Enhanced surface mobility is critical in producing stable glasses during physical vapor deposition. In amorphous selenium (a-Se) both the structure and dynamics of the surface can be altered when exposed to above-bandgap light. Here we investigate the effect of light on the properties of vapor-deposited a-Se glasses at a range of substrate temperatures and deposition rates. We demonstrate that deposition both under white light illumination and in the dark results in thermally and kinetically stable glasses. Compared to glasses deposited in the dark, stable a-Se glasses formed under white light have reduced thermal stability, as measured by lower density change, but show significantly improved kinetic stability, measured as higher onset temperature for transformation. While light induces enhanced mobility that penetrates deep into the surface, resulting in lower density during vapor deposition, it also acts to form more networked structures at the surface, which results in a state that is kinetically more stable with larger optical birefringence. We demonstrate that the structure formed during deposition with light is a state that is not accessible through liquid quenching, aging, or vapor deposition in the dark, indicating the formation of a unique amorphous solid state.
- NSF-PAR ID:
- 10347909
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 156
- Issue:
- 24
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- 244703
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
null (Ed.)By measuring the increments of dielectric capacitance (Δ C ) and dissipation (Δtan δ ) during physical vapor deposition of a 110 nm film of a molecular glass former, we provide direct evidence of the mobile surface layer that is made responsible for the extraordinary properties of vapor deposited glasses. Depositing at a rate of 0.1 nm s −1 onto a substrate at T dep = 75 K = 0.82 T g , we observe a 2.5 nm thick surface layer with an average relaxation time of 0.1 s, while the glass growing underneath has a high kinetic stability. The level of Δtan δ continues to decrease for thousands of seconds after terminating the deposition process, indicating a slow aging-like increase in packing density near the surface. At very low deposition temperatures, 32 and 42 K, the surface layer thicknesses and mobilities are reduced, as are the kinetic stabilities.more » « less
-
Glasses formed by physical vapor deposition (PVD) are an interesting new class of materials, exhibiting properties thought to be equivalent to those of glasses aged for thousands of years. Exerting control over the structure and properties of PVD glasses formed with different types of glass-forming molecules is now an emerging challenge. In this work, we study coarse-grained models of organic glass formers containing fluorocarbon tails of increasing length, corresponding to an increased tendency to form microstructures. We use simulated PVD to examine how the presence of the microphase-separated domains in the supercooled liquid influences the ability to form stable glasses. This model suggests that increasing molecule tail length results in decreased thermodynamic stability of the molecules in PVD films. The reduced stability is further linked to the reduced ability of these molecules to equilibrate at the free surface during PVD. We find that, as the tail length is increased, the relaxation times near the surface of the supercooled equilibrium liquid films of these molecules are slowed and become essentially bulk-like, due to the segregation of the fluorocarbon tails to the free surface. Surface diffusion is also markedly reduced due to clustering of the molecules at the surface. Based on these results, we propose a trapping mechanism where tails are unable to move between local phase-separated domains on the relevant deposition time scales.
-
When aged below the glass transition temperature,
, the density of a glass cannot exceed that of the metastable supercooled liquid (SCL) state, unless crystals are nucleated. The only exception is when another polyamorphic SCL state exists, with a density higher than that of the ordinary SCL. Experimentally, such polyamorphic states and their corresponding liquid–liquid phase transitions have only been observed in network-forming systems or those with polymorphic crystalline states. In otherwise simple liquids, such phase transitions have not been observed, either in aged or vapor-deposited stable glasses, even near the Kauzmann temperature. Here, we report that the density of thin vapor-deposited films of N ,N ′-bis(3-methylphenyl)-N ,N ′-diphenylbenzidine (TPD) can exceed their corresponding SCL density by as much as 3.5% and can even exceed the crystal density under certain deposition conditions. We identify a previously unidentified high-density supercooled liquid (HD-SCL) phase with a liquid–liquid phase transition temperature () ∼35 K below the nominal glass transition temperature of the ordinary SCL. The HD-SCL state is observed in glasses deposited in the thickness range of 25 to 55 nm, where thin films of the ordinary SCL have exceptionally enhanced surface mobility with large mobility gradients. The enhanced mobility enables vapor-deposited thin films to overcome kinetic barriers for relaxation and access the HD-SCL state. The HD-SCL state is only thermodynamically favored in thin films and transforms rapidly to the ordinary SCL when the vapor deposition is continued to form films with thicknesses more than 60 nm. -
Abstract When exposed to water, silicate glasses and minerals can form a hydrated gel surface layer concurrent with a decrease in their dissolution kinetics—a phenomenon known as the “passivation effect.” However, the atomic-scale origin of such passivation remains debated. Here, based on reactive molecular dynamics simulations, we investigate the hydration of a series of modified borosilicate glasses with varying compositions. We show that, upon the aging of the gel, the passivation effect manifests itself as a drop in hydrogen mobility. Nevertheless, only select glass compositions are found to exhibit some passivation. Based on these results, we demonstrate that the passivation effect cannot be solely explained by the repolymerization of the hydrated gel upon aging. Rather, we establish that the propensity for passivation is intrinsically governed by the reorganization of the medium-range order structure of the gel upon aging and, specifically, the formation of small silicate rings that hinder water mobility.