimental setup in Augsburg. Th.B. and M.M. performed the measurements and analysis of the Augsburg data. A.L. and P.L. conceived and supervised the project in Augsburg. G.B. and J.-P.B. derived the theoretical scaling analysis; and all authors were involved in the interpretation of the results and creation of this manuscript. Data are available as supplementary material. All authors have no competing financial interests. SUPPLEMENTARY MATERIALS www.sciencemag.org/content/352/6291/1308/suppl/DC1 Materials and Methods Figs. S1 to S3 References (29-42) Data files

a suitable distribution G(τ ) of relaxation times τ (26) caused by dynamical heterogeneities. Because the trivial response discussed above also obeys χ 1, trivial ∝ 1/(1 -iωτ ), we have used (18,[START_REF] Coffey | Dielectric and Kerr effect relaxation in alternating electric fields[END_REF] the same distribution G(τ ) to calculate the trivial responses χ (k) k, trivial for k = 3 and 5. For a given k > 1, a large difference exists between the experimental spectrum of |χ

k (0)| and its trivial counterpart (Fig 1C), which we can ascribe to correlation-induced effects. For k = 1 the experimental data agree with the trivial response [convoluted with G(τ )], consistent with the theoretical arguments stating that glassy correlations do not change the linear response [START_REF] Bouchaud | Nonlinear susceptibility in glassy systems: A probe for cooperative dynamical length scales[END_REF]. For k = 3 and 5 the difference to the trivial response increases, being much more important for k = 5 where it exceeds one order of magnitude. This quantitatively supports the scaling prediction obtained assuming that collective effects due to the growth of amorphous order play a key role in supercooled liquids.

We measured |χ

(5) 5 (ω)| at five different temperatures for propylene carbonate (Fig. 2). Propylene carbonate differs from glycerol in that its fragility [START_REF] Debenedetti | Supercooled liquids and the glass transition[END_REF][START_REF] Böhmer | Nonexponential relaxations in strong and fragile glass formers[END_REF] m ∝ [∂ log(τ α )/∂(1/T )] Tg (T g denotes the glass transition temperature) is twice as large and it has Van der Waals bonding, in contrast to hydrogen bonding. Despite these differences, the anomalous hump-like features of glycerol (Fig. 1A) are also observed in propylene carbonate (Fig. 2). We expect this behavior from our scaling framework, which relies on the predominant role of collective dynamical effects in supercooled liquids. The presence of similar anomalous features in two very different glass formers suggests they only weakly depend on the specific microscopic properties of the material.

To elicit the temperature dependence of collective effects, we introduced dimensionless quantities related to χ

3 , X

where 0 is the permittivity of free space, ∆χ 1 = χ 1 (0) -χ 1 (∞) is the dielectric strength, a 3 is the molecular volume and k B is the Boltzmann constant. The main advantage of these dimensionless non-linear susceptibilities is that in the trivial case of an ideal gas of dipoles, both X

3, trivial and X

5, trivial are independent of temperature when plotted versus scaled frequency (18,25). Hence, we ascribe their experimental variation to the non-trivial dynamical correlations in the supercooled liquid [START_REF] Bouchaud | Nonlinear susceptibility in glassy systems: A probe for cooperative dynamical length scales[END_REF][START_REF] Ladieu | Nonlinear dielectric susceptibilities in supercooled liquids: A toy model[END_REF]. This interpretation is strongly supported by previous findings [START_REF] Crauste-Thibierge | Evidence of growing spatial correlations at the glass transition from nonlinear response experiments[END_REF][START_REF] Th | Cooperativity and the freezing of molecular motion at the glass transition[END_REF][START_REF] Brun | Evidence of growing spatial correlations during the aging of glassy glycerol[END_REF][START_REF] Ladieu | Nonlinear dielectric susceptibilities in supercooled liquids: A toy model[END_REF] where the temperature dependence of |X 3 | no longer depends on temperature. This low frequency region corresponds to time scales much longer than τ α where the liquid flow destroys glassy correlations, making each molecule effectively independent of others, and yielding a dielectric response close to the aforementioned trivial case. This is why, to determine the temperature evolution of the glassy dynamical correlations, we focused on the region of the peak of |χ We expect the nonlinear susceptibilities to contain both a trivial contribution that would exist even for independent dipoles, and a "singular" contribution (i.e. diverging with ) as given in Eq. 2. We thus write:

