Yellow light-emitting diodes(LEDs) as soft light have attracted abundant attention in lithography room, museum and art gallery. However, the development of efficient yellow LEDs lags behind green and blue LEDs, and th...Yellow light-emitting diodes(LEDs) as soft light have attracted abundant attention in lithography room, museum and art gallery. However, the development of efficient yellow LEDs lags behind green and blue LEDs, and the available perovskites yellow LEDs suffer from the instability. Herein, a pressure-assisted cooling method is proposed to grow lead-free CsCu2I3single crystals, which possess uniform surface morphology and enhanced photoluminescence quantum yield(PLQY) stability, with only 10% PLQY losses after being stored in air after 5000 h.Then, the single crystals used for yellow LEDs without encapsulation exhibit a decent Correlated Color Temperature(CCT) of 4290 K, a Commission Internationale de l’Eclairage(CIE) coordinate of(0.38, 0.41), and an excellent 570-h operating stability under heating temperature of 100°C. Finally, the yellow LEDs facilitate the application in wireless visible light communication(VLC), which show a-3 dB bandwidth of 21.5 MHz and a high achievable data rate of 219.2 Mbps by using orthogonal frequency division multiplexing(OFDM) modulation with adaptive bit loading. The present work not only promotes the development of lead-free single crystals, but also inspires the potential of CsCu2I3in the field of yellow illumination and wireless VLC.展开更多
Recently,inorganic copper-based halide perovskites and their derivatives(CHPs)with chemical formulas AlCumXn(A=Rb and Cs;X=Cl,Br and I;l,m,and n are integers.),have received increasing attention in the photoluminescen...Recently,inorganic copper-based halide perovskites and their derivatives(CHPs)with chemical formulas AlCumXn(A=Rb and Cs;X=Cl,Br and I;l,m,and n are integers.),have received increasing attention in the photoluminescence field,due to their lead-free,cost-effective,earth-abundant and low electronic dimensionality.Ascribed to flexible valence charge of Cu(Cu1+and Cu2+)and complex competing phases,the crystal structures and phase stabilities of CHPs are complicated and ambiguous,which limits their experimental applications.Via comprehensive first-principles calculations,we have investigated thermodynamic stabilities of possible crystal phases for AlCumXn by considering all the possible secondary phases existing in inorganic crystal structure database(ICSD).Our results are in agreement with existing experiments and further predicted the existence of 10 stable CHPs,i.e.Rb3 Cu2 Br5,Rb3 Cu2 I5,Rb Cu2 Cl3,Rb2 Cu I3,Rb2 Cu Br4,Rb Cu Br3,Rb3 Cu2 Br7,Cs3 Cu2 Br7,Cs3 Cu2 Cl7 and Cs4 Cu5 Cl9,which have not yet been reported in experiments.This work provides a phase and compositional map that may guide experiments to synthesize more novel inorganic CHPs with diverse properties for potential functional applications.展开更多
Although lead-based perovskite solar cells have achieved more than 25%power conversion efficiency,the toxicity of lead and instability are still urgent problems faced in industrial application.Lead-free halide double ...Although lead-based perovskite solar cells have achieved more than 25%power conversion efficiency,the toxicity of lead and instability are still urgent problems faced in industrial application.Lead-free halide double perovskite(DP)materials are promising candidates to resolve these issues.Based on the density functional theory,we explore the geometric stability,thermodynamic stability,mechanical stability,electronic structures,and optical properties of theCs_(2)B 0BiI_(6)(B 0=Li,Na and K)DP materials.By analyzing the tolerance factor and octahedral factor,we find the geometric stabilities ofCs_(2)NaBiI_(6) andCs_(2)KBiI_(6) DPs are better thanCs_(2)LiBiI_(6).By calculating the total energy,formation energy and decomposition energy,we propose that the most favorable structure ofCs_(2)B 0BiI_(6) is the orthorhombic phase,andCs_(2)LiBiI_(6) is less stable relative to the other two counterparts from an energetic viewpoint.Mechanical stability evaluations reveal that the orthorhombicCs_(2)LiBiI_(6) material is less stable relative to the isostructuralCs_(2)NaBiI_(6) andCs_(2)KBiI_(6) DPs.The mechanical property calculations indicate that theCs_(2)B 0BiI_(6) DPs possess good ductility,which can be used as flexible materials.Electronic structures and optical property calculations show that the orthorhombicCs_(2)B 0BiI_(6) DPs have suitable band gap values,weaker exciton binding energies,and excellent optical absorption performance in the visible-light range.Based on the above comprehensive assessments,we can conclude that the orthorhombic Cs_(2)NaBiI_(6) and Cs_(2)KBiI_(6) DPs with good stability are promising candidates for solar cell applications.展开更多
