Low-temperature,ambient processing of high-quality CsPbBr_(3)films is demanded for scalable production of efficient,low-cost carbon-electrode perovskite solar cells(PSCs).Herein,we demonstrate a crystal orientation en...Low-temperature,ambient processing of high-quality CsPbBr_(3)films is demanded for scalable production of efficient,low-cost carbon-electrode perovskite solar cells(PSCs).Herein,we demonstrate a crystal orientation engineering strategy of PbBr_(2)precursor film to accelerate its reaction with CsBr precursor during two-step sequential deposition of CsPbBr_(3)films.Such a novel strategy is proceeded by adding CsBr species into PbBr_(2)precursor,which can tailor the preferred crystal orientation of PbBr_(2)film from[020]into[031],with CsBr additive staying in the film as CsPb_(2)Br_(5)phase.Theoretical calculations show that the reaction energy barrier of(031)planes of PbBr_(2)with CsBr is lower about 2.28 eV than that of(O2O)planes.Therefore,CsPbBr_(3)films with full coverage,high purity,high crystallinity,micro-sized grains can be obtained at a low temperature of 150℃.Carbon-electrode PSCs with these desired CsPbBr_(3)films yield the record-high efficiency of 10.27%coupled with excellent operation stability.Meanwhile,the 1 cm^(2)area one with the superior efficiency of 8.00%as well as the flexible one with the champion efficiency of 8.27%and excellent mechanical bending characteristics are also achieved.展开更多
CsPbCl_(3) perovskite is considered a highly promising material for ultraviolet (UV) photodetectors due to its exceptional thermal stability and excellent short-wavelength light response. However, its high lattice ene...CsPbCl_(3) perovskite is considered a highly promising material for ultraviolet (UV) photodetectors due to its exceptional thermal stability and excellent short-wavelength light response. However, its high lattice energy and low polarizability result in extremely low solubility in conventional solvents, making the synthesis of CsPbCl_(3) single crystals a significant challenge. In this study, we propose a novel thermodynamically induced crystal restructuring (TICR) process that can transform microcrystalline films (MCFs) into single crystal films (SCFs) within a short period. This method, for the first time, has successfully achieved the synthesis of centimeter-sized CsPbCl_(3) SCFs and the mechanism has been explored in depth using in-situ techniques. Furthermore, we report the first instance of a CsPbCl_(3) SCF UV photodiode, which exhibits a record-breaking on/off ratio of 3.32 × 10^(7) and a detectivity of up to 1.15 × 10^(14) Jones under 0 V bias. It demonstrates excellent response even under weak light conditions of 10 nW·cm^(−2) and maintains outstanding stability with almost no performance degradation after 15 months. This study provides a novel approach for the synthesis of perovskite single crystals and holds significant potential for advancing the development of high-performance optoelectronic devices.展开更多
Low-dimensional halide perovskites have become the most promising candidates for X-ray imaging,yet the issues of the poor chemical stability of hybrid halide perovskite,the high poisonousness of lead halides and the r...Low-dimensional halide perovskites have become the most promising candidates for X-ray imaging,yet the issues of the poor chemical stability of hybrid halide perovskite,the high poisonousness of lead halides and the relatively low detectivity of the lead-free halide perovskites which seriously restrain its commercialization.Here,we developed a solution inverse temperature crystal growth(ITCG)method to bring-up high quality Cs_(3)Cu_(2)I_(5)crystals with large size of centimeter order,in which the oleic acid(OA)is introduced as an antioxidative ligand to inhibit the oxidation of cuprous ions effieiently,as well as to decelerate the crystallization rate remarkalby.Based on these fine crystals,the vapor deposition technique is empolyed to prepare high quality Cs_(3)Cu_(2)I_(5)films for efficient X-ray imaging.Smooth surface morphology,high light yields and short decay time endow the Cs_(3)Cu_(2)I_(5)films with strong radioluminescence,high resolution(12 lp/mm),low detection limits(53 nGyair/s)and desirable stability.Subsequently,the Cs_(3)Cu_(2)I_(5)films have been applied to the practical radiography which exhibit superior X-ray imaging performance.Our work provides a paradigm to fabricate nonpoisonous and chemically stable inorganic halide perovskite for X-ray imaging.展开更多