Here the trivial contributions are calculated by assuming a set of independent Debye dipoles convoluted with the aforementioned distribution G(τ ) of relaxation times (18). We compared the temperature evolution of |X , to derive the value of the exponent µ, from which we deduce the fractal dimension d f of the dynamically correlated regions by using Eq. 3. In both glycerol and propylene carbonate, the value µ = 2, corresponding to compact domains of dimension d f = 3, is found to be consistent with experiments (triangles in Figs 3A andB). By fitting the T dependence of |X (3) 3,sing. (f peak (T ))| with a smooth function (18), we found the hatched area corresponding to µ = 2.2 ± 0.5 in glycerol and µ = 1.7 ± 0.4 in propylene carbonate (Fig. 3). The fact that, within experimental uncertainty, a value of µ 2 is common to each of the two liquids supports a picture of amorphous compact domains mostly independent of differences at the molecular level and validates the correlation length-scale for our scaling analysis. Considering that the temperature interval in Fig. 3B is smaller by a factor of 2, we note that the critical behavior in propylene carbonate is stronger 5 reported here are obtained directly (18) by monitoring the response of the sample at 5ω, when applying an electric field E at angular frequency ω. Two independent setups were used, designed either to maximize the field amplitude (Augsburg setup, spheres), or to optimize the sensitivity (Saclay setup, cubes). Lines are guides for the eyes. Errors are of the order of the scatter of neighboring data points around the lines. Both setups yield consistent results. For a given temperature T , |χ [START_REF] Tarjus | The frustration-based approach of supercooled liquids and the glass transition: a review and critical assessment[END_REF] 5 | has a humped shape, with a maximum occurring at the frequency f peak 0.22f α where f α is the relaxation frequency indicated by a colored arrow for each temperature. When decreasing T , the height of the hump increases strongly. The yellow plane emphasizes the fact that, for a given T , χ

5 is constant for f ≤ 0.05f α . (B) Projection onto the susceptibilityfrequency plane of the data of Fig. 1A at 204K and at 195K. The agreement around and below the peak is remarkable at 204K (see text). The relative evolution of the height of the peak is reasonably similar between 204K and 195K for the two setups (see Fig. 3A). (C) Comparison of the fifth-order, cubic, and linear susceptibilities of glycerol [the latter is noticed χ

1 for convenience, see (18)]. Symbols, with line to guide the eyes, are Saclay data at 204K; the error bars are of the order of the size of the symbols for k = 5 [except at the lowest frequencies, see (18)] and smaller for k = 3 and 1. The higher the order k, the stronger the hump of |χ (k) k |: this is a key result supporting the amorphous-order scenario. The dashed lines, emphasized by colored areas, correspond to the trivial response of an ideal gas of dipoles without amorphous order. In this case |χ have been added on the graph by scaling to the Saclay point at 204K: the Augsburg point at 195K is reasonably well within the hatched area, which shows that the relative evolution of X


C Brun

F Ladieu

D L'hôte

G Biroli

J-P Bouchaud

Evidence of growing spatial correlations during the aging of glassy glycerol

We have measured, as a function of the age ta, the aging of the nonlinear dielectric susceptibility χ3 of glycerol below the glass transition. Whereas the linear susceptibility can be accurately accounted for in terms of an age dependent relaxation time τα(ta), this scaling breaks down for χ3, suggesting an increase of the amplitude of χ3. This is a strong indication that the number Ncorr of molecules involved in relaxation events increases with ta. For T = 0.96 × Tg, we find that Ncorr increases by ∼ 10% when ta varies from 1ks to 100ks. This sheds new light on the relation between length scales and time scales in glasses.

An old plastic ruler under tension has a longer length than a newly made one [START_REF] Struik | Physical Aging in Amorphous Polymers and Other Materials[END_REF]. This is a striking illustration of the aging phenomenon, the hallmark of the physics of glasses. The physical properties of an aging system depend on the time t a elapsed since the material has fallen out of equilibrium; i.e., since the glass transition has been crossed. Understanding aging is of paramount importance [START_REF] Struik | Physical Aging in Amorphous Polymers and Other Materials[END_REF][START_REF] Berthier | [END_REF], both from a fundamental and a practical point of view (many daily-life materials do in fact age). Yet, there is no universally accepted theoretical description of the basic mechanisms of aging, although many scenarii have been proposed (see [START_REF] Berthier | [END_REF][3][START_REF] Vincent | Sitges Conference on Glassy Systems[END_REF][START_REF] Berthier | Dynamical heterogeneities in Glasses, Colloids and Granular Media[END_REF][START_REF] Lubchenko | [END_REF]).

