Spatially-resolved individual particle spectroscopy using photothermal modulation of Mie scattering

We report a photothermal modulation of Mie scattering (PMMS) method that enables concurrent spatial and spectral discrimination of individual micron-sized particles. This approach provides a direct measurement of the "fingerprint" infrared absorption spectrum with the spatial resolution of visible light. Trace quantities (tens of picograms) of material were deposited onto an infrared-transparent substrate and simultaneously illuminated by a wavelength-tunable intensity-modulated quantum cascade pump laser and a continuous-wave 532 nm probe laser. Absorption of the pump laser by the particles results in direct modulation of the scatter field of the probe laser. The probe light scattered from the interrogated region is imaged onto a visible camera, enabling simultaneous probing of spatially-separated individual particles. By tuning the wavelength of the pump laser, the IR absorption spectrum is obtained. Using this approach, we measured the infrared absorption spectra of individual 3 μm PMMA and silica spheres. Experimental PMMS signal amplitudes agree with modeling using an extended version of the Mie scattering theory for particles on substrates, enabling the prediction of the PMMS signal magnitude based on the material and substrate properties.