High-resolution cemical identification of polymer blend thin films using tip-enhanced raman mapping

Nanoscale chemical identification is required for the analysis of functional materials with fine structures. For the first time, high resolution tip-enhanced Raman mapping (TERM) was applied to a polymer system: poly(methyl methacrylate) (PMMA)/poly(styrene-co-acrylonitrile) (SAN) thin films. Before TERM measurements were performed, the linear enhancement of tip enhanced Raman spectroscopy (TERS) was optimized in terms of maximum Raman intensity. Up to 15 times of linear enhancement was obtained, as compared to the (conventional) confocal Raman intensity. The enhancement factor of TERS is greater than 1500 if taking the 100 times smaller probing area into account. As a result, a short exposure time was sufficient for high-resolution TERM measurements. Using TERM, the phase separation behavior of PMMA/SAN thin films was monitored by chemical recognition of local composition. The interface width (~200 nm) at the early stage of phase evolution was visualized. The comparison of TERM images at different stages of the phase separation process revealed an unexpected transition of PMMA from the dispersed phase to the continuous phase. This morphology transition of PMMA/SAN is briefly discussed in terms of the glass transition temperature, interface, and surface tension