One of the most distinctive features of aging is the increase of the physical relaxation time τ α with the age t a [START_REF] Struik | Physical Aging in Amorphous Polymers and Other Materials[END_REF][START_REF] Vincent | Sitges Conference on Glassy Systems[END_REF][7][8][9][10][11][12]. In the case of spin-glasses, this increase has been rather convincingly attributed to the growth of the number N corr of cooperatively relaxing spins. Both simulations [13] and experiments [14] are compatible with this scenario, and allow one to estimate the dynamical growth law N corr (t a ). The situation is much less clear for most other glassy systems, either experimentally or numerically [13,15]. In fact, while there are only two simulations [16,17] reporting the growth of a dynamical correlation length during the aging of model glasses, and few analytical studies [13,18,19], there is to our knowledge no available experimental result for real glass-formers. The last decade has witnessed an outburst of activity on dynamical heterogeneities and on the determination of the size N corr of dynamically correlated molecules in glasses [START_REF] Berthier | [END_REF][START_REF] Berthier | Dynamical heterogeneities in Glasses, Colloids and Granular Media[END_REF], but almost all these studies have been confined to equilibrated systems. Whereas a compelling positive correlation between N corr,eq (T ) and the equilibrium relaxation time τ α (T ) has been established above the glass temperature T g (see [START_REF] Berthier | Dynamical heterogeneities in Glasses, Colloids and Granular Media[END_REF] and refs. therein), its aging counterpart has not been investigated experimentally. The aim of the present study is to extend to the aging regime the experimental determination of N corr that relies on the cubic nonlinear dielectric susceptibility [20,21]. We will report, for the first time, clear experimental evidence of the growth of the size of dynamically correlated regions during the aging of glycerol -a prototypical glass former.

As argued in [19], non-linear susceptibilities are the ideal gambits that elicit the growth of amorphous order in glassy systems. Whereas linear susceptibilities (dielectric, magnetic, elastic, etc.) are blind to amorphous order and dynamical correlations, the equilibrium cubic nonlinear dielectric susceptibility χ 3 of deeply supercooled glass formers is given, at temperature T , by [19]:

χ 3 (ω, T ) ≈ Z(T )N corr,eq (T )H(ωτ α (T )) (1)
Z(T ) ≡ ǫ 0 ∆χ 2 1 (T )a 3 (T ) k B T , (2)
where ω = 2πf is the angular frequency, k B the Boltzmann constant, ǫ 0 the vacuum permittivity, a 3 (T ) the molecular volume, and ∆χ

1 (T ) = χ 1 (ω = 0, T )-χ 1 (ω ≫ τ -1 α )
is the contribution to the static linear susceptibility of the degrees of freedom associated with the glass transition. In Eq. ( 1), H(u), with u = ωτ α (T ) ≡ f /f α (T ), is a complex scaling function which goes to zero both for small and large arguments, and peaks in-between. Eq. ( 1) can be fully justified within the Mode-Coupling Theory of glasses [22]; it has been confirmed experimentally in [20,21], and used to extract precise estimates of N corr,eq (T ) in equilibrium. In the aging regime, it is natural to conjecture [19] that the above expression remains valid with τ α (T ) -→ τ α (t a ) and N corr,eq (T ) -→ N corr (t a ), therefore allowing one to infer information about the growing of N corr during aging. Strictly speaking, such a simple substitution is too naive: one expects on general ground that (a) the scaling function H should also be replaced by a different scaling function H; and (b) the prefactor Z(T ) might itself acquire an age dependence: the value of both ∆χ 1 and a could evolve with age, and the temperature T should in principle [19] be replaced by an "effective" temperature T ef f (t a ) that encodes the possible deviations to the equilibrium fluctuation-dissipation theorem [23][24][25]. However, our experiments are "weakly" out of equilibrium, since they reach equilibrium eventually. In this case we expect that the scaling assumption Eq. (1) generalized to the aging regime, with H = H and Z(t a ) = Z(T ), holds to a very good approximation. Our strategy will therefore be the following: (i) since the linear susceptibility does not depend on N corr , its age dependence should only come from that of τ α (t a ). Indeed, we will establish that χ ′′ 1 (ω, t a ) ≈ G ′′ (ωτ α (t a )), where G ′′ is the equilibrium scaling function (see Fig. 3). This allows us to determine τ α (t a ) directly; (ii) by waiting long enough (i.e. t a = 200ks) we measure the equilibrium non-linear susceptibility χ 3 (ω, T ) for various frequencies (see Fig. 3), thereby allowing one to obtain the scaling function H(u); (iii) inserting these informations into Eq. (1) in the aging regime, we can deduce the age dependence of N corr (up to the assumption that Z(t a ) = Z(T ), see Fig. 4) [26].