Large-scale growth and heterogeneous integration with existing semiconductors are the main obstacles to the application of metal halide perovskites in optoelectronics.Herein,a universal vacuum evaporation strategy is ...Large-scale growth and heterogeneous integration with existing semiconductors are the main obstacles to the application of metal halide perovskites in optoelectronics.Herein,a universal vacuum evaporation strategy is presented to prepare copper halide films with wafer-scale spatial homogeneity.Benefiting from the electric field manipulation method,the built-in electric fields are optimized and further boost the self-powered UV photodetecting performances of common wide-bandgap semiconductors by more than three orders of magnitude.Furthermore,with effective modulation of the interfacial charge dynamics,the as-fabricated GaN-substrate heterojunction photodetector demonstrates an ultrahigh on/off ratio exceeding 107,an impressive responsivity of up to 256 mA W^(-1),and a remarkable detectivity of 2.16×10^(13) Jones at 350 nm,0 V bias.Additionally,the device exhibits an ultrafast response speed(t r/t d=716 ns/1.30 ms),an ultra-narrow photoresponse spectrum with an FWHM of 18 nm and outstanding continuous operational stability as well as long-term stability.Subsequently,a 372-pixel light-powered imaging sensor array with the coefficient of variation of photocurrents reducing to 5.20%is constructed,which demonstrates exceptional electrical homogeneity,operational reliability,and UV imaging capability.This strategy provides an efficient way for large-scale integration of metal halide perovskites with commercial semiconductors for miniature optoelectronic devices.展开更多
Chiral organic-inorganic metal halide semiconductors(OIMHSs)have recently attracted numerous interests due to their unique chirality,structural tunability,and extensive physical properties.However,most reported chiral...Chiral organic-inorganic metal halide semiconductors(OIMHSs)have recently attracted numerous interests due to their unique chirality,structural tunability,and extensive physical properties.However,most reported chiral OIMHSs contain toxic lead,which will be a potential obstacle to their further applications.Herein,we successfully synthesized a novel chiral lead-free tin(IV)-based OIMHS[(R)-3-hydroxyquinuclidinium]_(2)SnCl_(6)([R-HQ]_(2)SnCl_(6)).It exhibits a wide band gap(Eg)of about 4.11 eV.Moreover,[R-HQ]_(2)SnCl6 undergoes a phase transition around 330 K(Tc)and shows distinct dielectric switching characteristics with good repeatability.This work enriches the chiral lead-free OIMHS family and stimulates further exploration of chiral lead-free OIMHS switching materials.展开更多
Lead halide perovskite materials exhibit excellent scintillation performance,which,however,suffer from serious stability and toxicity problems.In contrast,the heavy metal-free anti-perovskite materials[MX_(4)]XA_(3)(A...Lead halide perovskite materials exhibit excellent scintillation performance,which,however,suffer from serious stability and toxicity problems.In contrast,the heavy metal-free anti-perovskite materials[MX_(4)]XA_(3)(A=alkali metal;M=transition metal;X=Cl,Br,I),a class of electron-inverted perovskite derivatives,exhibit robust structural and photophysical stability.Here,we design and prepare a lead-free[MnBr_(4)]BrCs_(3) anti-perovskite nanocrystal(NC)-embedded glass for efficient X-ray-excited luminescence with high-resolution X-ray imaging with a spatial resolution of 19.1 Ip mm^(-1).Due to the unique crystal structure and the protection of the glass matrix,the Cs_(3)MnBr_(5) NC-embedded glass exhibits excellent X-ray irradiation stability,thermal stability,and water resistance.These merits enable the demonstration of real-time and durable X-ray radiography based on the developed glassy composite.This work could stimulate the research and development of novel metal halide anti-perovskite materials and open a new path for future development in the field of high-resolution and ultrastable X-ray imaging.展开更多
