Stable glasses (SGs) are formed through surface-mediated equilibration (SME) during physical vapor deposition (PVD). Unlike intermolecular interactions, the role of intramolecular degrees of freedom in this process remains unexplored. Here, using experiments and coarse-grained molecular dynamics simulations, we demonstrate that varying dihedral rotation barriers of even a single bond, in otherwise isomeric molecules, can strongly influence the structure and stability of PVD glasses. These effects arise from variations in the degree of surface mobility, mobility gradients, and mobility anisotropy, at a given deposition temperature ( T dep ). At high T dep , flexible molecules have access to more configurations, which enhances the rate of SME, forming isotropic SGs. At low T dep , stability is achieved by out of equilibrium aging of the surface layer. Here, the poor packing of rigid molecules enhances the rate of surface-mediated aging, producing stable glasses with layered structures in a broad range of T dep . In contrast, the dynamics of flexible molecules couple more efficiently to the glass layers underneath, resulting in reduced mobility and weaker mobility gradients, producing unstable glasses. Independent of stability, the flattened shape of flexible molecules can also promote in-plane orientational order at low T dep . These results indicate that small changes in intramolecular relaxation barriers can be used as an approach to independently tune the structure and mobility profiles of the surface layer and, thus, the stability and structure of PVD glasses.
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Generic packing motifs in vapor-deposited glasses of organic semiconductors
We study the structure of vapor-deposited glasses of five common organic semiconductors as a function of substrate temperature during deposition, using synchrotron X-ray scattering. For deposition at a substrate temperature of ∼0.8 T g (where T g is the glass transition temperature), we find a generic tendency towards “face-on” packing in glasses of anisotropic molecules. At higher substrate temperature however this generic behavior breaks down; glasses of rod-shaped molecules exhibit a more pronounced tendency for end-on packing. Our study provides guidelines to create face-on and end-on packing motifs in organic glasses, which can promote efficient charge transport in OLED and OFET devices respectively.
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- Award ID(s):
- 1720415
- NSF-PAR ID:
- 10135562
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 15
- Issue:
- 38
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 7590 to 7595
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Glasses prepared by physical vapor deposition (PVD) are anisotropic, and the average molecular orientation can be varied significantly by controlling the deposition conditions. While previous work has characterized the average structure of thick PVD glasses, most experiments are not sensitive to the structure near an underlying substrate or interface. Given the profound influence of the substrate on the growth of crystalline or liquid crystalline materials, an underlying substrate might be expected to substantially alter the structure of a PVD glass, and this near-interface structure is important for the function of organic electronic devices prepared by PVD, such as organic light-emitting diodes. To study molecular packing near buried organic–organic interfaces, we prepare superlattice structures (stacks of 5- or 10-nm layers) of organic semiconductors, Alq3 (Tris-(8-hydroxyquinoline)aluminum) and DSA-Ph (1,4-di-[4-(N,
N -diphenyl)amino]styrylbenzene), using PVD. Superlattice structures significantly increase the fraction of the films near buried interfaces, thereby allowing for quantitative characterization of interfacial packing. Remarkably, both X-ray scattering and spectroscopic ellipsometry indicate that the substrate exerts a negligible influence on PVD glass structure. Thus, the surface equilibration mechanism previously advanced for thick films can successfully describe PVD glass structure even within the first monolayer of deposition on an organic substrate. -
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
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X-ray scattering has been used to characterize glassy itraconazole (ITZ) prepared by cooling at different rates. Faster cooling produces ITZ glasses with lower (or zero) smectic order with more sinusoidal density modulation, larger molecular spacing, and shorter lateral correlation between the rod-like molecules. We find that each glass is characterized by not one, but two fictive temperatures Tf(the temperature at which a chosen order parameter is frozen in the equilibrium liquid). The higher Tfis associated with the regularity of smectic layers and lateral packing, while the lower Tfwith the molecular spacings between and within smectic layers. This indicates that different structural features are frozen on different timescales. The two timescales for ITZ correspond to its two relaxation modes observed by dielectric spectroscopy: the slower δ mode (end-over-end rotation) is associated with the freezing of the regularity of molecular packing and the faster α mode (rotation about the long axis) with the freezing of the spacing between molecules. Our finding suggests a way to selectively control the structural features of glasses.
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Abstract Ultra‐stable amorphous fluoropolymers glasses were created using vacuum pyrolysis deposition (VPD). Glass films with thickness ranging from 90 to 160 nm were grown at a substrate temperature of 0.86
T g, whereT gis the glass transition temperature of the virgin polymer and is in units of K. Atomic force microscope (AFM) dilatometry measurements were conducted to investigate density behavior of the ultra‐stable glasses. Thickness measurements were made in stepwise fashion over a range of temperatures from ambient to above theT g. Results show that the intersections of the line for the equilibrium liquid and those for the rejuvenated and stable glasses identifying the fictive temperatureT fresult inT f, rejuvenated = 347.3 K andT f, stable = 269.5 K, that is, nearly 80 K below theT gof the rejuvenated material and well below the notional Kauzmann temperature as estimated from the Vogel‐Fultcher‐Tammann (VFT) analysis of the cooling rate dependence of the calorimetric glass transition temperature reported previously. The results corroborate the published calorimetric results on the same ultra‐stable fluoropolymer glasses that witnessedT freductions of up to 62.6 K below theT gof the rejuvenated system. In addition, to demonstrate the versatility of the AFM dilatometry methodology for the thin film response, isothermal de‐aging experiments were carried out to illustrate the devitrification kinetics. We also carried out one of the Kovacs’ signature key experiments, the asymmetry of approach, to further illustrate the method.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c9sm01155b