Experiments. Ultrapure glycerol was purchased from VWR and placed in our dielectric setup described in Refs [20,21,27]. Glycerol was the dielectric layer of a capacitor made with stainless steel electrodes separated by a 8.25µm thick Mylar c ring. All the aging quantities were measured with the same T quench: The sample was first set to 196K ≈ T g + 8K (where τ α ≈ 1s) during 1hr, then it was cooled, without any undershoot, to the working temperature T = 180.1K (or T = 182.7K) in 1.8ks, and finally T was kept constant within a ±70mK interval during 200ks. We used a high harmonic purity a.c. field of amplitude ≤ 3MVrms/m to measure, separately, χ 3 (ω, t a ) as well as χ 1 (ω, t a ) and χ 1 (3ω, t a ) -see [28]. Once χ 3 (ω, t a ) is known, the key quantity is, according to Eq. ( 1), X 3 (ω, t a ) defined as:

X 3 (ω, t a ) ≡ χ 3 (ω, t a ) Z(t a ) ≈ N corr (t a )H(ωτ α (t a )) (3)
The equilibrium values of X 3,eq (ω, T ), obtained after the end of aging, are plotted as a function of f /f α,eq in Fig. 1 for T = 180.1K and for T = 182.7K (f α is defined as the peak frequency of χ ′′ 1,eq (ω, T ), [START_REF] Tg | was estimated by extrapolating the VFT law obtained for fα,eq(T > Tg): as some deviation to VFT behavior might arise below Tg [6, 10[END_REF]).

For comparison, we also plot the equilibrium data at 194.1K ≈ T g + 6K obtained in [20,21] which shows that the qualitative trend already found above T g [20,21] holds also below T g , i.e. |X 3,eq | for fixed f /f α,eq (T ) increases when T decreases, [30]. Scaling analysis. During aging both |χ 1 | and |X 3 | decrease for a given ω, because the dielectric spectrum shifts to lower frequencies [7][8][9][10][11][12]. This is illustrated by the series of symbols on Fig. 2. For not too deep quenches [7], such as ours, and for our limited range of 3.5 decades in frequencies, the shape of the spectrum of χ ′′ 1 is not expected to change during aging except for an overall scaling factor. This is confirmed by Fig. 2 where the χ ′′ 1 (ω, t a ) data for all frequencies and all ages can be very accurately reproduced by the equilibrium susceptibility χ ′′ 1,eq (ω, T = 180.1K), up to a rescaling of the frequency by a factor x(t a ) = f α (t a )/f α,eq (see the dotted lines in Fig. 2 obtained by adjusting the factor x(t a ) for each t a ). We have also checked that our values of x(t a ) are close to what is predicted by the ansatz introduced in Ref. [9], [START_REF]Note however that this ansatz requires the knowledge of fα(ta = 0) and fα,eq[END_REF]. We have checked that the very same x(t a ) factor also allows us to rescale the χ ′ 1 (ω, t a ) data onto the equilibrium curve. Note that since the χ ′′ 1 (ω, t a ) are not pure power-laws in frequency, horizontal and vertical shifts (in log-log) are not equivalent. Hence, the accurate rescaling of Fig. 2 implies that the amplitude of χ ′′ 1 (ω, t a ) does not depend on the age. A finer look at the rescaling suggests that this amplitude is constant within a 1% uncertainty range, and if anything, decreases with age. This is important for the discussion of the Z(t a ) factor in Eq. ( 1) that includes ∆χ 1 (t a ) to which χ ′′ 1 (ω, t a ) is proportional. To estimate the difference between Z(t a ) and Z(T ) we invoke the "fictive" temperature T f ict (t a ) [3,[START_REF] Lubchenko | [END_REF]7,[START_REF] Mossa | [END_REF] (not to be confused with the effective temperature T ef f ) defined such that χ ′′ 1 (ω, t a ) = χ ′′ 1,eq (ω, T f ict (t a )). This phenomenological recipe leads to T f ict (t a > 0.3ks) < T +2K. By extrapolating the T dependence of ∆χ 1 above T g , we estimate that ∆χ 1 (t a ) may increase by at most 1.1% during aging. The order of magnitude is similar to the one suggested by the rescaling analysis above, albeit with an opposite sign. Similarly, we estimate that a 3 might decrease by ∼ 0.2% during aging. Finally, close to 180K, T /T ef f (t a ) was found to increase in glycerol during aging, by ∼ 2% according to [24], but by at most 0.7% according to the recent work of Ref. [25]. Altogether, we conclude that Z(t a )/Z(T ) remains very close to unity, with a probably much overestimated maximum increase of 4% during aging. This effect is therefore smaller than the ∼ 12% increase of N corr (t a ) that we infer from our analysis below.

