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M. D. Ediger

Publications and source records attributed to M. D. Ediger.

At least 19 recordsLinked to original sources
arXiv2026

Comparison of mechanical and molecular measures of mobility during constant strain rate deformation of a PMMA glass

We performed constant strain rate deformation and stress relaxation on a poly(methyl methacrylate) glass at Tg - 19 K, utilizing three strain rates and initiating the stress relaxation over a large range of strain values. Following previous workers, we interpret the initial rate of decay of the stress during the relaxation experiment as a purely mechanical measure of mobility for the system. In our experiments, the mechanical mobility obtained in this manner changes by less than a factor of 3 prior to yield. During these mechanical experiments, we also performed an optical measurement of segmental mobility based upon the reorientation of a molecular probe; we observe that the probe mobility increases up to a factor of 100 prior to yield. In the post-yield regime, in contrast, the mobilities determined mechanically and by probe reorientation are quite similar and show a similar dependence upon the strain rate. Dynamic heterogeneity is found to initially decrease during constant strain rate deformation and then remain constant in the post-yield regime. These combined observations of mechanical mobility, probe mobility, and dynamic heterogeneity present a challenge for theoretical modeling of polymer glass deformation.

cond-mat.soft↗
arXiv2026

Highly Stable Glasses of cis-Decalin and cis/trans-Decalin Mixtures

In situ AC nanocalorimetry was used to measure the reversing heat capacity of vapor-deposited glasses of decahydronaphthalene (decalin). Glasses with low heat capacity and high kinetic stability, as compared to the corresponding liquid-cooled glass, were prepared from cis-decalin and from several cis/trans-decalin mixtures. This is the first report of highly stable glass formation for molecular mixtures. The 50/50 cis/trans-decalin mixture is the highest fragility material reported to produce an ultrastable glass. The 50/50 mixture exhibited high kinetic stability, with an ~500 nm film deposited at 116 K (0.86 Tg,) displaying a transformation time equivalent to 104.4 times the structural relaxation time of the supercooled liquid at the annealing temperature. Cis-decalin and the decalin mixture formed stable glasses that had heat capacities as much as 4.5% lower than the liquid-cooled glass.

cond-mat.soft↗
arXiv2026

One micron length scale controls kinetic stability of low energy glasses

AC nanocalorimetry was used to measure the reversing heat capacity Cp of low energy indomethacin glasses as they isothermally transform into the supercooled liquid. As the film thickness increases from 75 to 600 nm, the transformation time increases by more than an order of magnitude, consistent with a surface-initiated transformation mechanism. Eventually, the transformation time becomes constant for films between 1.4 and 30 microns indicating a distinct bulk transformation pathway. The observation of size-dependent transformation kinetics for glass samples approaching 1 micron is unprecedented. We interpret the crossover in thickness dependence at 1 micron to signify the average distance between transformation initiation sites in the bulk low energy glass.

cond-mat.soft↗
arXiv2026

Highly organized smectic-like packing in vapor-deposited glasses of a liquid crystal

Glasses of a model smectic liquid crystal-forming molecule, itraconazole, were prepared by vapor deposition onto substrates with temperatures ranging from Tsubstrate = 0.78 Tg to 1.02 Tg, where Tg = 330 K is the glass transition temperature. The films were characterized using x-ray scattering techniques. For Tsubstrate near and below Tg, glasses with layered smectic-like structures can be prepared and the layer spacing can be tuned by 16% through choice of Tsubstrate. Remarkably, glasses prepared with Tsubstrate above Tg exhibit much higher structural organization than a thermally annealed film. These results are explained by a mechanism based upon preferred molecular orientation and enhanced molecular motion at the free surface, indicating that molecular organization in the glass is independent of the anchoring preferred at the substrate. These results suggest new strategies of optimizing molecular packing within active layers of organic electronic and optoelectronic devices.

