Abstract
Sum-frequency vibrational spectroscopy has recently been used to investigate the surface of the various polymers and was able to find the chemical compositions and structures specific to the surface. Here we report our studies on two specific polymer samples to demonstrate its capability. Polyimide thin films were made by spin coating on fused quartz and $CaF_2$ substrates. The sum-frequency signal originating mainly from the air/polymer interface showed markedly different spectra, indicating the structural change of the polymer surface depending on the underlying substrate. Various polyethylene surfaces were also investigated by sum-frequency vibrational spectroscopy. The surface of polyethylene samples in the CH-region showed different sum-frequency spectra, presumably due to the trace amount of additives having much higher concentration at the air/polymer interface. These examples demonstrate the surface and interface of the polymer could have different structure and chemical composition from those of a bulk, which can be studied effectively by surface nonlinear optical spectroscopy.