Our central experimental result is summarized in Fig. 3 where we now show both χ ′′ 1 (ω, t a ) and |X 3 (ω, t a )| as a function of f /f α (t a ) for 1ks ≤ t a ≤ 200ks. As expected from the results of Fig. 2, χ ′′ 1 (ω, t a ) collapses very well onto the equilibrium curve. However, this collapse is not observed for |X 3 (ω, t a )| (Fig. 3, filled triangles and left x(t a )

FIG. 2: (Color online) Aging of the out-of-phase susceptibility χ ′′ 1 (ω, ta) of glycerol at T = 180.1K (filled symbols), in log-log coordinates. The thick (resp. thin) solid line correspond to the equilibrium spectrum at T = 180.1K (resp. at T = 182.7K). The dotted lines superimposed to the filled symbols are obtained by translating horizontally the 180.1K equilibrium spectrum by a factor x(ta) (see text). Inset: Resulting curve for the scaling factor x(ta) = fα(ta)/fα,eq. axis). The rightmost points of these series of triangle correspond to the equilibrium values |X 3,eq (ω, T )| and are singled out as large black squares. The thick line joining these black squares is an interpolation that corresponds to the equilibrium value of |X 3,eq (ω, T )| for intermediate frequencies. At variance with the good superposition obtained for χ ′′ 1 , Fig. 3 reveals that, for a given f /f α (t a ), the value of |X 3 (ω, t a )| is systematically below the corresponding value at equilibrium. This is exactly what is expected from Eq. ( 3): the ratio between these two values should be equal to N corr (t a )/N corr,eq (T ), and should thus increase with age, precisely as observed in Fig. 3. Defining the vertical logarithmic distance δ, in Fig. 3, as:

δ(u, t a ) ≡ Z(t a )X 3 (uf α (t a ), t a ) Z(T )X 3,eq (uf α,eq ) = Z(t a )N corr (t a ) Z(T )N corr,eq (T ) , (4)
we obtain the last equality if Eq. (3) holds, in which case δ(u, t a ) should be independent of frequency. With Z(t a )/Z(T ) ≈ 1 justified above, we conclude that δ(u, t a ) directly measures N corr (t a )/N corr,eq (T ).

The values of δ(u, t a ) are plotted in Fig. 4, [START_REF] At | K, as expected, we find weaker aging effects: aging lasts ≃ 20ks, and yields a relative increase of Ncorr with ta typically 2 -3 times smaller than that of Fig. 4. These results are thus consistent with those at 180[END_REF]. We indeed observe that, up to the precision of our measurements, δ(u, t a ) does not depend on frequency. This is an important consistency test of our scaling assumption, Eqs. [START_REF] Struik | Physical Aging in Amorphous Polymers and Other Materials[END_REF]3). From Fig. 4, we deduce that δ(u, t a ) increases by ≈ 12% when t a increases from 1ks to 100ks. Since the ratio Z(t a )/Z(T ) increases by at most 4%, we interpret the data of Fig. 4 as giving the first experimental evidence that the size of the dynamically correlated clusters increases with the age in a glass former, see [START_REF]Extrapolating the T dependence of Ncorr,eq(T ) measured above Tg[END_REF]. The increase of N corr (t a ) during aging can be approximately accounted for by extending the observation made in [20,21]: the temperature dependence of N corr,eq deduced from non-linear susceptibility measurements can alternatively be obtained as: ∂N corr,eq /∂T ≈ 1.5∂(T χ T )/∂T , where T χ T = T × max ω | ∂(χ ′ 1,eq (ω, T )/∆χ 1 )/∂T |, see [21,[START_REF] Berthier | [END_REF][36][37]. We now surmise that this can be extended to the out-of-equilibrium regime by simply translating the f α (t a ) dependence of Fig. 2 in terms of T f ict (t a ) (see [START_REF]This is somehow justified theoretically[END_REF]). This heuristic procedure leads to the solid curve shown in Fig. 4, which is indeed close to the values of δ(u, t a ) directly drawn from our experiments. This suggests that it might be possible to extend the theoretical work of [START_REF] Berthier | [END_REF]36] to aging, and get a simplified way of estimating N corr (t a ) using linear susceptibilities.