All inorganic CsPbX_(3)(X=Cl,Br,and I)perovskite nanocrystals have made unprecedented radical progresses for opto-electronic applications,but their instability and toxicity of lead impede their wide applications.Herei...All inorganic CsPbX_(3)(X=Cl,Br,and I)perovskite nanocrystals have made unprecedented radical progresses for opto-electronic applications,but their instability and toxicity of lead impede their wide applications.Herein,we report the first precipitation of leadfree Mn:Cs_(2)ZnX_(4) nanocrystals in glasses.Efficient green and red photoluminescence are realized from these Mn:Cs_(2)ZnX_(4 )nanocrystals in glasses.By adjusting the size and halide component in these nanocrystals,coordination environment of Mn^(2+)ions can be tuned,leading to tunable photoluminescence with improved quantum efficiency.It is illustrated that in-situ precipitation of these Mn:Cs_(2)ZnX_(4) nanocrystals in glasses significantly improves their thermal-,chemical-,and photo-stabilities,making them promising for light-emitting diodes with stable chromaticity coordinates.展开更多
The high exciton binding energy and lack of a positive oxidation band potential restrict the photocatalytic CO_(2)reduction efficiency of lead-free Bi-based halide perovskites Cs_(3)Bi_(2)X_(9)(X=Br,I).In this study,a...The high exciton binding energy and lack of a positive oxidation band potential restrict the photocatalytic CO_(2)reduction efficiency of lead-free Bi-based halide perovskites Cs_(3)Bi_(2)X_(9)(X=Br,I).In this study,a sequential growth method is presented to prepare a visible-light-driven(λ>420 nm)Z-scheme heterojunction photocatalyst composed of BiVO_(4)nanocrystals decorated on a Cs_(3)Bi_(2)I_(9)nanosheet for photocatalytic CO_(2)reduction coupled with water oxidation.The Cs_(3)Bi_(2)I_(9)/BiVO_(4)Z-scheme heterojunction photocatalyst is stable in the gas-solid photocatalytic CO_(2)reduction system,demonstrating a high visible-light-driven photocatalytic CO_(2)-to-CO production rate of 17.5μmol/(g·h),which is approximately three times that of pristine Cs_(3)Bi_(2)I_(9).The high efficiency of the Cs_(3)Bi_(2)I_(9)/BiVO_(4)heterojunction was attributed to the improved charge separation in Cs_(3)Bi_(2)I_(9).Moreover,the Z-scheme charge-transfer pathway preserves the negative reduction potential of Cs_(3)Bi_(2)I_(9)and the positive oxidation potential of BiVO_()4.This study off ers solid evidence of constructing Z-scheme heterojunctions to improve the photocatalytic performance of lead-free halide perovskites and would inspire more ideas for developing leadfree halide perovskite photocatalysts.展开更多
The development of deep-red emitting lead-free metal-halide perovskites with high photoluminescence quantum yields (PLQYs) and outstanding stability remains a major challenge for displays and deep-tissue bioimaging.In...The development of deep-red emitting lead-free metal-halide perovskites with high photoluminescence quantum yields (PLQYs) and outstanding stability remains a major challenge for displays and deep-tissue bioimaging.In this work,we report a facile and convenient solvothermal method to synthesize metal halides Cs_(2)Zn X_(4)(X=Cl,Br) that however is PL innert at room temperature.Upon composition engineering utilizing Sn^(2+) as the dopant,the resulting Cs_(2)Zn Cl_(4):Sn not only emits strong deep-red PL peaked at700 nm with the highest 99.4%PLQY among the similar materials so far,but also exhibits excellent structure stability in air (PLQY remains 96%after one year exposure to the atmosphere).Detailed experimental characterizations and theoretical calculations reveal that the deep-red emission stems from self-trapped excitons induced by the Sn^(2+) dopant.Particularly,triplet emission (^(3)P_(2)→^(1)S_(0)) from Sn-5s^(2) orbitals has been observed at low temperature due to the break of parity-forbidden transition.This work provides an important guidance for the development of deep-red light-emitting materials with low price,high efficiency and excellent stability.展开更多
Copper-based metal halides have become important materials in the feld of X-ray and photodetection due to their excellent optical properties,good environmental stability and low toxicity.This review presents the progr...Copper-based metal halides have become important materials in the feld of X-ray and photodetection due to their excellent optical properties,good environmental stability and low toxicity.This review presents the progress of research on crystal structure/morphology,photophysics/optical properties and applications of copper-based metal halides.We also discuss the challenges of copper-based metal halides with a perspective of their future research directions.展开更多
