Observation of Selective Excitation of Raman Inactive Phonon Mode of Strontium Titanate Through Anti-Stokes Hyper-Raman Scattering Process

Pump-probe excitation technique using mid-infrared free electron laser and Nd:YVO4 ps-laser from Kyoto University free electron laser facility was implied to selectively excite a Raman inactive phonon mode of a semiconductor single crystal sample. The LO3 phonon mode of strontium titanate was chosen and the MIR-FEL photon energy was adjusted to match the target phonon mode energy, which corresponded to a wavelength of 12.5 mu m. Temporal and spatial overlapping of MIR-FEL pulses and probe laser pulses were performed and confirmed through sum frequency generation from ZnS cleartran (R). Confirmation of the Raman forbidden mode excitation was achieved through the anti-Stokes hyper-Raman scattering (ASHRS) spectroscopy method. Successful excitation was observed at 5 K, where thermal excitation of all other phonon modes was suppressed. The recorded spectrum showed a signal that was red-shifted from 800 to around 761 cm-1. The broadened line width (FWHM) and the red-shifting phenomenon in the recorded result have been observed due to the restraint of the spectrometer slit width function and the intense irradiation of the picosecond laser for hyper-Raman scattering spectroscopy, which have also led to surface damage on the crystal sample.