AIB3IIC3IIIQsI: A New Family for the Design of Infrared Nonlinear Optical Materials by Coupling Octahedra and Tetrahedra Units

Large second-harmonic generation (SHG) response and broad band gap are two important and competitive parameters. It is difficult to balance them out in one material. In this work, by coupling alkali earth metal (AEM) octahedra with large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap and nonlinear optical (NLO)-active tetrahedra units, nine noncentrosymmetric (NCS) compounds, belonging to a new quaternary chalcogenide family AIBI3IC3IIIQ8VI with unique windmill-like [Mg3M3IIIQ24] (MIII = Al, Ga; Q = S, Se) units constructed by alternated [MgQ6] octahedra and [MIIIQ4] tetrahedra, are rationally designed and fabricated. The compounds show a stable structural framework but adjustable optical properties. Among them, NaMg3Ga3Se8 shows a large SHG response (-,1 x AgGaS2 (AGS)), wide band gap (in selenide) (2.77 eV), high laser-induced damage threshold (LIDT) (-,2.3 x AGS), and suitable birefringence (0.079@546 nm). It should be a potential candidate for infrared (IR) nonlinear optical (NLO) materials. The results enrich the chemical diversity of chalcogenides and open an avenue for the development of new IR NLO materials through the octahedra and tetrahedra coupled strategy.

Automated summary

In this work, nine new noncentrosymmetric compounds are designed and fabricated by coupling alkali earth metal octahedra and nonlinear optical active tetrahedra units. The compound NaMg3Ga3Se8 shows potential as an infrared nonlinear optical material with its large SHG response, wide band gap, high laser-induced damage threshold, and suitable birefringence.