Time and length scales. Finally, we take advantage of the wide range of time scales over which the evolution of N corr has been measured to revisit one of the most crucial aspect of glassy dynamics, namely the relation between time and length scales. Within the Random First Order Transition theory [START_REF] Biroli | Structural Glasses and Supercooled Liquids: Theory, Experiment, and Applications[END_REF][START_REF] Lubchenko | [END_REF], one expects ln(τ α /τ 0 ) = Υℓ ψ P S /k B T , where τ 0 is a microscopic time scale, Υ a typical molecular energy barrier, ℓ P S the pointto-set correlation length [START_REF] Berthier | Dynamical heterogeneities in Glasses, Colloids and Granular Media[END_REF][START_REF] Biroli | Structural Glasses and Supercooled Liquids: Theory, Experiment, and Applications[END_REF], which sets the size of the clusters that must rearrange cooperatively for the system to relax, and ψ the so-called barrier exponent. In Wolynes' version of RFOT, Υ = κk B T where κ is a number that depends weakly on molecular details, and ψ = 3/2 [START_REF] Lubchenko | [END_REF]. In order to compare with our results, Values of δ(u, ta) = Z(ta)Ncorr(ta)/Z(T )Ncorr(eq) ≈ Ncorr(ta)/Ncorr(eq) extracted from Fig. 3. δ(u, ta) is found to be independent of frequency, as predicted by Eqs. (3,[START_REF] Vincent | Sitges Conference on Glassy Systems[END_REF]. The solid line is the estimation based on phenomenological fictive temperature T f ict (ta), see text. Inset: Estimation of the exponent ψ (see text) using all aging and equilibrium data, starting from 204K where τα,eq = 20ms. The x-axis is R(τα) = Ncorr(τα)/Ncorr,eq(20ms) with τα = τα(ta) or τα,eq. For the y-axis, we chose either Υ = Υ0 which amounts to V = v(τα, T )/v(20ms, 204K) and yields ψ ≈ 1; or Υ = κkBT which amounts to W = w(τα)/w(20ms) and yields ψ ≈ 3/2.

one should postulate that the size of dynamically correlated clusters N corr is proportionnal to ℓ 3 P S . This relation is not unreasonable, but sharp theoretical arguments are still lacking to relate unambiguously "cooperative" regions to "dynamically correlated regions". In any case, we collect all our past and present data in the inset of Fig. 4, where we plot v(τ α , T ) = T ln(τ α /τ 0 ) and w(τ α ) = ln(τ α /τ 0 ) as a function of N corr , where τ α = τ α (t a ) or τ α,eq . In Fig. 4, V and W correspond respectively to Υ = Υ 0 independent of temperature and to Υ = κk B T . We fix the value of τ 0 to 10 -14 s, leaving ψ as the only free parameter. To our surprise, we find that the best choice for ψ within the first hypothesis (Υ = Υ 0 ) is ψ ≈ 1, which is the value found numerically in [41], whereas in the second hypothesis (Υ = κk B T ), we find ψ ≈ 3/2, as predicted by Wolynes et al.! Our data is compatible with both hypotheses [START_REF]The fit τα ∝ N z corr proposed in [16-18] is of similar quality but leads, here[END_REF], although slightly favoring the first one, in particular in the aging regime (see Fig. 4). Note that a factor 10 on τ 0 changes the value of ψ by ∼ 10%.

Conclusion. We have reported the first direct observation of the increase of N corr in the aging regime of a structural glass. For glycerol at T = 0.96T g , our quench protocol yields an increase of N corr by ∼ 10%, which lasts ∼ 100ks [START_REF]Extrapolating the T dependence of Ncorr,eq(T ) measured above Tg[END_REF]. These results deepen our microscopic understanding of aging and give precious information about the relation between time and length scales in glasses. Our study opens a new path for studying aging in many other systems. It could also be extended to the more complicated thermal histories designed to probe the memory and rejuvenation effects [START_REF] Vincent | Sitges Conference on Glassy Systems[END_REF]8]. Monitoring the behaviour of N corr in these experiments should shed a new light on these phenomena.

