Molecular packing in highly stable glasses of vapor-deposited tris-naphthylbenzene isomers

Abstract

Physical vapor deposition of organic molecules can produce glasses with high kinetic stability and low enthalpy. Previous experiments utilizing wide-angle x-ray scattering (WAXS) have shown that, relative to the ordinary glasses prepared by cooling the supercooled liquid, such glasses exhibit excess scattering characteristic of anisotropic packing. We have used vapor deposition to prepare glasses of four isomers of tris-naphthylbenzene (TNB), and measured both the WAXS patterns and the kinetic stability. While vapor-deposited glasses of all four TNB isomers exhibit high and nearly uniform kinetic stability, the level of excess scattering varies significantly. In addition, for α,α,β-TNB, glasses of essentially identical kinetic stability can have excess scattering levels that vary by a factor of two. These results indicate that anisotropic packing is not the source of kinetic stability in vapor-deposited glasses but rather a secondary feature that depends upon the chemical structure of the glass-forming molecules. We also show that the time required for these stable vapor-deposited glasses to transform into the supercooled liquid greatly exceeds the structural relaxation time τ(α) of the liquid and scales approximately as τ(α) (0.6). The kinetic stability of the vapor-deposited TNB glasses matches that expected for ordinary glasses that have been aged for 10(2) to 10(7) years.