Ultrafast impulsive Raman spectroscopy across the terahertz-fingerprint region

Broadband Raman spectroscopy (detection bandwidth >1000 cm-1) is a valuable and widely used tool for understanding samples via label-free measurements of their molecular vibrations. Two important Raman spectral regions are the chemically specific "fingerprint"(200 to 1800 cm-1) and "low-frequency"or "terahertz"(THz) (<200 cm-1; <6 THz) regions, which mostly contain intramolecular and intermolecular vibrations, respectively. These two regions are highly complementary; broadband simultaneous measurement of both regions can provide a big picture comprising information about molecular structures and interactions. Although techniques for acquiring broadband Raman spectra covering both regions have been demonstrated, these methods tend to have spectral acquisition rates <10 spectra/s, prohibiting high-speed applications, such as Raman imaging or vibrational detection of transient phenomena. Here, we demonstrate a single-laser method for ultrafast (24,000 spectra/s) broadband Raman spectroscopy covering both THz and fingerprint regions. This is achieved by simultaneous detection of Sagnac-enhanced impulsive stimulated Raman scattering (SE-ISRS; THz-sensitive) and Fourier-transform coherent anti-Stokes Raman scattering (FT-CARS; fingerprint-sensitive). With dual-detection impulsive vibrational spectroscopy, the SE-ISRS signal shows a >500 × enhancement of <6.5 THz sensitivity compared with that of FT-CARS, and the FT-CARS signal shows a >10 × enhancement of fingerprint sensitivity above 1000 cm-1 compared with that of SE-ISRS.