The two samples bridge is a technique measuring a differential voltage V m ≡ V thin -V thick and relying on the "balancing relation" ensuring that V m (1ω) = 0: this happens provided one has z thick Y thick = z thin Y thin where Y is the admittance of one sample and z is the impedance relating the sample to the ground. An important feature of the two samples bridge is that once the balancing condition is met at 1ω it is also met at any other frequency. Thus the balancing condition enables, at the same time, to suppress the contribution coming from the nonlinear character of the input voltage amplifiersince V thin (1ω) -V thick (1ω) = 0-; and to suppress the 3ω spurious component of the source -since the linear response of the samples cancels at any frequency-. The two samples bridge is thus the most efficient technique to get I(3ω, t), provided one has a way to check that the condition V thin (1ω) -V thick (1ω) = 0 remains true during the I(3ω, t) acquisition. This condition might indeed not remain true in the case where some uncontrolled slight disymetry between the two samples happens, such as the one resulting from a slight difference in the temperature of the two samples. Fortunately, when measuring at equilibrium, one varies the field E: one thus checks all along the 3ω acquisitions that I(3ω, t) is accurately -up to ±1%-proportional to E 3 , which ensures that the condition V thin (1ω) -V thick (1ω) = 0 is metenough-during all the acquisitions. However, in the aging case, one monitors I(3ω, t) as a function of the age t a , for a constant E. Thus, if some violation of the condition V thin (1ω)-V thick (1ω) = 0 happened, it might pollute the age dependence of the 3ω response of the samples, and we would have no way to correct this imperfection.

This is why we have decided to work with only one sample and to use the "Twin-T notch filter" -see Fig. 5-: its transmission coefficient T f ilt (ω) is smaller than 10 -4 for the frequency f 0 = 1/(2πRC) and of order 1 for 3f 0 . Therefore, by choosing the components R, C so as to set 2πf 0 = 1ω, we are absolutely sure that the 1ω voltage at the input of the Lock-in amplifier is small enough during the 3ω acquisitions in the aging regime. Besides, by setting the voltage source to one of the few values where the DS360 voltage source is nearly perfectly harmonic, one gets a setup where the 3ω spurious contribution of the source is nearly negligible -this very little spurious contribution can, of course, be easily measured and subtracted from the measured signal-. This is why we have choosen the twin T notch filter for our 3ω measurements in the aging regime.

At 3ω the sample is equivalent to a pure current source I(3ω, t) with an impedance Z(3ω) = 1/[Y(3ω)] placed in parallel. Neglecting for simplicity any remaining spurious contribution of the DS360 source, one gets for the voltage V meas (3ω, t) measured by the lock-in amplifier:

V meas (3ω, t) = α(3ω)Z(3ω)I(3ω, t) (9)
3 (ω, ta) in the aging regime. Note that the quantity defined as χ

(3) 3 in Eq. ( 6) of this Supplementary Material has been noted χ3 in the main letter, to simplify the notations. The "twin-T" notch-filter damps the response at 1ω by a factor larger than 10 4 . Inset: Two samples bridge, see ref. [27].

where α(3ω) is the global transmission coefficient between the sample and the Lock-in. In the simplest case where (r, |Z|) ≪ (R, 1/[C3ω]) the coefficients multiply and one gets α(3ω) = T f ilt (3ω) × r/[r + Z(3ω)]. In any case, α(3ω) is directly measured by setting the fundamental angular frequency of the source to Ω ≡ 3ω, and by using α(Ω) ≡ V meas (Ω)/V source (Ω).

Eq. ( 9) is written at equilibrium, when all the involved quantities no longer depend on the age t a . At equilibrium, we have of course carefully checked, both at T = 180.1K and at T = 182.7K, that V meas (3ω, t) is proportionnal to the cube of the voltage source V 3 s . In the aging case, all the susceptibilities of the sample -linear and nonlinear-depend on the age t a . As a result, all the quantities involved in Eq. ( 9) depend on the age t a . This is why, by repeating for each quantity the very same T quench, we have separately measured the age dependence of I(3ω, t, t a ) but also of Z(3ω, t a ), Z(1ω, t a ), α(3ω, t a ), and of V appl (1ω, t, t a ) = V s (1ω, t)-V a (1ω, t, t a ) where V appl (1ω, t, t a ) is the voltage applied onto the sample at age t a and at time t -see Fig. 5-. We have made all the possible consistency checks -for example, given R, C, Z(1ω, t, t a ) one can predict the age dependence of V appl (1ω, t, t a )-. A single T quench lasts 200ks at 180.1K, and for each of the 5 different frequencies ranging from 12mHz to 11Hz, we have measured the age dependence of the 5 different quantities mentionned above. As a result, with all the cross-checks, the data acquisition, for 180.1K and 182.7K altogether, took a bit more than 10 4 ks, i.e. a bit more than 4 months.