Ferroelastic materials with switchable spontaneous strain possess widely potential applications in the field of energy and information conversion.Recently,organic-inorganic hybrid halide double perovskites (OIHHDPs) h...Ferroelastic materials with switchable spontaneous strain possess widely potential applications in the field of energy and information conversion.Recently,organic-inorganic hybrid halide double perovskites (OIHHDPs) have become a charming new platform for developing various functional materials,such as ferroelectrics,fluorescence and X–ray detection.Nevertheless,OIHHDP ferroelastic materials,especially high-temperature ones,are rare.Herein,we initially synthesized an OIHHDP ferroelastic,(2,2-difluoroethanamine)_(2)[(NH_(4))InCl_6](1),which possesses a ferroelastic phase transition at 407 K.Moreover,thanks to the flexible B-site for OIHHDPs,we replaced the NH_(4)^(+) ions within[(NH_(4))InCl_6]_n^(2n–)formworks with K^(+)ions,which endows with coordination bonds between 2,2-difluoroethanamine organic cations and[KInCl_6]_n^(2n–)formworks.Due to the existence of coordination bonds,the phase transition temperature of (2,2-difluoroethanamine)_(2)[KInCl_6](2) can reach 458 K.As far as we know,this value is the highest reported in OIHHDP ferroelastics.This work offers inspiration for the design of high-temperature OIHHDP phase transition materials including ferroelectrics and ferroelastics.展开更多
基金This work is funded by National Natural Science Foundation of China(Nos.61904023,11974063)Fundamental Research Funds for the Cen-tral Universities(2021CDJQY-022)Natural Science Foundation of Chongqing(No.cstc2019jcyj-bshX0078,cstc2020jcyj-jqX0028).
文摘Yellow light-emitting diodes(LEDs) as soft light have attracted abundant attention in lithography room, museum and art gallery. However, the development of efficient yellow LEDs lags behind green and blue LEDs, and the available perovskites yellow LEDs suffer from the instability. Herein, a pressure-assisted cooling method is proposed to grow lead-free CsCu2I3single crystals, which possess uniform surface morphology and enhanced photoluminescence quantum yield(PLQY) stability, with only 10% PLQY losses after being stored in air after 5000 h.Then, the single crystals used for yellow LEDs without encapsulation exhibit a decent Correlated Color Temperature(CCT) of 4290 K, a Commission Internationale de l’Eclairage(CIE) coordinate of(0.38, 0.41), and an excellent 570-h operating stability under heating temperature of 100°C. Finally, the yellow LEDs facilitate the application in wireless visible light communication(VLC), which show a-3 dB bandwidth of 21.5 MHz and a high achievable data rate of 219.2 Mbps by using orthogonal frequency division multiplexing(OFDM) modulation with adaptive bit loading. The present work not only promotes the development of lead-free single crystals, but also inspires the potential of CsCu2I3in the field of yellow illumination and wireless VLC.
基金funding support from National Natural Science Foundation of China(grant No.11674237 and 51602211)National Key Research and Development Program of China(grant No.2016YFB0700700)+2 种基金Natural Science Foundation of Jiangsu Province of China(grant No.BK20160299)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)China Post-doctoral Foundation(grant No.7131705619).
文摘Recently,inorganic copper-based halide perovskites and their derivatives(CHPs)with chemical formulas AlCumXn(A=Rb and Cs;X=Cl,Br and I;l,m,and n are integers.),have received increasing attention in the photoluminescence field,due to their lead-free,cost-effective,earth-abundant and low electronic dimensionality.Ascribed to flexible valence charge of Cu(Cu1+and Cu2+)and complex competing phases,the crystal structures and phase stabilities of CHPs are complicated and ambiguous,which limits their experimental applications.Via comprehensive first-principles calculations,we have investigated thermodynamic stabilities of possible crystal phases for AlCumXn by considering all the possible secondary phases existing in inorganic crystal structure database(ICSD).Our results are in agreement with existing experiments and further predicted the existence of 10 stable CHPs,i.e.Rb3 Cu2 Br5,Rb3 Cu2 I5,Rb Cu2 Cl3,Rb2 Cu I3,Rb2 Cu Br4,Rb Cu Br3,Rb3 Cu2 Br7,Cs3 Cu2 Br7,Cs3 Cu2 Cl7 and Cs4 Cu5 Cl9,which have not yet been reported in experiments.This work provides a phase and compositional map that may guide experiments to synthesize more novel inorganic CHPs with diverse properties for potential functional applications.
