Polarized Raman Spectra and Complex Raman Tensors of Antiferromagnetic Semiconductor CrPS₄

Chromium thiophosphate (CrPS4), a monoclinic crystal of C23 space group, is a ternary-layered semiconductor with an optical band gap of 1.4 eV and exhibits antiferromagnetism below 36 K. Despite its potential in optoelectronic and magnetic applications, the symmetry of its lattice vibrations has not been systematically studied. In this work, we performed polarized Raman spectroscopy of bulk CrPS4 using three different excitation wavelengths of 457, 514, and 633 nm. High-quality crystals grown by the chemical vapor transport method were mechanically exfoliated or polished to expose three orthogonal crystallographic facets. Polarized Raman spectra were obtained in parallel and cross configurations by rotating samples about the surface normal to each of the facets. Among 33 Raman active modes (16 A and 17 B) at the Brillouin zone center, 19 (8) peaks observed in the parallel (cross) configuration were assigned as A (B) modes. Complex-valued Raman tensors were determined for 7 major A modes using the angle-dependent Raman spectra of the three facets. The results can also be used in determining the crystallographic orientations of CrPS4 unequivocally.