Lead-based organic–inorganic metal halides(OIMHs)have recently attracted special attention due to their efficient broadband photoluminescence.However,the toxicity of lead poses a challenge for their further developme...Lead-based organic–inorganic metal halides(OIMHs)have recently attracted special attention due to their efficient broadband photoluminescence.However,the toxicity of lead poses a challenge for their further development.Here,we selected Sn(IV)as the metal center to synthesize the environmentally friendly and stable luminescent OIMHs(C_(9)H_(15)N_(3))_(2)SnCl_(8)and(C_(9)H_(15)N_(3))_(2)SnBr_(8)(C_(9)H_(13)N_(3)is 1-(_(2)-pyridyl)piperazine).展开更多
Low-dimensional hybrid organic-inorganic metal halides(OIMHs)have been extensively investigated for their structural tunability and unique optoelectronic properties.However,the synthesis of highly photoluminescent lea...Low-dimensional hybrid organic-inorganic metal halides(OIMHs)have been extensively investigated for their structural tunability and unique optoelectronic properties.However,the synthesis of highly photoluminescent lead-free OIMHs remains challenging.To address this issue,we synthesized a series of hybrid OIMHs(DETA)_(3)InCl_(6):xSb^(3+)(DETA=diethylenetriamine,x=0-15%).With Sb^(3+)doping,the photoluminescence quantum yield(PLQY)is greatly improved from 4.84%to nearly 100%.Moreover,(DETA)_(3)InCl_(6):10%Sb^(3+)single crystals exhibit strong yellow broadband emission originating from selftrapped exciton(STE)radiative recombination.Interestingly,when Sb^(3+)doping is 0.005%,the single crystal doped Sb emits white light at an excitation wavelength of 365 nm with CIE coordinates of(0.35,0.36).We also explored the effect of Sb^(3+)dopants and STE state formation by DFT calculations and ultrafast transient absorption techniques.This research provides new insights into the design of high-performance photoluminescent materials based on hybrid metal halides.展开更多
In the quest for organic–inorganic metal halides(OIMHs)that harmoniously combine large second harmonic generation(SHG)efficiency with broad bandgaps,our study introduces a series of noncentrosymmetric and polar piper...In the quest for organic–inorganic metal halides(OIMHs)that harmoniously combine large second harmonic generation(SHG)efficiency with broad bandgaps,our study introduces a series of noncentrosymmetric and polar piperazine zinc halides,(C_(4)H_(11)N_(2))ZnX_(3)(X=Cl,Br,I).The distinct influence of halide anion size on the configuration of ZnNX_(3)tetrahedra is uncovered,revealing a design principle for enhancing SHG activity and manipulating bandgap characteristics.Specifically,(C_(4)H_(11)N_(2))ZnCl_(3)is the first example of deep-ultraviolet(deep-UV)nonlinear optical(NLO)OIMHs,with UV transparency lower than 190 nm and moderate SHG effect,0.8 times KH_(2)PO_(4)(KDP).Meanwhile,compared with(C_(4)H_(11)N_(2))ZnI_(3)(2.1 times KDP,4.52 eV),(C_(4)H_(11)N_(2))ZnBr_(3)boasts a widened bandgap of 5.53 eV while maintaining a striking SHG response(2.5 times KDP),representing a pinnacle in the SHG-bandgap balance among OIMHs with Eg exceeding 5.0 eV.Computational analyses underscore the critical roles of halide orbitals and ZnNX_(3)distortions in dictating SHG efficiency,with increasing halide polarizability correlating with heightened SHG contributions.This study paves the way for a novel approach to designing short-UV NLO crystals based on OIMHs.展开更多
基金supported by The National Key Research and Development Program of China(2021YFA0718900)the National Natural Science Foundation of China(51972021)the Fundamental Research Funds for the Central Universities FRF-IDRY-19-005SHand cW are supported by the US Department of Energy,Office of Science and Office of Basic Energy Sciences|under award number DE-SC0014520.
文摘Lead-based organic–inorganic metal halides(OIMHs)have recently attracted special attention due to their efficient broadband photoluminescence.However,the toxicity of lead poses a challenge for their further development.Here,we selected Sn(IV)as the metal center to synthesize the environmentally friendly and stable luminescent OIMHs(C_(9)H_(15)N_(3))_(2)SnCl_(8)and(C_(9)H_(15)N_(3))_(2)SnBr_(8)(C_(9)H_(13)N_(3)is 1-(_(2)-pyridyl)piperazine).
基金supported by the National Natural Science Foundation of China(22275075)the Natural Science Foundation of Jiangxi Province(20204BCJ22015 and 20202ACBL203001)the Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry(20212BCD42018).
文摘Low-dimensional hybrid organic-inorganic metal halides(OIMHs)have been extensively investigated for their structural tunability and unique optoelectronic properties.However,the synthesis of highly photoluminescent lead-free OIMHs remains challenging.To address this issue,we synthesized a series of hybrid OIMHs(DETA)_(3)InCl_(6):xSb^(3+)(DETA=diethylenetriamine,x=0-15%).With Sb^(3+)doping,the photoluminescence quantum yield(PLQY)is greatly improved from 4.84%to nearly 100%.Moreover,(DETA)_(3)InCl_(6):10%Sb^(3+)single crystals exhibit strong yellow broadband emission originating from selftrapped exciton(STE)radiative recombination.Interestingly,when Sb^(3+)doping is 0.005%,the single crystal doped Sb emits white light at an excitation wavelength of 365 nm with CIE coordinates of(0.35,0.36).We also explored the effect of Sb^(3+)dopants and STE state formation by DFT calculations and ultrafast transient absorption techniques.This research provides new insights into the design of high-performance photoluminescent materials based on hybrid metal halides.
基金supported by the National Natural Science Foundation of China(No.22205037 and 22373014)Natural Science Foundation of Fujian Province(2023J01498).
文摘In the quest for organic–inorganic metal halides(OIMHs)that harmoniously combine large second harmonic generation(SHG)efficiency with broad bandgaps,our study introduces a series of noncentrosymmetric and polar piperazine zinc halides,(C_(4)H_(11)N_(2))ZnX_(3)(X=Cl,Br,I).The distinct influence of halide anion size on the configuration of ZnNX_(3)tetrahedra is uncovered,revealing a design principle for enhancing SHG activity and manipulating bandgap characteristics.Specifically,(C_(4)H_(11)N_(2))ZnCl_(3)is the first example of deep-ultraviolet(deep-UV)nonlinear optical(NLO)OIMHs,with UV transparency lower than 190 nm and moderate SHG effect,0.8 times KH_(2)PO_(4)(KDP).Meanwhile,compared with(C_(4)H_(11)N_(2))ZnI_(3)(2.1 times KDP,4.52 eV),(C_(4)H_(11)N_(2))ZnBr_(3)boasts a widened bandgap of 5.53 eV while maintaining a striking SHG response(2.5 times KDP),representing a pinnacle in the SHG-bandgap balance among OIMHs with Eg exceeding 5.0 eV.Computational analyses underscore the critical roles of halide orbitals and ZnNX_(3)distortions in dictating SHG efficiency,with increasing halide polarizability correlating with heightened SHG contributions.This study paves the way for a novel approach to designing short-UV NLO crystals based on OIMHs.