cond-mat.soft↗
arXiv2026

Reversing strain deformations probe mechanisms for enhanced segmental mobility of polymer glasses

Optical probe reorientation measurements were performed to monitor changes in segmental dynamics resulting from the nonlinear deformation of a polymer glass. Segmental dynamics were monitored in a poly(methyl methacrylate) glass near Tg before and after a series of reversing deformations in which the sample was extended at constant strain rate and then allowed to retract back to zero stress at constant strain rate. Evidence of a rejuvenation mechanism, as quantified by a departure of the segmental dynamics from the quiescent aging dynamics after the reversing deformation, is observed for deformations which reach 60% of the yield strain or greater. By this measure, a saturation of the rejuvenation mechanism is not observed until at least five times the yield strain. For comparison, purely mechanical measurements of rejuvenation, based upon the reduction of the yield stress in a subsequent deformation, were also performed. These purely mechanical experiments show broad qualitative agreement with the probe reorientation experiments, but quantitatively differ in the pre-yield regime. The results are discussed in the context of recent theoretical approaches and simulations which provide a molecular-level description of polymer glass deformation.

cond-mat.soft↗
arXiv2026

A molecular perspective on the yield and flow of polymer glasses: The role of enhanced segmental dynamics during active deformation

The mechanical properties of polymer glasses are often critical in determining the best material for a particular application. Extremely stiff materials (high modulus) may be important for some applications while avoiding catastrophic failure due to fracture (high toughness) may be more important for others. The mechanical properties of a polymer glass will depend upon both molecular structure and many experimental variables, including temperature and the mode of deformation (tension, compression, or shear). In this chapter we discuss the mechanical response of polymer glasses from a molecular perspective. In particular, we consider how deformation changes the rate at which polymer segments rearrange and how this in turn influences the mechanical response of the material. It will be shown that this focus on the changes in dynamics provides an understanding of many important features of polymer glass deformation. Of course, it is also true that the structure of a polymer glass must be altered by nonlinear deformation. Although not a major focus, we will make some comments about these structural changes at the end of this chapter.

cond-mat.soft↗
arXiv2026

Rejuvenation versus overaging: The effect of cyclic loading/unloading on the segmental dynamics of PMMA glasses

The acceleration of structural relaxation or physical aging by deformation, known as overaging, has been reported in experiments and simulations of polymer and colloid glasses, and correctly accounting for overaging is important for the prediction of the long-term behavior of polymer glasses in engineering applications. Here the effects of cyclic loading/unloading on the segmental dynamics and mechanical properties of PMMA glasses are investigated using a probe reorientation technique and time-aging time superposition of the mechanical response, respectively. Sets of 5000 tensile loading/unloading cycles were performed at temperatures between Tg - 10 K and Tg - 25 K with cycle extension strains ranging from 0.003 to 0.007. After cycling, the segmental dynamics measured with the probe reorientation technique either remained unchanged or were faster relative to an undeformed sample. The relaxation times of cycled glasses recovered with a common time scale on the order of their aging time, indicating that they retain a memory of their original age, as opposed to a full erasure of their thermal and mechanical history. Surprisingly, changes as a result of cycling were more obvious in probe reorientation measurements than in the mechanical properties, suggesting that the probe reorientation technique can sensitively detect nonlinear effects of deformation. No evidence of overaging was observed in the optical or mechanical measurements as a result of these cyclic loading/unloading experiments.

cond-mat.soft↗
arXiv2026

Over what length scale does an inorganic substrate perturb the structure of a glassy organic semiconductor?

