Observation of Nanoscale Opto-Mechanical Molecular Damping; Origin of Spectroscopic Contrast in Photo Induced Force Microscopy

Abstract: We experimentally investigated the contrast mechanism of infrared photoinduced force microscopy (PiFM) for recording vibrational resonances. Extensive experiments have demonstrated that spectroscopic contrast in PiFM is mediated by opto-mechanical damping of the cantilever oscillation as the optical wavelength is scanned through optical resonance. To our knowledge, this is the first time opto-mechanical damping has been observed in the AFM. We hypothesize that this damping force is a consequence of the dissipative interaction between the sample and the vibrating tip; the modulated light source in PiFM modulates the effective damping constant of the 2nd eigenmode of the cantilever which in turn generate side-band signals producing the PiFM signal at the 1st eigenmode. A series of experiments have eliminated other mechanisms of contrast. By tracking the frequency shift of the PiFM signal at the 1st cantilever eigenmode as the excitation wavenumber is tuned through a mid-infrared absorption band, we showed that the near-field optical interaction is attractive. By using a vibrating piezoelectric crystal to mimic sample thermal expansion in a PiFM operating in mixing mode, we determined that the minimum thermal expansion our system can detect is 30 pm limited by system noise. We have confirmed that van der Waal mediated thermal-expansion forces have negligible effect on PiFM signals by detecting the resonant response of a 4-methylbenzenethiol mono molecular layer deposited on template-stripped gold, where thermal expansion was expected to be < 3 pm, i.e., 10 times lower than our system noise level. Finally, the basic theory for dissipative tip-sample interactions was introduced to model the photoinduced opto-mechanical damping. Theoretical simulations are in excellent agreement with experiment.