Doppler dual-comb coherent Raman spectromicroscopy

Chemical imaging enabled by Raman processes is crucial to investigating biological and chemical samples in a label-free manner. Stimulated Raman spectroscopy (SRS) overcomes the key limitation associated with low signal levels in spontaneous Raman spectroscopy, however, at the expense of probing only narrow Raman bands. Time-domain implementation of coherent anti-Stokes Raman spectroscopy (CARS) by dual frequency combs can achieve broad Raman bandwidths; nevertheless, its execution is demanding due to strenuous temporal-synchronization of two independent ultrashort laser sources. Here, we introduce time-domain coherent Raman spectroscopy utilizing two frequency combs generated by the Doppler effect from a single ultra-broadband laser source. In contrast to CARS, in our approach, the interference of impulsively launched vibrations by two broadband frequency combs (τ ~ 6 fs) periodically modulates the Kerr nonlinear response of the medium, leading to cross-phase modulation (XPM) experienced by both the combs. This phase modulation leads to spectral broadening and periodic modulation in the anti-Stokes region of the combs. Down-conversion by a factor of ~ 10-8 in the frequency of the vibrations enabled by the dual-comb approach empowered us to use photon-counting methodology in the anti-Stokes region. This makes our technique extremely versatile, background-free, sensitive and fast (millisecond acquisition times), in probing a range of samples from wide bandgap dielectrics and liquids to individual micro-particles with nondestructive pulse energies (~ 100 pJ) incident on the sample. Owing to the higher-order nonlinearity involved in the XPM process, we achieved ~ 2.5 times improvement in diffraction-limited spatial resolution (~ 280 nm) in ultra-broadband chemical imaging of a ~ 8 μm bead of poly-methyl-methacrylate.