Optical Imaging of the Molecular Mobility of Single Polystyrene Nanospheres

An ultrathin surface layer with extraordinary molecular mobility has been discovered and intensively investigated on thin-film polymer materials for decades. However, because of the lack of suitable characterization techniques, it remains largely unexplored whether such a surface mobile layer also exists on individual polymeric nanospheres. Here, we propose a thermal-optical imaging technique to determine the glass transition (Tg) and rubber-fluid transition (Tf) temperatures of single isolated polystyrene nanospheres (PSNS) in a high-throughput and nonintrusive manner for the first time. Two distinct steps, corresponding to the glass transition and rubber-fluid transition, respectively, were clearly observed in the optical trace of single PSNS during temperature ramping. Because the transition temperature and size of the same individuals were both determined, single nanoparticle measurements revealed the reduced apparent Tf and increased Tg of single PSNS on the gold substrate with a decreasing radius from 130 to 70 nm. Further experiments revealed that the substrate effect played an important role in the increased Tg. More importantly, a gradual decrease in the optical signal was detected prior to the glass transition, which was consistent with a surface layer with enhanced molecular mobility. Quantitative analysis further revealed the thickness of this layer to be ∼8 nm. This work not only uncovered the existence and thickness of a surface mobile layer in single isolated nanospheres but also demonstrated a general bottom-up strategy to investigate the structure–property relationship of polymeric nanomaterials by correlating the thermal property (Tg and Tf) and structural features (size) at single nanoparticle level.