Fast equilibration mechanisms in disordered materials mediated by slow liquid dynamics.

The rate at which a nonequilibrium system decreases its free energy is commonly ascribed to molecular relaxation processes, arising from spontaneous rearrangements at the microscopic scale. While equilibration of liquids usually requires density fluctuations at time scales quickly diverging upon cooling, growing experimental evidence indicates the presence of a different, alternative pathway of weaker temperature dependence. Such equilibration processes exhibit a temperature-invariant activation energy, on the order of 100 kJ mol-1. Here, we identify the underlying molecular process responsible for this class of Arrhenius equilibration mechanisms with a slow mode (SAP), universally observed in the liquid dynamics of thin films. The SAP, which we show is intimately connected to high-temperature flow, can efficiently drive melts and glasses toward more stable, less energetic states. Our results show that measurements of liquid dynamics can be used to predict the equilibration rate in the glassy state.

Substrate Roughness Speeds Up Segmental Dynamics of Thin Polymer Films.

We show that the segmental mobility of thin films of poly(4-chlorostyrene) prepared under nonequilibrium conditions gets enhanced in the proximity of rough substrates. This trend is in contrast to existing treatments of roughness which conclude it is a source of slower dynamics, and to measurements of thin films of poly(2-vinylpiridine), whose dynamics is roughness invariant. Our experimental evidence indicates the faster interfacial dynamics originate from a reduction in interfacial density, due to the noncomplete filling of substrate asperities. Importantly, our results agree with the same scaling that describes the density dependence of bulk materials, correlating segmental mobility to a term exponential in the specific volume, and with empirical relations linking an increase in glass transition temperature to larger interfacial energy.

Density of Obstacles Affects Diffusion in Adsorbed Polymer Layers.

The translational diffusion of molecules dispersed into polymer matrices slows down tremendously when approaching a nonrepulsive interface. To unravel the origin of this phenomenon, we investigated the diffusion of molecular probes in the direction normal to an adsorbing wall. Using adsorbed polymer layers as matrices, we were able to decouple interfacial and finite size effects and determined the relation between the diffusion time and the area available at the polymer/solid interface. Based on the results of our investigation, we present a physical picture, suggesting that the reduction in diffusion rate is correlated to the degree of chain adsorption onto the substrate, that is, the density of surface obstacles encountered by tracer molecules.

Surface-Bulk Interplay in Vapor-Deposited Glasses: Crossover Length and the Origin of Front Transformation.

Thin film stable glasses transform into a liquid by a moving front that propagates from surfaces or interfaces with higher mobility. We use calorimetric data of vapor-deposited glasses of different thicknesses and stabilities to identify the role of glassy and liquid dynamics on the transformation process. By invoking the existence of an ultrathin intermediate layer whose transformation strongly depends on the properties of both the liquid and the glass, we show that the recovery to equilibrium is driven by the mismatch in the dynamics between glass and liquid. The lifetime of this intermediate layer associated with the moving front is the geometric mean between the bulk transformation time and the alpha relaxation time. Within this view, we explain the observed dependencies of the growth front velocity and the crossover length with both stability and temperature. Extrapolation of these results points towards ordinary thin film glasses transforming via a frontlike transformation mechanism if heated sufficiently fast, establishing a close connection between vapor-deposited and liquid-cooled glasses.

Kinetic arrest of front transformation to gain access to the bulk glass transition in ultrathin films of vapour-deposited glasses.

Physical vapour deposition has emerged as the technique to obtain glasses of unbeatable stability. However, vapour deposited glasses exhibit a different transformation mechanism to ordinary glasses produced from liquid. Vapour deposited glasses of different thermodynamic stability, from ultrastable to those similar to ordinary glasses, transform into the liquid state via front propagation starting at the most mobile surfaces/interfaces, at least for the first stages of the transformation, eventually dynamiting the high thermal stability achieved for some of these glasses. A previous study showed that it was possible to avoid this transformation front by capping the films with a higher Tg material. We show here fast calorimetry measurements on TPD and IMC vapour deposited glasses capped respectively with TCTA and TPD. This capped configuration is very effective in suppressing the heterogeneous transformation of the stable glasses into the supercooled liquid and shifts the devitrification temperature to much higher values, where the bulk homogeneous mechanism becomes active. This approach may be useful to further study the bulk glass transition in thin films.

Why is the change of the Johari-Goldstein ß-relaxation time by densification in ultrastable glass minor?

