Physical aging of glasses of an organic semiconductor

Abstract

All glasses, including organic semiconductor glasses, are non-equilibrium materials whose properties will change with time. This “physical aging” process is poorly understood for organic semiconductors, hindering the rational design of highly durable devices. In this study, we investigated the volume and enthalpy recovery processes in both thin films and bulk glasses of N,N'-Bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD). Our results revealed that volume recovery kinetics exhibit negligible dependence on film thickness for liquid-cooled TPD films between 400 nm and 100 nm. Additionally, the volume recovery process in TPD films was strongly coupled to the enthalpy recovery observed in bulk TPD glasses during annealing near the glass transition temperature. Remarkably, TPD films prepared by physical vapor deposition at room temperature demonstrated exceptional resistance to physical aging, with an aging rate approximately one order of magnitude lower than that of their liquid-cooled counterparts. These results not only enhance our understanding of the non-equilibrium dynamics in amorphous systems but also offer valuable insights for the design of next-generation organic devices with significantly improved stability and durability.