Achieving the second-order nonlinear optical(NLO)effect necessitates a non-centrosymmetric(NCS)structure,which is a prerequisite,but obtaining it effectively remains greatly challenging.In pursuit of this,a strategy k...Achieving the second-order nonlinear optical(NLO)effect necessitates a non-centrosymmetric(NCS)structure,which is a prerequisite,but obtaining it effectively remains greatly challenging.In pursuit of this,a strategy known as“dimensionality elevation”has been operated to create a high-dimensional NCS framework based on a low-dimensional centrosymmetric(CS)structure.Concretely,the acentric[CdS_(4)]tetrahedral unit serves as a linkage point in the zerodimensional(0D)[Si_(4)S_(10)]T2-supertetrahedra,leading to the formation of the 3D NCS rigid sulfide,Cs_(2)CdSi_(4)S_(10)(1),which exhibits moderate second-harmonic generation(SHG)effect(0.5×AgGaS_(2)@1.91μm).To enhance the SHG coefficient,a structural modification has been made by replacing the Si-based framework with a Ga-based one and re-employing the“dimensionality elevation”strategy.This alteration prompted the tetrahedral[CdS_(4)]units to connect with 0D T2-supertetrahedral[Ga_(4)S_(10)]motifs,creating the 3D NCS salt-inclusion chalcogenide[Ba_(4)Cl_(2)][CdGa_(4)S_(10)](2).Notably,compared with 1,compound 2 not only demonstrates an increased SHG response(1.3×AgGaS_(2)@1.91μm)but also retains a broad band gap(3.74 eV for 1 and 3.50 eV for 2)for exceptional laser-induced damage thresholds(LIDTs,9.3×and 7.3×AgGaS_(2)@1.06μm for 1 and 2,respectively),suggesting that compound 2 is an advanced infrared NLO material.This research pioneers new pathways for discovering NCS NLO materials through the“dimensionality elevation”strategy.展开更多
基金supported by the National Natural Science Foundation of China(92161125,21921001,22075283,22175172,U21A20508)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2020ZZ108)the Youth Innovation Promotion Association of Chinese Academy of Sciences(2021300)。
文摘Achieving the second-order nonlinear optical(NLO)effect necessitates a non-centrosymmetric(NCS)structure,which is a prerequisite,but obtaining it effectively remains greatly challenging.In pursuit of this,a strategy known as“dimensionality elevation”has been operated to create a high-dimensional NCS framework based on a low-dimensional centrosymmetric(CS)structure.Concretely,the acentric[CdS_(4)]tetrahedral unit serves as a linkage point in the zerodimensional(0D)[Si_(4)S_(10)]T2-supertetrahedra,leading to the formation of the 3D NCS rigid sulfide,Cs_(2)CdSi_(4)S_(10)(1),which exhibits moderate second-harmonic generation(SHG)effect(0.5×AgGaS_(2)@1.91μm).To enhance the SHG coefficient,a structural modification has been made by replacing the Si-based framework with a Ga-based one and re-employing the“dimensionality elevation”strategy.This alteration prompted the tetrahedral[CdS_(4)]units to connect with 0D T2-supertetrahedral[Ga_(4)S_(10)]motifs,creating the 3D NCS salt-inclusion chalcogenide[Ba_(4)Cl_(2)][CdGa_(4)S_(10)](2).Notably,compared with 1,compound 2 not only demonstrates an increased SHG response(1.3×AgGaS_(2)@1.91μm)but also retains a broad band gap(3.74 eV for 1 and 3.50 eV for 2)for exceptional laser-induced damage thresholds(LIDTs,9.3×and 7.3×AgGaS_(2)@1.06μm for 1 and 2,respectively),suggesting that compound 2 is an advanced infrared NLO material.This research pioneers new pathways for discovering NCS NLO materials through the“dimensionality elevation”strategy.
