Authors: Hongshan Wang, Ran An, Zhihua Yang, Shilie Pan, Junjie Li
Published: 2025-03-24
Source: Full article
AbstractDeveloping superior infrared nonlinear optical (IR NLO) materials with broad bandgap (Eg) 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 Eg and longboard effect of NLO response, four new IR NLO candidates AIIBIISiSe4 (AII = Sr, Ba; BII = Cd, Hg) derived from the centrosymmetric (CS) SrIn2Se4, with a structural transition from Ama2 (AIIHgSiSe4 and SrCdSiSe4) to Fdd2 (BaCdSiSe4), are rationally designed and fabricated by synergically assembling advantageous structural groups. Among them, AIICdSiSe4 displays the optimal comprehensive performance in the known AIIBIICIVSe4 family compounds, including a strong NLO response (≈2.1–2.7 × AgGaS2), a wide selenide Eg (≈2.67–2.78 eV) and a high laser‐induced damage threshold (≈4.0 × AgGaS2). Theoretical investigations uncover that the superior properties in the compounds can be contributed to the synergic‐assembly of advantageous [AIISe8], [CdSe4], and [SiSe4] 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.