Polysubstitution Induced Centrosymmetric-to-Noncentrosymmetric Structural Transformation and Nonlinear-Optical Behavior: The Case of Na0.45Ag0.55Ga3Se5

Jun Li; Jia-Nuo Li; Li-Yun Hu; Jun-Jie Ni; Wen-Dong Yao; Wenfeng Zhou; Wenlong Liu; Sheng-Ping Guo

doi:10.1021/acs.inorgchem.4c00785

Polysubstitution Induced Centrosymmetric-to-Noncentrosymmetric Structural Transformation and Nonlinear-Optical Behavior: The Case of Na_0.45Ag_0.55Ga₃Se₅

Inorg Chem. 2024 Apr 8;63(14):6116-6121. doi: 10.1021/acs.inorgchem.4c00785. Epub 2024 Mar 22.

Authors

Jun Li¹, Jia-Nuo Li², Li-Yun Hu¹, Jun-Jie Ni¹, Wen-Dong Yao¹, Wenfeng Zhou¹, Wenlong Liu¹, Sheng-Ping Guo¹

Affiliations

¹ School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, P. R. China.
² Graduate School of Engineering, Nagoya University, Nagoya 4648601, Japan.

PMID: 38518373
DOI: 10.1021/acs.inorgchem.4c00785

Abstract

Obtaining compounds with large nonlinear-optical (NLO) coefficients and wide band gaps is challenging due to their competitive requirements for chemical bonds. Herein, the first member with mixed cations on the A site in the A-M₃-Q₅ or A-Ag-M₆-Q₁₀ (A = alkali metal; M = Ga, In; Q = S, Se, Te) family, viz. Na_0.45Ag_0.55Ga₃Se₅ (NAGSe), was obtained by a solid-state reaction. Its structure features [GaSe₄] tetrahedra built three-dimensional {[Ga₃Se₅]^-}_∞ network, with Na and Na/Ag cations located at the octahedral cavities. Noncentrosymmetric (R32) NAGSe can also be transformed from centrosymmetric RbGa₃S₅ (P2₁/c) via multiple-site cosubstitution. NAGSe exhibits the highest NLO response (1.9 × AGS) in the A-Ag-M-Q family. Crystal structure analysis and theoretical calculations suggest that the NLO response is mainly contributed by the regularly arranged [GaSe₄] units. This work enriches the exploration of the undeveloped A-M₃-Q₅ or A-Ag-M₆-Q₁₀ family as potential infrared NLO materials.