Second-Harmonic Generation-Positive Na₂Ga₂SiS₆ with a Broad Band Gap and a High Laser Damage Threshold

The development of high-power solid-state lasers is in urgent need of new infrared nonlinear optical (IR NLO) materials with a wide band gap and a high laser-induced damage threshold. A new infrared nonlinear optical material Na₂Ga₂SiS₆ has been synthesized for the first time, crystallizing in the Fdd2 (no. 43) noncentrosymmetric space group. Its three-dimensional tunnel framework consists of two typical NLO active motifs [GaS₄] and [SiS₄], with Na⁺ cations located inside the tunnels. Na₂Ga₂SiS₆ exhibits comprehensive optical properties, namely, a wide transmission range, a high laser-induced damage threshold (10 × AgGaS₂), a type-I phase-matching second-harmonic generation response (0.2 × AgGaS₂), and especially a wide band gap (3.93 eV), which is the largest in the A₂M^III₂M^IVQ₆ (A = alkali metals; M^III = IIIA elements; M^IV = IVA elements; Q = S and Se) family. Therefore, Na₂Ga₂SiS₆ does not produce two-photon absorption under a 1064 nm laser pump and could be used in high-energy laser systems, which makes Na₂Ga₂SiS₆ a promising candidate for high-energy IR NLO applications.