First-Principles High-Throughput Screening and Experimental Verification of III-VIB Transition Metal Chalcogenides Nonlinear Optical Crystals

Infrared nonlinear optical materials (IR NLO) have shown important and useful applications in industries and science research. Transition-metal (TM)-based chalcogenides have diverse coordination and broad transparent windows, which make them excellent candidates for IR NLO crystals. However, III-VIB TM-based chalcogenides have been little explored as IR NLO materials. Herein, a first-principles high-throughput screening pipeline (FHSP) has been used for searching promising IR NLO materials in III-VIB TM-based chalcogenides. 89 known TM-based chalcogenides have been selected from 330 noncentrosymmetric (NCS) materials included in the Inorganic Crystal Structure Database (ICSD), which have been systematically surveyed for further investigation. Finally, we successfully synthesized two materials Na3VS4 and CuScS2 with superior predicted performances. The results show that Na3VS4 owns balanced properties, such as giant SHG response (4.19 × AGS), reasonable band gap (2.18 eV), suitable birefringence (0.03 @1064 nm), and long shortest IR absorption (abs.) mode (21.7 μm). CuScS2 has no obvious vibration absorption peak in the region of 4000–400 cm–1 (2.5–25 μm) and exhibits moderate SHG response (1.44 × AGS). In addition, this work will afford an orientation to discover more crystal materials.