Infrared Optical Anisotropy in Quasi‐1D Hexagonal Chalcogenide BaTiSe₃

Abstract Polarimetric infrared (IR) detection bolsters IR thermography by leveraging the polarization of light. Optical anisotropy, i.e., birefringence and dichroism, can be leveraged to achieve polarimetric detection. Recently, giant optical anisotropy is discovered in quasi‐1D narrow‐bandgap hexagonal perovskite sulfides, A_1+xTiS₃, specifically BaTiS₃ and Sr_9/8TiS₃. In these materials, the critical role of atomic‐scale structure modulations in the unconventional electrical, optical, and thermal properties raises the broader question of the nature of other materials that belong to this family. To address this issue, for the first time, high‐quality single crystals of a largely unexplored member of the A_1+xTiX₃ (X = S, Se) family, BaTiSe₃ are synthesized. Single‐crystal X‐ray diffraction determined the room‐temperature structure with the P31c space group, which is a superstructure of the earlier reported P6₃/mmc structure. The crystal structure of BaTiSe₃ features antiparallel c‐axis displacements similar to but of lower symmetry than BaTiS₃, verified by the polarization dependent Raman spectroscopy. Fourier transform infrared (FTIR) spectroscopy is used to characterize the optical anisotropy of BaTiSe₃, whose refractive index along the ordinary (E ⊥ c) and extraordinary (E ‖ c) optical axes is quantitatively determined by combining ellipsometry studies with FTIR. With a giant birefringence Δn ∼ 0.9, BaTiSe₃ emerges as a new candidate for miniaturized birefringent optics for mid‐wave infrared to long‐wave infrared imaging.