Surface Glass Transition Temperature Region of Diarylethene Films Determined by Nano-Marangoni Effect

For the last two decades, research has addressed whether the glass transition temperature and the molecular motions on the surface of organic films are significantly different from those inside the bulk glasses. It is reported that the surface of the photochromic diarylethene film prepared by vacuum deposition has fluidity and the vacuum deposition of small amount of rubrene molecules induces surface tension fluctuations, generating dents due to the Marangoni flow in nanoscale. The depth of the dents increases in proportion to these radii for the colorless diarylethene film with a bulk glass transition temperature (Tg) close to room temperature. On the other hand, in the colored diarylethene obtained by UV irradiation to the colorless film, the depth becomes constant at a certain level. The Tg distribution in the depth direction is clarified based on an analysis of the dent depth. By approximating the obtained Tg depth distribution with an exponential function, the outermost surface Tg is about 100 K lower than the bulk Tg in the case of photoisomerized diarylethene.