Localized photothermal infrared spectroscopy using a proximal probe

A near-field thermal probe, as used in scanning thermal microscopy, is used to obtain photothermalFourier transform infrared (FT-IR) spectra of polymers, as a first step toward developing FT-IR microscopy at a spatial resolution better than the diffraction limit. The signal from the probe after amplification provides an interferogram, and the resultant spectra are consistent with those obtained by means of the established technique of attenuated total reflection FT-IR spectroscopy. We have extended this technique to the analysis of “real-world” industrial samples, both solid (a fungicide in a fine powder form) and liquid (a concentrated surfactant solution). The overall shapes of the main peaks or bands reflect the fact that the spectrum is a convolution of different contributions from both optical and thermal properties. To confirm the feasibility of subsurface detection of polymers, we demonstrate the ability of the technique to perform spectroscopic detection of a model polymeric bilayer system, polyisobutylene on top of polystyrene. A quantitative analysis of the variation of peak height with coating thickness allows values of thermal diffusion length to be derived. This investigation provides a preliminary result for the understanding of the depth sensitivity of the current setup. Relative intensity distortions are seen, and are attributed to photothermal saturation. A complementary technique has been developed that uses tunable monochromatic radiation, using an optical parametric generator as the infrared source. Spectra have successfully been obtained using the same localized photothermal detection principle.