This paper discusses the use of optical photothermal infrared (O-PTIR) spectroscopy combined with Raman analysis. The new technique overcomes many of the limitations of conventional FTIR and Raman spectroscopy when used alone. It is based on an infrared-visible pump-probe system that incorporates a wavelength-tunable IR laser that emits a pulsed beam that is combined colinearly with the output of a 532-nm green laser. As the paper explains, infrared radiation is partially absorbed by the test target when the wavelength of the laser resonates with the vibrational mode of the material. This excitation process causes the area under the infrared spot to heat up, in turn, causing local expansion along with changes in the refractive indices. These photothermal effects cycle on and off in synch with the pulsed IR beam and the amplitudes of the on-off states are captured by the co-located visible beam and plotted as a function of wavelength over the tunable range of the IR laser. The diffraction limited spot size of the visible beam is approximately 416 nm, corresponding to a spatial resolution of about 1 μm, which is 30 times more precise than conventional FTIR. In addition, by measuring photothermal effects in localized regions, it is possible to identify chemicals in quantities of matter as small as 0.4 pg. By comparison, the sensitivity of transmission mode FTIR is significantly less at around 100 pg.

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