Synergically Assembling Advantageous Groups toward High‐Performance Infrared Nonlinear Optical Materials AIICdSiSe4 (AII = Sr, Ba)

Abstract Developing superior infrared nonlinear optical (IR NLO) materials with broad bandgap ( E g ) and large NLO response is an urgent need for the highly expected mid‐/far‐IR solid‐state lasers, but challenging due to the contradiction between the critical parameters. Herein, guided by the short board effect of E g and longboard effect of NLO response, four new IR NLO candidates A II B II SiSe 4 (A II = Sr, Ba; B II = Cd, Hg) derived from the centrosymmetric (CS) SrIn 2 Se 4 , with a structural transition from Ama 2 (A II HgSiSe 4 and SrCdSiSe 4 ) to Fdd 2 (BaCdSiSe 4 ), are rationally designed and fabricated by synergically assembling advantageous structural groups. Among them, A II CdSiSe 4 displays the optimal comprehensive performance in the known A II B II C IV Se 4 family compounds, including a strong NLO response (≈2.1–2.7 × AgGaS 2 ), a wide selenide E g (≈2.67–2.78 eV) and a high laser‐induced damage threshold (≈4.0 × AgGaS 2 ). Theoretical investigations uncover that the superior properties in the compounds can be contributed to the synergic‐assembly of advantageous [A II Se 8 ], [CdSe 4 ], and [SiSe 4 ] units. The results enrich the chemical and structural diversities of chalcogenides, and open an avenue for the design of high‐performance IR NLO materials from the known CS compound by the aliovalent group substitution and synergically assembling strategy.