AAg3Ga8Se14 (A = Rb, Cs): second-harmonic generation responses realized through the parallel arrangement of AgSe4 and GaSe4 tetrahedrons

Zhi-Xin Qiu; Shao-Min Pei; Wen-Fa Chen; Xiao-Ming Jiang; Bin-Wen Liu; Guo-Cong Guo

doi:10.1039/d2dt01614a

AAg₃Ga₈Se₁₄ (A = Rb, Cs): second-harmonic generation responses realized through the parallel arrangement of AgSe₄ and GaSe₄ tetrahedrons

Dalton Trans. 2022 Jul 26;51(29):11048-11053. doi: 10.1039/d2dt01614a.

Authors

Zhi-Xin Qiu^{1

2}, Shao-Min Pei¹, Wen-Fa Chen¹, Xiao-Ming Jiang¹, Bin-Wen Liu¹, Guo-Cong Guo¹

Affiliations

¹ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China. bwliu@fjirsm.ac.cn.
² Fujian Normal University, College of Chemistry and Materials science, Fuzhou, Fujian, 350007, P. R. China.

PMID: 35796155
DOI: 10.1039/d2dt01614a

Abstract

Two new quaternary selenides AAg₃Ga₈Se₁₄, (A = Rb, 1; Cs, 2) were synthesised via solid-state reaction in sealed silica tubes. Compounds 1 and 2 crystallised in the monoclinic space group Cm (no. 8) and their three-dimensional [Ag₃Ga₈Se₁₄]^- anionic frameworks were comprised of AgSe₄ and GaSe₄ tetrahedrons. Their UV-Vis-near infrared diffuse reflectance spectra showed that 1 and 2 possessed wide band gaps of 2.17 and 2.10 eV, respectively. Notably, under incident laser irradiation at 1910 nm, compounds 1 and 2 presented moderate second-harmonic generation responses of 0.6 and 0.7 × AgGaS₂, respectively, with phase-matching behaviours due to the parallel arrangement of nonlinear optical (NLO) functional tetrahedral AgSe₄ and GaSe₄ units. The laser-induced damage thresholds of 1 and 2 were estimated to be 25.4 and 18.0 MW cm^-2, respectively, which were 2.1 and 1.5 times the threshold of AgGaS₂. This study revealed that the title selenides, which were constructed from tetrahedral units arranged in a parallel array, are promising infrared NLO materials.