基金supported by the National Natural Science Foundation of China(Grant No.11864008)Guangxi Natural Science Foundation,China(Grant Nos.2018GXNSFAA138185,2018AD19200,and 2019GXNSFGA245006).
文摘Although lead-based perovskite solar cells have achieved more than 25%power conversion efficiency,the toxicity of lead and instability are still urgent problems faced in industrial application.Lead-free halide double perovskite(DP)materials are promising candidates to resolve these issues.Based on the density functional theory,we explore the geometric stability,thermodynamic stability,mechanical stability,electronic structures,and optical properties of theCs_(2)B 0BiI_(6)(B 0=Li,Na and K)DP materials.By analyzing the tolerance factor and octahedral factor,we find the geometric stabilities ofCs_(2)NaBiI_(6) andCs_(2)KBiI_(6) DPs are better thanCs_(2)LiBiI_(6).By calculating the total energy,formation energy and decomposition energy,we propose that the most favorable structure ofCs_(2)B 0BiI_(6) is the orthorhombic phase,andCs_(2)LiBiI_(6) is less stable relative to the other two counterparts from an energetic viewpoint.Mechanical stability evaluations reveal that the orthorhombicCs_(2)LiBiI_(6) material is less stable relative to the isostructuralCs_(2)NaBiI_(6) andCs_(2)KBiI_(6) DPs.The mechanical property calculations indicate that theCs_(2)B 0BiI_(6) DPs possess good ductility,which can be used as flexible materials.Electronic structures and optical property calculations show that the orthorhombicCs_(2)B 0BiI_(6) DPs have suitable band gap values,weaker exciton binding energies,and excellent optical absorption performance in the visible-light range.Based on the above comprehensive assessments,we can conclude that the orthorhombic Cs_(2)NaBiI_(6) and Cs_(2)KBiI_(6) DPs with good stability are promising candidates for solar cell applications.
基金financially supported by the National Natural Science Foundation of China(Nos.92263106,62204047,and 12061131009)Science and Technology Commission of Shanghai Municipality(Nos.21520712600 and 19520744300).
文摘Large-scale growth and heterogeneous integration with existing semiconductors are the main obstacles to the application of metal halide perovskites in optoelectronics.Herein,a universal vacuum evaporation strategy is presented to prepare copper halide films with wafer-scale spatial homogeneity.Benefiting from the electric field manipulation method,the built-in electric fields are optimized and further boost the self-powered UV photodetecting performances of common wide-bandgap semiconductors by more than three orders of magnitude.Furthermore,with effective modulation of the interfacial charge dynamics,the as-fabricated GaN-substrate heterojunction photodetector demonstrates an ultrahigh on/off ratio exceeding 107,an impressive responsivity of up to 256 mA W^(-1),and a remarkable detectivity of 2.16×10^(13) Jones at 350 nm,0 V bias.Additionally,the device exhibits an ultrafast response speed(t r/t d=716 ns/1.30 ms),an ultra-narrow photoresponse spectrum with an FWHM of 18 nm and outstanding continuous operational stability as well as long-term stability.Subsequently,a 372-pixel light-powered imaging sensor array with the coefficient of variation of photocurrents reducing to 5.20%is constructed,which demonstrates exceptional electrical homogeneity,operational reliability,and UV imaging capability.This strategy provides an efficient way for large-scale integration of metal halide perovskites with commercial semiconductors for miniature optoelectronic devices.
基金supported by the National Natural Science Foundation of China(Nos.22175082,91856114 and 21703033).
文摘Chiral organic-inorganic metal halide semiconductors(OIMHSs)have recently attracted numerous interests due to their unique chirality,structural tunability,and extensive physical properties.However,most reported chiral OIMHSs contain toxic lead,which will be a potential obstacle to their further applications.Herein,we successfully synthesized a novel chiral lead-free tin(IV)-based OIMHS[(R)-3-hydroxyquinuclidinium]_(2)SnCl_(6)([R-HQ]_(2)SnCl_(6)).It exhibits a wide band gap(Eg)of about 4.11 eV.Moreover,[R-HQ]_(2)SnCl6 undergoes a phase transition around 330 K(Tc)and shows distinct dielectric switching characteristics with good repeatability.This work enriches the chiral lead-free OIMHS family and stimulates further exploration of chiral lead-free OIMHS switching materials.