Ultrastable glasses (USG) formed by vapor deposition are considerably denser. The onset temperature of devitrification, Ton, is significantly higher than Ton or Tg of ordinary glass (OG) formed by cooling, which implies an increase of the structural α-relaxation time by many orders of magnitude in USG compared to that in OG at the same temperature. However, for a special type of secondary relaxation having properties strongly connected to those of the α-relaxation, called the Johari-Goldstein ß-relaxation, its relaxation time in USG is about an order of magnitude slower than that in OG and it has nearly the same activation energy, Eß. The much smaller change in τß and practically no change in Eß by densification in USG are in stark contrast to the behavior of the α-relaxation. This cannot be explained by asserting that the Johari-Goldstein (JG) ß-relaxation is insensitive to densification in USG, since the JG ß-relaxation strength is significantly reduced in USG to such a level that it would require several thousands of years of aging for an OG to reach the same state, and therefore the JG ß-relaxation does respond to densification in USG like the α-relaxation. Here, we provide an explanation based on two general properties established from the studies of glasses and liquids at elevated pressures and applied to USG. The increase in density of the glasses formed under high pressure can be even larger than that in USG. One property is the approximate invariance of the ratio τα(Ton)/τß(Ton) to density change at constant τα(Ton), and the other is the same ργ/T-dependence of τß in USG and OG where ρ is the density and γ is a material constant. These two properties are derived using the Coupling Model, giving a theoretical explanation of the phenomena. The explanation is also relevant for a full understanding of the experimental result that approximately the same surface diffusion coefficient is found in USG and OG with and without physical aging, and ultrathin films of a molecular glass-former.

Distinguishing different classes of secondary relaxations from vapour deposited ultrastable glasses.

Secondary relaxations persistent in the glassy state after structural arrest are especially relevant for the properties of the glass. A major thrust in research in dynamics of glass-forming liquids is to identify what secondary relaxations exhibit a connection to the structural relaxation and are hence more relevant. Via the Coupling Model, secondary relaxations having such connection have been identified by properties similar to the primitive relaxation of the Coupling Model and are called the Johari-Goldstein (JG) ß-relaxations. They involve the motion of the entire molecule and act as the precursor of the structural α-relaxation. The change in dynamics of the secondary relaxation by aging an ordinary glass is one way to understand the connection between the two relaxations, but the results are often equivocal. Ultrastable glasses, formed by physical vapour deposition, exhibit density and enthalpy levels comparable to ordinary glasses aged for thousands of years, as well as some particular molecular arrangement. Thus, ultrastable glasses enable the monitoring of the evolution of secondary processes in case aging does not provide any definitive information. Here, we study the secondary relaxation of several ultrastable glasses to identify different types of secondary relaxations from their different relationship with the structural relaxation. We show the existence of two clearly differentiated groups of relaxations: those becoming slower in the ultrastable state and those becoming faster, with respect to the ordinary unaged glass. We propose ultrastability as a way to distinguish between secondary processes arising from the particular microstructure of the system and those connected in properties to and acting as the precursor of the structural relaxation in the sense of the Coupling Model.

Secondary relaxation in ultrastable etoricoxib: evidence of correlation with structural relaxation.

Secondary relaxations are fundamental for their impact in the properties of glasses and for their inseparable connection to the structural relaxation. Understanding their density dependence and aging behavior is key to fully address the nature of glasses. Ultrastable glasses establish a new benchmark to study the characteristics of secondary relaxations, since their enthalpy and density levels are unattainable by other routes. Here, we use dielectric spectroscopy at ambient and elevated pressures to study the characteristics of the secondary relaxation in ultrastable etoricoxib, reporting a 71% decrease in dielectric strength and one decade increase in relaxation time compared to the ordinary glass. Interestingly, we find an unprecedented connection between secondary and structural relaxations in ultrastable etoricoxib in exactly the same manner as in the ordinary glass, manifested through different properties, such as aging and devitrification. These results further support and extend the general validity of the connection between the secondary and structural relaxation.

Emergence of a substrate-temperature-dependent dielectric process in a prototypical vapor deposited hole-transport glass.

