It is challenging to cooperatively improve the nonlinear optical(NLO)efficiency and the laser-induced damage threshold(LIDT).This work reports a novel IR NLO materials CsInP_(2)S_(7)(CIPS)designed by combination the s...It is challenging to cooperatively improve the nonlinear optical(NLO)efficiency and the laser-induced damage threshold(LIDT).This work reports a novel IR NLO materials CsInP_(2)S_(7)(CIPS)designed by combination the strategies of alkali metals substitution and microscopic NLO units PS4 introduction based on AgGaS_(2).CIPS was composed of strongly distorted[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers constructed by corner-sharing[PS_(4)]^(3-),which increase the NLO efficiency and decrease thermal expansion anisotropy simultaneously.Compared with AgGaS_(2),CIPS exhibited strong phase matchable NLO response ca.1.1×AGS@2.1μm,high LIDT ca.20.8×AgGaS_(2),and IR transparency up to 15.3μm.Structural analysis and theoretical investigation confirmed that large SHG effect and ultrahigh LIDT of CIPS originated from the synergistic contribution of[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers.These results indicate that CIPS is a promising NLO candidate in the mid-IR region,and this study provides a new approach for developing potential NLO-LIDT compatible materials.展开更多
Diamond-like AgGaS_(2)(DL AGS),as the typical infrared nonlinear optical(IR NLO)material,has suffered from its intrinsic drawbacks like narrow band gap(E_(g))and low laser-induced damage threshold(LIDT).In this work,b...Diamond-like AgGaS_(2)(DL AGS),as the typical infrared nonlinear optical(IR NLO)material,has suffered from its intrinsic drawbacks like narrow band gap(E_(g))and low laser-induced damage threshold(LIDT).In this work,by first introducing[NaS_(8)]polyhedral unit into the A_(2)^(Ⅰ)Q^(Ⅵ)-Ag_(2)Q^(Ⅵ)-C_(2)^(Ⅲ)Q_(3)^(Ⅵ) system,a new Ag-based sulfide NaAg_(3)Ga_(8)S_(14) with diamond-like framework(DLF)has been successfully synthesized via a high-temperature solid-state method in experiment.The compound shows a wide Eg(~3.0 eV),high LIDT(3.0×AGS)and moderate phase-matching NLO response(~0.7×AGS),effectively balancing the E_(g)(≥3.0 eV)and NLO response(≥0.5×AGS),demonstrating its promise for IR NLO applications.Theoretical calculations elucidate the orbital hybridization between Na 3s,Ag 4d5s and S 3p enhances E_(g),and the aligned NLO-active units([AgS_(4)]and[GaS_(4)])induce moderate NLO response in the compound.These findings not only expand the chemical and structural diversities of Ag-based chalcogenides,but also provide effective strategies for designing DLF functional materials derived from diamond-like structures.展开更多
基金the Natural Science Foundation of China(No.22105218).
文摘It is challenging to cooperatively improve the nonlinear optical(NLO)efficiency and the laser-induced damage threshold(LIDT).This work reports a novel IR NLO materials CsInP_(2)S_(7)(CIPS)designed by combination the strategies of alkali metals substitution and microscopic NLO units PS4 introduction based on AgGaS_(2).CIPS was composed of strongly distorted[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers constructed by corner-sharing[PS_(4)]^(3-),which increase the NLO efficiency and decrease thermal expansion anisotropy simultaneously.Compared with AgGaS_(2),CIPS exhibited strong phase matchable NLO response ca.1.1×AGS@2.1μm,high LIDT ca.20.8×AgGaS_(2),and IR transparency up to 15.3μm.Structural analysis and theoretical investigation confirmed that large SHG effect and ultrahigh LIDT of CIPS originated from the synergistic contribution of[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers.These results indicate that CIPS is a promising NLO candidate in the mid-IR region,and this study provides a new approach for developing potential NLO-LIDT compatible materials.
基金supported by the Tianshan Talent Training Program(2024TSYCLJ0035)the Natural Science Foundation of the Xinjiang Uygur Autonomous Region(2024D01E30,2025D01B157)+3 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0880000)the Open Fund of the Anhui Key Laboratory of Photonic Materials and Devices(AHKL2024KF02)the National Natural Sci-ence Foundation of China(22475234,52402017)the support from Tianchi Doctor Plan of Xinjiang Uygur Autonomous Region.
文摘Diamond-like AgGaS_(2)(DL AGS),as the typical infrared nonlinear optical(IR NLO)material,has suffered from its intrinsic drawbacks like narrow band gap(E_(g))and low laser-induced damage threshold(LIDT).In this work,by first introducing[NaS_(8)]polyhedral unit into the A_(2)^(Ⅰ)Q^(Ⅵ)-Ag_(2)Q^(Ⅵ)-C_(2)^(Ⅲ)Q_(3)^(Ⅵ) system,a new Ag-based sulfide NaAg_(3)Ga_(8)S_(14) with diamond-like framework(DLF)has been successfully synthesized via a high-temperature solid-state method in experiment.The compound shows a wide Eg(~3.0 eV),high LIDT(3.0×AGS)and moderate phase-matching NLO response(~0.7×AGS),effectively balancing the E_(g)(≥3.0 eV)and NLO response(≥0.5×AGS),demonstrating its promise for IR NLO applications.Theoretical calculations elucidate the orbital hybridization between Na 3s,Ag 4d5s and S 3p enhances E_(g),and the aligned NLO-active units([AgS_(4)]and[GaS_(4)])induce moderate NLO response in the compound.These findings not only expand the chemical and structural diversities of Ag-based chalcogenides,but also provide effective strategies for designing DLF functional materials derived from diamond-like structures.