While the bulk structure of vapor-deposited glasses has been extensively studied, structure at buried interfaces has received little attention, despite being important for organic electronic applications. To learn about glass structure at buried interfaces, we study the structure of vapor-deposited glasses of the organic semiconductor DSA-Ph (1,4-di-[4-(N,N-diphenyl)amino]styryl-benzene) as a function of film thickness; structure is probed with grazing incidence X-ray scattering. We deposit on silicon and gold substrates and span a film thickness range of 10-600 nm. Our experiments demonstrate that interfacial molecular packing in vapor-deposited glasses of DSA-Ph is more disordered compared to the bulk. At a deposition temperature near room temperature, we estimate ~ 8 nm near the substrate can have modified molecular packing. Molecular dynamics simulations of a coarse-grained representation of DSA-Ph reveal a similar length scale. In both the simulations and the experiments, deposition temperature controls glass structure beyond this interfacial layer of a few nanometers.

cond-mat.mtrl-sci↗
arXiv2026

Stable Glasses of Organic Semiconductor Resist Crystallization

The instability of glassy solids poses a key limitation to their use in several technological applications. Well-packed organic glasses, prepared by physical vapor deposition (PVD), have drawn attention recently because they can exhibit significantly higher thermal and chemical stability than glasses prepared from more traditional routes. We show here that PVD glasses can also show enhanced resistance to crystallization. By controlling the deposition temperature, resistance towards crystallization can be enhanced by at least a factor of ten in PVD glasses of the model organic semiconductor Alq3 (Tris(8-hydroxyquinolinato) aluminum). PVD glasses of Alq3 first transform into a supercooled liquid before crystallizing. By controlling the deposition temperature, we increase the glass to liquid transformation time thereby also increasing the overall time for crystallization. We thus demonstrate a new strategy to stabilize glasses of organic semiconductors against crystallization, which is a common failure mechanism in OLED (organic light emitting diode) devices.

cond-mat.mtrl-sci↗
arXiv2026

Using Deposition Rate and Substrate Temperature to Manipulate Liquid Crystal-like Order in a Vapor-deposited Hexagonal Columnar Glass

We investigate vapor-deposited glasses of a phenanthroperylene-ester, known to form an equilibrium hexagonal columnar phase, and show that liquid crystal-like order can be manipulated by the choice of deposition rate and substrate temperature during deposition. We find that rate-temperature superposition (RTS), the equivalence of lowering deposition rate and raising substrate temperature, can be used to predict and control the molecular orientation in vapor-deposited glasses over a wide range of substrate temperatures (0.75Tg to 1.0Tg). This work extends RTS to a new structural motif, hexagonal columnar liquid crystal order, which is being explored for organic electronics applications. By several metrics, including the apparent average face-to-face nearest-neighbor distance, PVD glasses of the phenanthroperylene-ester are as ordered as the glass prepared by cooling the equilibrium liquid crystal. By other measures, the PVD glasses are less ordered than the cooled liquid crystal. We explain the difference in the maximum attainable order with the existence of a gradient in molecular mobility at the free surface of a liquid crystal, and its impact upon different mechanisms of structural rearrangement. This free surface equilibration mechanism explains the success of the RTS principle and provides guidance regarding the types of order most readily enhanced by vapor deposition. This work extends the applicability of RTS to include molecular systems with a diverse range of higher-order liquid crystalline morphologies that could be useful for new organic electronic applications.

cond-mat.soft↗
arXiv2026

Surface Equilibration Mechanism Controls the Stability of a Model Co-deposited Glass Mixture of Organic Semiconductors

While previous work has identified the conditions for preparing ultrastable single-component organic glasses by physical vapor deposition (PVD), little is known about the stability of co-deposited mixtures. Here, we prepared binary PVD glasses of organic semiconductors, TPD (N,N-Bis(3-methylphenyl)-N,N-diphenylbenzidine) and m-MTDATA (4,4,4-Tris[phenyl(m-tolyl)amino]triphenylamine), with 50:50 mass concentration over a wide range of substrate temperatures (Tsub). The enthalpy and kinetic stability are evaluated with differential scanning calorimetry and spectroscopic ellipsometry. Binary organic semiconductor glasses with exceptional thermodynamic and kinetic stability comparable to the most stable single-component organic glasses are obtained when deposited at Tsub=0.78-0.90Tg (where Tg is the conventional glass transition temperature). When deposited at 0.94Tg, the enthalpy of m-MTDATA/TPD glass equals that expected for the equilibrium liquid at that temperature. Thus, the surface equilibration mechanism previously advanced for single-component PVD glasses is also applicable for these co-deposited glasses. These results provide an avenue for designing high-performance organic electronic devices.

cond-mat.mtrl-sci↗
arXiv2026

Overaging with stress in polymer glasses? Faster segmental dynamics despite larger yield stress!

