Design of Infrared Nonlinear Optical Compounds with Diamond-like Structures and Balanced Optical Performance

Infrared (IR) nonlinear optical (NLO) crystals are the major materials to widen the output range of solid-state lasers to mid-infrared regions, but they are still inadequate for application due to the difficulties in balancing the large band gaps and strong NLO response. The diamond-like structure is a potential structural template to explore IR NLO materials. Herein, a computational workflow is proposed for exploring compounds with diamond-like structures, a series of LiMgGaSe₃ structures were predicted successfully through this workflow, and LiMgGaSe₃-I-III exhibited good optical performances in a large band gap (2.75-2.92 eV), strong SHG response (1.2-1.3 × AGS), and suitable birefringence (0.0470-0.0783 at 1064 nm). The in-depth mechanism explorations strongly demonstrate that the synergistic effect of alkaline earth metal tetrahedral [MgSe₄] and [GaSe₄] units is the main origin of large SHG response. The foregoing results suggest that our workflow can accelerate the discovery of new mid-IR NLO materials with diamond-like structures.