Since the discovery of ultrastability, vapor deposition has emerged as a relevant tool to further understand the nature of glasses. By this route, the density and average orientation of glasses can be tuned by selecting the proper deposition conditions. Dielectric spectroscopy, on the other hand, is a basic technique to study the properties of glasses at a molecular level, probing the dynamics of dipoles or charge carriers. Here, and for the first time, we explore the dielectric behavior of vapor deposited N,N-Diphenyl-N,N'bis(methylphenyl)-1,1'-biphenyl-4,4'-diamines (TPD), a prototypical hole-transport material, prepared at different deposition temperatures. We report the emergence of a new relaxation process which is not present in the ordinary glass. We associate this process to the Maxwell-Wagner polarization observed in heterogeneous systems, and induced by the enhanced mobility of charge carriers in the more ordered vapor deposited glasses. Furthermore, the associated activation energy establishes a clear distinction between two families of glasses, depending on the selected substrate-temperature range. This finding positions dielectric spectroscopy as a unique tool to investigate the structural and electronic properties of charge transport materials and remarks the importance of controlling the deposition conditions, historically forgotten in the preparation of optoelectronic devices.

Why is surface diffusion the same in ultrastable, ordinary, aged, and ultrathin molecular glasses?

Recently Fakhraai and coworkers measured surface diffusion in ultrastable glass produced by vapor deposition, ordinary glass with and without physical aging, and ultrathin films of the same molecular glass-former, N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD). Diffusion on the surfaces of all these glasses is greatly enhanced compared with the bulk diffusion similar to that previously found by others, but remarkably the surface diffusion coefficients DS measured are practically the same. The observed independence of DS from changes of structural α-relaxation due to densification or finite-size effect has an impact on the current understanding of the physical origin of enhanced surface diffusion. We have demonstrated before and also here that the primitive relaxation time τ0 of the coupling model, or its analogue τß, the Johari-Goldstein ß-relaxation, can explain quantitatively the enhancement found in ordinary glasses. In this paper, we assemble together considerable experimental evidence to show that the changes in τß and τ0 of ultrastable glasses, aged ordinary glasses, and ultrathin-films are all insignificant when compared with ordinary glasses. Thus, in the context of the explanation of the enhanced surface diffusion given by the coupling model, these collective experimental facts on τß and τ0 further explain approximately the same DS in the different glasses of TPD as found by Fakhraai and coworkers.

The role of thermodynamic stability in the characteristics of the devitrification front of vapour-deposited glasses of toluene.

Physical vapour deposition (PVD) has settled in as an alternative method to prepare glasses with significantly enhanced properties, providing new insights into the understanding of glass transition. One of the striking properties of some PVD glasses is their transformation into liquid via a heterogeneous mechanism that initiates at surfaces/interfaces. Here, we use membrane-based fast-scanning nanocalorimetry (104 K s-1) to analyse the variables that govern the transformation mechanism of vapour-deposited toluene glasses with different stabilities. Thin films ranging from 20 to 250 nm were prepared at deposition temperatures between 0.70 and 1.15 times the glass transition temperature. We show how a propagating growth front is the initial transformation mechanism in all the vapour deposited samples, revealing a clear tendency to faster front velocities for less stable samples. Contrary to other glass-formers such as indomethacin, toluene shows a one-to-one relationship between limiting fictive temperature and front velocity. We associate this behaviour with the much simpler molecular geometry of toluene, which would prevent the presence of strong preferential molecular arrangements in the glass. However, the propagation distance of the growth front before the homogenous transformation mechanism dominates the transition is found to be dependent on the preparation conditions rather than on the thermal stability of the glass. Understanding the link between the growth variables and the properties of PVD glasses is crucial for finding and developing potential applications of this type of glass.

Transformation kinetics of vapor-deposited thin film organic glasses: the role of stability and molecular packing anisotropy.

While ordinary glasses transform into supercooled liquid via a homogeneous bulk mechanism, thin film glasses of higher stability transform heterogeneously by a front propagating from the surface and/or the interfaces. In this work, we use quasi-adiabatic fast scanning nanocalorimetry to determine the heat capacity of thin glassy layers of indomethacin vapor-deposited in a broad temperature range of 110 K below the glass transition temperature. Their variation in fictive temperature amounts to 40 K. We show that a propagating front is the initial transformation mechanism in all cases. Using an ad hoc surface normalization procedure we determine the corresponding growth front velocity for the whole range of deposition temperatures. Although the transformation rate changes by a factor of 10 between the most and less stable samples, the relation between the mobility of the front and the thermodynamic stability of the glass is not uniquely defined. Glasses grown above 280 K, which are at equilibrium with the supercooled liquid, present a different dependence of the growth front velocity on fictive temperature compared to glasses grown out of equilibrium at Tdep < 250 K. These glasses transform faster with increasing Tf. Our data clarify previous reports and support the evidence that the fictive temperature alone is not an absolute indicator of the properties of the glass, at least when its structure is not completely isotropic. To interpret the data, we propose that the growth front velocity depends on three terms: the mobility of the liquid at a given temperature, the mobility of the glass and the arrangement of the molecules in the glass.

