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

Abstract

Tailored structural regulation to obtain a new noncentrosymmetric (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 BaGa 2 Si 2 O 8 was selected as a template structure, and a novel NCS oxychalcogenide, namely, Ba 5 Ga 2 SiO 4 S 6 , was successfully designed via the introduction of heteroanions under high-temperature solidstate conditions. Ba 5 Ga 2 SiO 4 S 6 adopts the monoclinic space group of Cc (no. 9) and is formed by charges balancing Ba 2+ cations and discrete [Ga 2 SiO 4 S 6 ] clusters made of corner-sharing [SiO 4 ] and [GaOS 3 ] tetrahedra. Notably, Ba 5 Ga 2 SiO 4 S 6 exhibits the critical requirements as a potential UV NLO candidate, including a phasematching 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.

Synthesis and structure-dependent optical properties of two new organic–inorganic hybrid antimony(iii) chlorides

“…It has long been known that the electronic transition between the VBM and the CBM is the major factor affecting the PL properties and SHG responses of optoelectronic materials. [42][43][44][45] Therefore, the SbCl 6 octahedra have a dominant contribution to the SHG efficiency and PL emission of compound 2, and the contribution from organic SDAs is negligible. The contribution of SbCl 6 octahedra to the optical properties of compound 2 is further confirmed by the calculated electronic density difference map, which clearly…”

Solvent-free synthesis of magnesium phosphite-oxalates that show second-harmonic generation responses

“…It is well known that the electron transition between the VB top and CB bottom can affect the NLO properties of noncentrosymmetric materials. 14 The results suggest that the oxalate ligands in compounds 1 and 2 make a major contribution to their SHG efficiencies. The calculated electronic density difference maps of compounds 1 and 2 show highly asymmetric lobes around the oxalate ligands, confirming the contributions of oxalate ligands to the SHG efficiencies (Fig.…”

Sr6Ge3OSe11: A Rationally Designed Noncentrosymmetric Oxyselenide with Polar [GeOSe3] Building Blocks

“…To increase the band gap while maintaining large polarizability, a strategy of combining oxygen with less electronegative anions in a single compound has been developed. This has been implemented successfully to produce several new noncentrosymmetric (NCS) oxychalcogenides such as SrZn 2 OS 2 (space group Pmn2 1 ), 11 SrGeOS 2 (P2 1 2 1 2 1 ), 12 BaGeOS 2 (P2 1 2 1 2 1 ), 12 Ba 3 Ge 2 O 4 Te 3 (R3m), 13 Ba 5 Ga 2 SiO 4 S 6 (Cc), 14 Sr 4 Pb 1.5 Sb 5 O 5 Se 8 (Cm), 15 and Sr 2 MGe 2 OS 6 (P4̅ 2 1 m), where M = Mn, Zn, or Cd. 16 Herein, we outline the strategy that was used to synthesize the NCS compound Sr 6 Ge 3 OSe 11 .…”