FIG. 1 :

 1 FIG. 1: (Color online) Equilibrium values of the modulus and the phase of X3, measured in glycerol for three temperatures around Tg ≃ 188K.

FIG. 3 :

 3 FIG.3:(Color online) T = 180.1K. Solid curves: equilibrium quantities vs f /fα,eq . Small symbols: aging quantities vs f /fα(ta) -the value of f labels each data set-. Note the collapse of the aging and equilibrium curves for χ ′′ 1 (right axis). This contrasts with what is observed for |X3| (left axis) where the aging values are systematically below the equilibrium ones. This reflects the increase of Ncorr(ta) during aging; see text, Eqs.(3,[START_REF] Vincent | Sitges Conference on Glassy Systems[END_REF] and Fig.4.

FIG. 4 :

 4 FIG.4: (Color online) T = 180.1K. Values of δ(u, ta) = Z(ta)Ncorr(ta)/Z(T )Ncorr(eq) ≈ Ncorr(ta)/Ncorr(eq) extracted from Fig.3. δ(u, ta) is found to be independent of frequency, as predicted by Eqs.(3,[START_REF] Vincent | Sitges Conference on Glassy Systems[END_REF]. The solid line is the estimation based on phenomenological fictive temperature T f ict (ta), see text. Inset: Estimation of the exponent ψ (see text) using all aging and equilibrium data, starting from 204K where τα,eq = 20ms. The x-axis is R(τα) = Ncorr(τα)/Ncorr,eq(20ms) with τα = τα(ta) or τα,eq. For the y-axis, we chose either Υ = Υ0 which amounts to V = v(τα, T )/v(20ms, 204K) and yields ψ ≈ 1; or Υ = κkBT which amounts to W = w(τα)/w(20ms) and yields ψ ≈ 3/2.

FIG. 5 :

 5 FIG. 5: Main figure: Electronic setup used for the measurements of χ

We thank C. Alba-Simionesco, S. Nakamae, G. Tarjus, R. Tourbot for help and discussions. GB acknowledges financial support from the ERC grant NPRG-GLASS.

SUPPLEMENTARY INFORMATION:

For the sake of completness, we give here the main ingredients of the 3ω measurements in the aging regime. Note that the quantity defined as χ

(3) 3 in Eq. ( 6) below has been noted χ 3 in the main letter, to simplify the notations.

As explained in Refs. [21,27], when a field E(t) is applied onto a dielectric liquid, the macroscopic polarisation P can be expressed as :

where the function χ 1 (t) corresponds to the experimental macroscopic linear response while χ 3 (t 1 , t 2 , t 3 ) is the experimental macroscopic nonlinear response. This expression is valid as long as the non linear terms are small, i.e. as long as, for any integer k,

. This is why Eq. ( 5) is restricted to the cubic response, and neglects higher order terms.

It is shown in ref. [27], that for a field E(t) = E cos(ωt) one gets, from Eq. ( 5):

+3/4E 3 χ

3 )

3 ) + ...

The time dependent polarisation amounts to an electrical current given by

where S is the surface of the electrodes. Inserting Eq. ( 6) into Eq. ( 7), one finds that I(t) is the sum of a current I(1ω, t), oscillating at the fundamental frequency, and of a current I(3ω, t) oscillating at 3ω. As for the field range E ≤ 3MVrms/m involved in our experiments the condition mentionned above

secondly that the value of I(1ω, t) is fully dominated by χ 1 and thus I(1ω, t) can be, to a very good approximation, analysed by using the usual framework of complex admittance Y(ω). The small third harmonics current is given by:

3 ) (8) This quantity is so small that carefully designed electronic setups must be used to avoid to mix the sought I(3ω, t) with the nonlinear imperfections of the voltage source and of the voltage amplifier [27]. It was shown in Ref [27] that two kinds of setups can be used: either a "two samples bridge" involving two samples of different thicknesses -see the inset of Fig. 5-; or a "twin-T notch filter", see the main part of Fig. 5.