Spatial Resolution, Sensitivity and Surface Selectivity in Resonant Mode Photothermal Induced Resonance Spectroscopy

Abstract: Photothermal-Induced Resonance (PTIR) is increasingly used in the measurement of infrared absorption spectra of sub-micrometer objects. The technique measures IR absorption spectra by relying on the photothermal effect induced by a rapid pulse of light and the excitation of the resonance spectrum of an AFM cantilever in contact with the sample. In this work we assess the spatial resolution and depth response of PTIR in resonant mode while systematically varying the pulsing frequency of the excitation laser and the cantilever resonance. The spatial resolution shows a shallow linear dependence on the inverse of the pulse frequency, which rules out tip size as a limiting factor for resolution in the frequency range under investigation. Measured resolution values are also one order of magnitude lower than in the thermal diffusion limit, excluding thermal wave propagation as a limiting factor. We also show that the pulsing frequency of the laser and choice of cantilever resonance affect the intensity of the signal and the surface selectivity in PTIR images, with higher frequencies providing increased surface selectivity. The results confirm a difference in signal generation between resonant PTIR and other photothermal techniques and indicate that photothermal induced heating and expansion cannot fully account for observed intensity and resolution.