Nonlinear optical(NLO)crystals are vital materials in optoelectronics and laser technology,as they can expand laser applications by converting the light beam wavelength and amplitude.In this study,two hybrid metal hal...Nonlinear optical(NLO)crystals are vital materials in optoelectronics and laser technology,as they can expand laser applications by converting the light beam wavelength and amplitude.In this study,two hybrid metal halides,namely(C_(14)H_(14)N_(2))ZnCl_(4) and(C_(14)H_(14)N_(2))CdCl_(4),were successfully synthesised by combining planar π-conjugated(C_(14)H_(14)N_(2))^(2+)cationic groups,and[ZnCl_(4)]^(2-)/[CdCl_(4)]^(2-)anionic tetrahedral genes.They both crystallize in the non-centrosymmetric space groups,monoclinic Cm and orthorhombic Cmc2_(1) for(C_(14)H_(14)N_(2))ZnCl_(4) and(C_(14)H_(14)N_(2))CdCl_(4),respectively.They exhibit excellent optical properties,including significant phase-matched second-harmonic generation responses(1.63 and 1.36×KDP),wide band gaps(3.20 and 3.13 eV),and large birefringence(0.325 and 0.341 at 1064 nm),making them promising NLO materials.Meanwhile,both crystals show broadband green photoluminescence.Theoretical studies and crystal structure analyses reveal that their large SHG effects and birefringence are primarily from the synergistic interaction between π-conjugated organic cations and distorted[ZnCl_(4)]^(2-)/[CdCl_(4)]^(2-)tetrahedra.This work provides a new way for designing high-performance hybrid metal halide NLO materials with broad luminescence.展开更多
基金financially supported by the Natural Science Foundation of Shandong Province(ZR2020MF128)the Shandong Provincial Key Laboratory of Monocrystalline Silicon Semiconductor Materials and Technology(2023KFKT010 and 2025KFKT001).
文摘Nonlinear optical(NLO)crystals are vital materials in optoelectronics and laser technology,as they can expand laser applications by converting the light beam wavelength and amplitude.In this study,two hybrid metal halides,namely(C_(14)H_(14)N_(2))ZnCl_(4) and(C_(14)H_(14)N_(2))CdCl_(4),were successfully synthesised by combining planar π-conjugated(C_(14)H_(14)N_(2))^(2+)cationic groups,and[ZnCl_(4)]^(2-)/[CdCl_(4)]^(2-)anionic tetrahedral genes.They both crystallize in the non-centrosymmetric space groups,monoclinic Cm and orthorhombic Cmc2_(1) for(C_(14)H_(14)N_(2))ZnCl_(4) and(C_(14)H_(14)N_(2))CdCl_(4),respectively.They exhibit excellent optical properties,including significant phase-matched second-harmonic generation responses(1.63 and 1.36×KDP),wide band gaps(3.20 and 3.13 eV),and large birefringence(0.325 and 0.341 at 1064 nm),making them promising NLO materials.Meanwhile,both crystals show broadband green photoluminescence.Theoretical studies and crystal structure analyses reveal that their large SHG effects and birefringence are primarily from the synergistic interaction between π-conjugated organic cations and distorted[ZnCl_(4)]^(2-)/[CdCl_(4)]^(2-)tetrahedra.This work provides a new way for designing high-performance hybrid metal halide NLO materials with broad luminescence.
