Three‐in‐One Strategy Constructing the First High‐Performance Nonlinear Optical Sulfide Crystallizing with the P4₃ Space Group

Abstract The balance between large nonlinear optical (NLO) effect and wide bandgap is the key scientific issue for the exploration of infrared NLO materials. Targeting this issue, two new pentanary chalcogenides KGaGe_1.37Sn_0.63S₆ (1) and KGaGe_1.37Sn_0.63Se₆ (2) are obtained by the three‐in‐one strategy, viz. three types of fourfold‐coordinated metal elements co‐occupying the same site. They crystallize in the tetragonal P4₃ (1) and monoclinic Cc (2) space group. Their structures can be evolved from benchmark AgGaS₂ (AGS) by suitable substitution. Remarkably, 1 is the first NLO sulfide crystallizing with the P4₃ space group, representing a new structure‐type NLO material. The structural relationship between 1 and 2 and the evolution from 1, 2 to AGS are also analyzed. Both 1 and 2 show balanced NLO properties. Specifically, 1 exhibits phase‐matchable SHG response of 0.6 × AGS, a wide bandgap of 3.50 eV, and a high laser damage threshold of 6.24 × AGS. Theoretical calculation results suggest that the Ga/Ge/Sn element ratios of the co‐occupied sites of 1 and 2 are the most appropriate for stabilizing the structures. The strategy adopted here will provide some inspiration for exploring new high‐performance NLO materials.