Ba₅Ga₂SiO₄S₆: a Phase-Matching Nonlinear Optical Oxychalcogenide Design via Structural Regulation Originated from...

Tailored structural regulation to obtain a new non-centrosymmetric (NCS) compound with excellent optical properties is highly desirable but remains a challenge for nonlinear optical (NLO) material design. In this work, centrosymmetric celsian-type BaGa₂Si₂O₈ was selected as a template structure, and a novel NCS oxychalcogenide, namely, Ba₅Ga₂SiO₄S₆, was successfully designed via the introduction of heteroanions under high-temperature solid-state conditions. Ba₅Ga₂SiO₄S₆ adopts the monoclinic space group of Cc (no. 9) and is formed by charges balancing Ba²⁺ cations and discrete [Ga₂SiO₄S₆] clusters made of corner-sharing [SiO₄] and [GaOS₃] tetrahedra. Notably, Ba₅Ga₂SiO₄S₆ exhibits the critical requirements as a potential UV NLO candidate, including a phase-matching second-harmonic generation intensity (∼1.0 × KDP), a beneficial laser-induced damage threshold (1.2 × KDP), a large birefringence (Δn = 0.10@546 nm), and a short UV absorption cutoff edge (ca. 0.26 μm). Furthermore, the theoretical calculation is implemented to provide a deeper analysis of the structure-activity relationship. The investigated example of structural regulation originated from heteroanion introduction in this study may offer a feasible strategy for high-performance NLO candidate design.