Vapor deposited thin films (∼100 nm thickness) of toluene and ethylbenzene grown by physical vapor deposition show enhanced stability with respect to samples slowly cooled from the liquid at a rate of 5 K min⁻¹. The heat capacity is measured in situ immediately after growth from the vapor or after re-freezing from the supercooled liquid at various heating rates using quasi-adiabatic nanocalorimetry. Glasses obtained from the vapor have low enthalpies and large heat capacity overshoots that are shifted to high temperatures. The stability is maximized at growth temperatures in the vicinity of 0.8 T_g for both molecules, although glasses of ethylbenzene show superior stabilization. Our data is consistent with previous results of larger organic molecules suggesting a generalized behavior on the stability of organic glasses grown from the vapor. In addition, we find that for the small molecules analyzed here, slowing the growth rate below 0.1 nm s⁻¹ does not result in increased thermodynamic stability.

In this work, we describe the design and first experimental results of a new setup that combines evaporation of liquids in ultrahigh vacuum conditions with in situ high sensitivity thermal characterization of thin films. Organic compounds are deposited from the vapor directly onto a liquid nitrogen cooled substrate, permitting the preparation and characterization of glassy films. The substrate consists of a microfabricated, membrane-based nanocalorimeter that permits in situ measurements of heat capacity under ultrafast heating rates (up to 105 K/s) in the temperature range of 100–300 K. Three glass forming liquids—toluene, methanol, and acetic acid—are characterized. The spikes in heat capacity related to the glass-transition temperature, the fictive temperature and, in some cases, the onset temperature of crystallization are determined for several heating rates.

We report the thermodynamic measurement of the enthalpy released during the aging of supported films of a molecular glass former, toluene, at temperatures well below the glass transition temperature. By using microfabricated devices with very short equilibration times (below 1~s), we evidence a remarkable variation of the relaxation rate on decreasing film thickness from 100~nm down to a 7~nm thick film. Our results demonstrate that surface atoms are more efficient than bulk atoms in attaining low energy configurations within the potential energy landscape.

Nanocalorimetry at ultrafast heating rates is used to investigate the glass transition of nanometer thick films of metastable amorphous solid water grown by vapor deposition in an ultrahigh vacuum environment. Apparent heat capacity curves exhibit characteristic features depending on the deposition temperature. While films grown at T ≥ 155 K are completely crystallized, those deposited at 90 K show a relaxation exotherm prior to crystallization. Films grown between 135 and 140 K and subsequently cooled down to 90 K reveal a clear endothermic feature before crystallization, which is compatible with a glass-to-liquid transition. The onset temperature is located at 174 K at a heating rate of 2.4 × 10⁴ K/s and is independent of film thickness in the range of 16–150 nm. Comparison of our data with other calorimetric measurements at various heating rates suggests that water is a strong glass former in the deeply supercooled state.