基金financially supported by the National Natural Science Foundation of China (62122027, 52002128, 62075063, 62205109, 12204179, 52202004)Key R&D Program of Guangzhou (202007020003)+6 种基金fellowship of the China Postdoctoral Science Foundation (2022M711185, 2021M691054)National Postdoctoral Program for Innovative Talents of China (BX20220113)Guangdong Basic and Applied Basic Research Foundation (2021A1515110911, 2021A1515110475, 2022A1515011289, 2023A1515012666)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01X137)Fundamental Research Funds for the Central Universities (2022ZYGXZR030)Guangzhou Basic and Applied Basic Research Foundation (202201010428)State Key Laboratory of Luminescent Materials and Devices, South China University of Technology
文摘Lead halide perovskite materials exhibit excellent scintillation performance,which,however,suffer from serious stability and toxicity problems.In contrast,the heavy metal-free anti-perovskite materials[MX_(4)]XA_(3)(A=alkali metal;M=transition metal;X=Cl,Br,I),a class of electron-inverted perovskite derivatives,exhibit robust structural and photophysical stability.Here,we design and prepare a lead-free[MnBr_(4)]BrCs_(3) anti-perovskite nanocrystal(NC)-embedded glass for efficient X-ray-excited luminescence with high-resolution X-ray imaging with a spatial resolution of 19.1 Ip mm^(-1).Due to the unique crystal structure and the protection of the glass matrix,the Cs_(3)MnBr_(5) NC-embedded glass exhibits excellent X-ray irradiation stability,thermal stability,and water resistance.These merits enable the demonstration of real-time and durable X-ray radiography based on the developed glassy composite.This work could stimulate the research and development of novel metal halide anti-perovskite materials and open a new path for future development in the field of high-resolution and ultrastable X-ray imaging.
基金supported by the Key Research and Development Program of Hubei Province,China(No.2021BAA206).
文摘All inorganic CsPbX_(3)(X=Cl,Br,and I)perovskite nanocrystals have made unprecedented radical progresses for opto-electronic applications,but their instability and toxicity of lead impede their wide applications.Herein,we report the first precipitation of leadfree Mn:Cs_(2)ZnX_(4) nanocrystals in glasses.Efficient green and red photoluminescence are realized from these Mn:Cs_(2)ZnX_(4 )nanocrystals in glasses.By adjusting the size and halide component in these nanocrystals,coordination environment of Mn^(2+)ions can be tuned,leading to tunable photoluminescence with improved quantum efficiency.It is illustrated that in-situ precipitation of these Mn:Cs_(2)ZnX_(4) nanocrystals in glasses significantly improves their thermal-,chemical-,and photo-stabilities,making them promising for light-emitting diodes with stable chromaticity coordinates.
基金support from the National Key R&D Plan Project(No.2022YFA1505000)Prospective Basic Research Projects of CNPC(Nos.2021DQ03(2022Z-29)+4 种基金2022DJ5406,2022DJ5407,2022DJ5408,2022DJ4507,and TGRI-2021-1)the Natural Science Foundation of Shaanxi Province(No.2022JQ-078)the Natural Science Foundation of China(No.52302308)the Outstanding Youth Science Foundation Project of the National Natural Science Foundation of China(Overseas)(No.GYKP033)the Qinchuangyuan Cited High-Level Innovative and Entrepreneurial Talents Project(No.QCYRCXM-2022-143).