Simultaneous nanocalorimetry and fast XRD measurements to study the silicide formation in Pd/a-Si bilayers.

The use of a membrane-based chip nanocalorimeter in a powder diffraction beamline is described. Simultaneous wide-angle X-ray scattering and scanning nanocalorimetric measurements are performed on a thin-film stack of palladium/amorphous silicon (Pd/a-Si) at heating rates from 0.1 to 10 K s(-1). The nanocalorimeter works under a power-compensation scheme previously developed by the authors. Kinetic and structural information of the consumed and created phases can be obtained from the combined techniques. The formation of Pd2Si produces a broad calorimetric peak that contains overlapping individual processes. It is shown that Pd consumption precedes the formation of the crystalline Pd2Si phase and that the crystallite size depends on the heating rate of the experiment.

Probing equilibrium glass flow up to exapoise viscosities.

Glasses are out-of-equilibrium systems aging under the crystallization threat. During ordinary glass formation, the atomic diffusion slows down, rendering its experimental investigation impractically long, to the extent that a timescale divergence is taken for granted by many. We circumvent these limitations here, taking advantage of a wide family of glasses rapidly obtained by physical vapor deposition directly into the solid state, endowed with different "ages" rivaling those reached by standard cooling and waiting for millennia. Isothermally probing the mechanical response of each of these glasses, we infer a correspondence with viscosity along the equilibrium line, up to exapoise values. We find a dependence of the elastic modulus on the glass age, which, traced back to the temperature steepness index of the viscosity, tears down one of the cornerstones of several glass transition theories: the dynamical divergence. Critically, our results suggest that the conventional wisdom picture of a glass ceasing to flow at finite temperature could be wrong.

Evaluation of growth front velocity in ultrastable glasses of indomethacin over a wide temperature interval.

Ultrastable thin film glasses transform into supercooled liquid via propagating fronts starting from the surface and/or interfaces. In this paper, we analyze the consequences of this mechanism in the interpretation of specific heat curves of ultrastable glasses of indomethacin for samples with varying thickness from 20 nm up to several microns. We demonstrate that ultrastable films above 20 nm have identical fictive temperatures and that the apparent change of onset temperature in the specific heat curves originates from the mechanism of transformation and the normalization procedure. An ad hoc surface normalization of the heat capacity yields curves which collapse into a single one irrespective of their thickness. Furthermore, we fit the surface-normalized specific heat curves with a heterogeneous transformation model to evaluate the velocity of the growth front over a much wider temperature interval than previously reported. Our data expands previous values up to Tg + 75 K, covering 12 orders of magnitude in relaxation times. The results are consistent with preceding experimental and theoretical studies. Interestingly, the mobility of the supercooled liquid in the region behind the transformation front remains constant throughout the thickness of the layers.

Suppression of tunneling two-level systems in ultrastable glasses of indomethacin.

Glasses and other noncrystalline solids exhibit thermal and acoustic properties at low temperatures anomalously different from those found in crystalline solids, and with a remarkable degree of universality. Below a few kelvin, these universal properties have been successfully interpreted using the tunneling model, which has enjoyed (almost) unanimous recognition for decades. Here we present low-temperature specific-heat measurements of ultrastable glasses of indomethacin that clearly show the disappearance of the ubiquitous linear contribution traditionally ascribed to the existence of tunneling two-level systems (TLS). When the ultrastable thin-film sample is thermally converted into a conventional glass, the material recovers a typical amount of TLS. This remarkable suppression of the TLS found in ultrastable glasses of indomethacin is argued to be due to their particular anisotropic and layered character, which strongly influences the dynamical network and may hinder isotropic interactions among low-energy defects, rather than to the thermodynamic stabilization itself. This explanation may lend support to the criticisms by Leggett and others [Yu CC, Leggett AJ (1988) Comments Condens Matter Phys 14(4):231-251; Leggett AJ, Vural DC (2013) J Phys Chem B 117(42):12966-12971] to the standard tunneling model, although more experiments in different kinds of ultrastable glasses are needed to ascertain this hypothesis.