It is well known that physical aging of polymer glasses increases their yield stress and affects their failure behavior. Studies indicate that application of moderate levels of stress during aging results in higher yield stress compared to aging in the absence of stress (quiescent aging). This has been interpreted to indicate that stress accelerates physical aging, and has been described as overaging. In this study, we age PMMA glasses under stress, and carry out direct measurement of segmental dynamics during and after aging by using a probe reorientation technique. We observe that samples aged under stress, despite having higher yield stress, have faster segmental dynamics after stress release than quiescently aged samples. This contradicts the overaging interpretation, for the range of conditions explored here. Our results indicate that yield stress is not a simple function of structural relaxation time and theoretical models based on this understanding need to be revised.

cond-mat.soft↗
arXiv2026

Segmental Dynamics in the Strain-hardening Regime for Poly(methyl methacrylate) Glasses with and without Melt-stretching

Strain-hardening is a feature of polymer glasses during large deformation, which helps to stabilize the glasses against breakage. Experimentally, little is known about the segmental dynamics during strain-hardening, and such data is important for building a molecular-level theory of polymer glasses deformed in this regime. Here, using a photobleaching technique, we measured the segmental dynamics of lightly-crosslinked poly(methyl methacrylate) (PMMA) glasses with and without melt-stretching, which were deformed into the strain-hardening regime with local engineering strain rates from 10^-4.6 s^-1 to 10^-4 s^-1 at Tg-23K and Tg-33K. We find that melt-stretched PMMA glasses show a more prominent strain-hardening feature and faster segmental dynamics by a factor of about 15% compared to PMMA without melt-stretching. At a given true strain rate, the segmental dynamics of PMMA without melt-stretching are accelerated in the deep strain-hardening regime from the value just beyond yield, by up to 40% at 0.8 true strain. Our observations are in agreement with previously published simulation results.

cond-mat.soft↗
arXiv2026

High density two-component glasses of organic semiconductors prepared by physical vapor deposition

Physical Vapor Deposition (PVD) is widely utilized for the production of organic semiconductor devices due to its ability to form thin layers with exceptional properties. Although the layers in the device usually consist of two or more components, there is limited understanding about the fundamental characteristics of such multi-component vapor-deposited glasses. Here, spectroscopic ellipsometry was employed to characterize the densities, thermal stabilities and optical properties of co-vapor deposited NPD and TPD glasses across the entire range of composition. We find that co-deposited NPD and TPD form high density glasses with enhanced thermal stability. The dependences of density and stability upon substrate temperature are correlated, and the birefringence of the co-deposited glasses is determined by the reduced substrate temperature of mixtures. Additionally, we observe that the transformation of a highly stable and dense two component glass into its supercooled liquid initiates from the free surface and propagates into the bulk at constant velocity, like single component PVD glasses. All these features are consistent with the surface equilibration mechanism.