文摘The high exciton binding energy and lack of a positive oxidation band potential restrict the photocatalytic CO_(2)reduction efficiency of lead-free Bi-based halide perovskites Cs_(3)Bi_(2)X_(9)(X=Br,I).In this study,a sequential growth method is presented to prepare a visible-light-driven(λ>420 nm)Z-scheme heterojunction photocatalyst composed of BiVO_(4)nanocrystals decorated on a Cs_(3)Bi_(2)I_(9)nanosheet for photocatalytic CO_(2)reduction coupled with water oxidation.The Cs_(3)Bi_(2)I_(9)/BiVO_(4)Z-scheme heterojunction photocatalyst is stable in the gas-solid photocatalytic CO_(2)reduction system,demonstrating a high visible-light-driven photocatalytic CO_(2)-to-CO production rate of 17.5μmol/(g·h),which is approximately three times that of pristine Cs_(3)Bi_(2)I_(9).The high efficiency of the Cs_(3)Bi_(2)I_(9)/BiVO_(4)heterojunction was attributed to the improved charge separation in Cs_(3)Bi_(2)I_(9).Moreover,the Z-scheme charge-transfer pathway preserves the negative reduction potential of Cs_(3)Bi_(2)I_(9)and the positive oxidation potential of BiVO_()4.This study off ers solid evidence of constructing Z-scheme heterojunctions to improve the photocatalytic performance of lead-free halide perovskites and would inspire more ideas for developing leadfree halide perovskite photocatalysts.
基金the financial supports from National Natural Science Foundation of China (Nos. 91741105, 22109130)Chongqing Municipal Natural Science Foundation (Nos. cstc2018jcyj AX0625, cstc2021jcyj-msxm X1180)Program for Innovation Team Building at Institutions of Higher Education in Chongqing (No. CXTDX201601011)。
文摘The development of deep-red emitting lead-free metal-halide perovskites with high photoluminescence quantum yields (PLQYs) and outstanding stability remains a major challenge for displays and deep-tissue bioimaging.In this work,we report a facile and convenient solvothermal method to synthesize metal halides Cs_(2)Zn X_(4)(X=Cl,Br) that however is PL innert at room temperature.Upon composition engineering utilizing Sn^(2+) as the dopant,the resulting Cs_(2)Zn Cl_(4):Sn not only emits strong deep-red PL peaked at700 nm with the highest 99.4%PLQY among the similar materials so far,but also exhibits excellent structure stability in air (PLQY remains 96%after one year exposure to the atmosphere).Detailed experimental characterizations and theoretical calculations reveal that the deep-red emission stems from self-trapped excitons induced by the Sn^(2+) dopant.Particularly,triplet emission (^(3)P_(2)→^(1)S_(0)) from Sn-5s^(2) orbitals has been observed at low temperature due to the break of parity-forbidden transition.This work provides an important guidance for the development of deep-red light-emitting materials with low price,high efficiency and excellent stability.
基金funded by the National Natural Science Foundation of China(Grant Nos.22279049 and 52073131)the Fundamental Research Funds for the Central Universities(Nos.lzujbky-2021-ct15 and lzujbky-2021-sp69).
文摘Copper-based metal halides have become important materials in the feld of X-ray and photodetection due to their excellent optical properties,good environmental stability and low toxicity.This review presents the progress of research on crystal structure/morphology,photophysics/optical properties and applications of copper-based metal halides.We also discuss the challenges of copper-based metal halides with a perspective of their future research directions.
基金supported financially by the National Key Research and Development Program of China (No. 2017YFA0204800)National Natural Science Foundation of China (Nos. 22175079 and 21875093)+1 种基金Natural Science Foundation of Jiangxi Province (Nos. 20204BCJ22015 and 20202ACBL203001)Jiangxi Provincial Department of Education Science and Technology Research Project (No. GJJ210812)。
文摘Ferroelastic materials with switchable spontaneous strain possess widely potential applications in the field of energy and information conversion.Recently,organic-inorganic hybrid halide double perovskites (OIHHDPs) have become a charming new platform for developing various functional materials,such as ferroelectrics,fluorescence and X–ray detection.Nevertheless,OIHHDP ferroelastic materials,especially high-temperature ones,are rare.Herein,we initially synthesized an OIHHDP ferroelastic,(2,2-difluoroethanamine)_(2)[(NH_(4))InCl_6](1),which possesses a ferroelastic phase transition at 407 K.Moreover,thanks to the flexible B-site for OIHHDPs,we replaced the NH_(4)^(+) ions within[(NH_(4))InCl_6]_n^(2n–)formworks with K^(+)ions,which endows with coordination bonds between 2,2-difluoroethanamine organic cations and[KInCl_6]_n^(2n–)formworks.Due to the existence of coordination bonds,the phase transition temperature of (2,2-difluoroethanamine)_(2)[KInCl_6](2) can reach 458 K.As far as we know,this value is the highest reported in OIHHDP ferroelastics.This work offers inspiration for the design of high-temperature OIHHDP phase transition materials including ferroelectrics and ferroelastics.