cond-mat.mtrl-sci↗
arXiv2026

Thermal stability of vapor-deposited stable glasses of an organic semiconductor

Vapor-deposited organic glasses can show enhanced kinetic stability relative to liquid-cooled glasses. When such stable glasses of model glassformers are annealed above the glass transition temperature Tg, they lose their thermal stability and transform into the supercooled liquid via constant velocity propagating fronts. In this work, we show that vapor-deposited glasses of an organic semiconductor, N,N-bis(3-methylphenyl)-N,N-diphenylbenzidine (TPD), also transform via propagating fronts. Using spectroscopic ellipsometry and a new high-throughput annealing protocol, we measure transformation front velocities for TPD glasses prepared with substrate temperatures (TSubstrate) from 0.63 to 0.96 Tg, at many different annealing temperatures. We observe that the front velocity varies by over an order of magnitude with TSubstrate, while the activation energy remains constant. Using dielectric spectroscopy, we measure the structural relaxation time of supercooled TPD. We find that the mobility of the liquid and the structure of the glass are independent factors in controlling the thermal stability of TPD films. In comparison to model glassformers, the transformation fronts of TPD have similar velocities and a similar dependence on TSubstrate, suggesting universal behavior. These results may aid in designing active layers in organic electronic devices with improved thermal stability.

cond-mat.soft↗
arXiv2026

Limited surface mobility inhibits stable glass formation for 2-ethyl-1-hexanol

Previous work has shown that vapor-deposition can prepare organic glasses with extremely high kinetic stabilities and other properties that would be expected from liquid-cooled glasses only after aging for thousands of years or more. However, recent reports have shown that some molecules form vapor-deposited glasses with only limited kinetic stability when prepared using conditions expected to yield a stable glass. In this work, we vapor deposit glasses of 2-ethyl-1-hexanol over a wide range of deposition rates and test several hypotheses for why this molecule does not form highly stable glasses under normal deposition conditions. The kinetic stability of 2-ethyl-1-hexanol glasses is found to be highly dependent on the deposition rate. For deposition at Tsubstrate = 0.90 Tg, the kinetic stability increases by 3 orders of magnitude (as measured by isothermal transformation times) when the deposition rate is decreased from 0.2 nm/s to 0.005 nm/s. We also find that, for the same preparation time, a vapor-deposited glass has much more kinetic stability than an aged liquid-cooled glass. Our results support the hypothesis that the formation of highly stable 2-ethyl-1-hexanol glasses is inhibited by limited surface mobility. We compare our deposition rate experiments to similar ones performed with ethylcyclohexane (which readily forms glasses of high kinetic stability); we estimate that the surface mobility of 2-ethyl-1-hexanol is more than 4 orders of magnitude less than that of ethylcyclohexane at 0.85 Tg.

cond-mat.soft↗
arXiv2026

Perspective: Highly stable vapor-deposited glasses

This article describes recent progress in understanding highly stable glasses prepared by physical vapor deposition and provides perspective on further research directions for the field. For a given molecule, vapor-deposited glasses can have higher density and lower enthalpy than any glass that can be prepared by the more traditional route of cooling a liquid, and such glasses also exhibit greatly enhanced kinetic stability. Because vapor-deposited glasses can approach the bottom of the amorphous part of the potential energy landscape, they provide insights into the properties expected for the ideal glass. Connections between vapor-deposited glasses, liquid-cooled glasses, and deeply supercooled liquids are explored. The generality of stable glass formation for organic molecules is discussed along with the prospects for stable glasses of other types of materials.

cond-mat.soft↗
arXiv2023

Using 4D STEM to probe mesoscale order in molecular glass films prepared by physical vapor deposition

Physical vapor deposition can be used to prepare highly stable organic glass systems where the molecules show orientational and translational ordering at the nanoscale. We have used low-dose four-dimensional scanning transmission electron microscopy (4D STEM), enabled by a fast direct electron detector, to map columnar order in glassy samples of a discotic mesogen using a 2 nm probe. Both vapor deposited and liquid cooled glassy films show domains of similar orientation, but their size varies from tens to hundreds of nanometers, depending on processing. Domain sizes are consistent with surface diffusion mediated ordering during film deposition. These results demonstrate the ability of low-dose 4D STEM to characterize mesoscale structure in a molecular glass system which may be relevant to organic electronics.

cond-mat.mtrl-sci↗