Adding Na_(2)CO_(3) to the NaHCO_(3) cooling crystallizer, using the common ion effect to promote crystallization and improve product morphology, is a new process recently proposed in the literature. However, the mech...Adding Na_(2)CO_(3) to the NaHCO_(3) cooling crystallizer, using the common ion effect to promote crystallization and improve product morphology, is a new process recently proposed in the literature. However, the mechanism of the impact of Na_(2)CO_(3)on the crystal morphology is still indeterminate. In this work, the crystallization of NaHCO_(3)in water and Na_(2)CO_(3)–NaHCO_(3) aqueous solution was investigated by experiments and molecular dynamics simulations(MD). The crystallization results demonstrate that the morphology of NaHCO_(3) crystal changed gradually from needle-like to flake structure with the addition of Na_(2)CO_(3). The simulation results indicate that the layer docking model and the modified attachment energy formula without considering the roughness of crystal surface can obtain the crystal morphology in agreement with the experimental results, but the lower molecules of the crystal layer have to be fixed during MD. Thermodynamic calculation of the NaHCO_(3) crystallization process verifies that the common ion effect from Na^(+)and the ionization equilibrium transformation from CO_(3)^(2-) jointly promote the precipitation of NaHCO_(3) crystal. The radial distribution function analysis indicates that the oxygen atoms of Na_(2)CO_(3) formed strong hydrogen bonds with the hydrogen atoms of the(0 1 1) face, which weakened the hydration of water molecules at the crystal surface, resulting in a significant change in the attachment energy of this crystal surface. In addition, Na+and CO_(3)^(2-) are more likely to accumulate on the(011) face,resulting in the fastest growth rate on this crystal surface, which eventually leads to a change in crystal morphology from needle-like to flake-like.展开更多
The effect of substitution La_(2)O_(3)and YF_(3)as network modifiers respectively for Y_(2)O_(3),and ZnO as intermediate oxide for Al_(2)O_(3)on crystallization and viscous behavior of Y_(2)O_(3)-Al_(2)O_(3)-SiO_(2)gl...The effect of substitution La_(2)O_(3)and YF_(3)as network modifiers respectively for Y_(2)O_(3),and ZnO as intermediate oxide for Al_(2)O_(3)on crystallization and viscous behavior of Y_(2)O_(3)-Al_(2)O_(3)-SiO_(2)glass was studied.La_(2)O_(3)and YF_(3)substitution for Y_(2)O_(3)decreases the melting temperature of studied glass from 1402 to 1346 and 1379℃,and the activation energy of viscous flow decreases from 340 to 250 and 265 kJ/mol.Meanwhile,ZnO substitution for Al_(2)O_(3)decreases the melting temperature to 1379℃while increases the activation energy of viscous flow to 542 kJ/mol,due to their different role in glass structure.Substitution ZnO for Al_(2)O_(3)refines and homogenizes the crystals size and lowers crystallinity because the nucleation and crystal growth are depressed by higher activation energy of crystallization and change of crystallization mechanism from bulk crystallization to surface crystallization.Replacement of Y_(2)O_(3)by La_(2)O_(3)and YF_(3)respectively also decreases the crystallinity of Y_(2)O_(3)-Al_(2)O_(3)-SiO_(2)glass ceramic due to competitive and hindering effect on the rearranged atoms,structural units and groups required by precipitated two crystals.Besides,y-Y2Si2O7,precipitation of Y4.67(SiO4)3O,ZnAl_(2)O_(4),and Y3Si3O10F were observed respectively due to incorporation of La_(2)O_(3),ZnO,and YF_(3).展开更多
基金the financial support from the National Key R&D program of China(2021YFF0500501 and 2021YFF0500504)the Fundamental Research Funds for the Central Universities(YJS2213 and JB211408)+1 种基金the National Natural Science Foundation of China(61874083)the Joint Research Funds of Department of Science&Technology of Shaanxi Province and Northwestern Polytechnical University(No.2020GXLH-Z-014)
文摘Low-temperature,ambient processing of high-quality CsPbBr_(3)films is demanded for scalable production of efficient,low-cost carbon-electrode perovskite solar cells(PSCs).Herein,we demonstrate a crystal orientation engineering strategy of PbBr_(2)precursor film to accelerate its reaction with CsBr precursor during two-step sequential deposition of CsPbBr_(3)films.Such a novel strategy is proceeded by adding CsBr species into PbBr_(2)precursor,which can tailor the preferred crystal orientation of PbBr_(2)film from[020]into[031],with CsBr additive staying in the film as CsPb_(2)Br_(5)phase.Theoretical calculations show that the reaction energy barrier of(031)planes of PbBr_(2)with CsBr is lower about 2.28 eV than that of(O2O)planes.Therefore,CsPbBr_(3)films with full coverage,high purity,high crystallinity,micro-sized grains can be obtained at a low temperature of 150℃.Carbon-electrode PSCs with these desired CsPbBr_(3)films yield the record-high efficiency of 10.27%coupled with excellent operation stability.Meanwhile,the 1 cm^(2)area one with the superior efficiency of 8.00%as well as the flexible one with the champion efficiency of 8.27%and excellent mechanical bending characteristics are also achieved.
基金the National Key Research and Development Program of China(Nos.2022YFB3803300 and 2023YFE0116800)Beijing Natural Science Foundation(No.IS23037).
文摘CsPbCl_(3) perovskite is considered a highly promising material for ultraviolet (UV) photodetectors due to its exceptional thermal stability and excellent short-wavelength light response. However, its high lattice energy and low polarizability result in extremely low solubility in conventional solvents, making the synthesis of CsPbCl_(3) single crystals a significant challenge. In this study, we propose a novel thermodynamically induced crystal restructuring (TICR) process that can transform microcrystalline films (MCFs) into single crystal films (SCFs) within a short period. This method, for the first time, has successfully achieved the synthesis of centimeter-sized CsPbCl_(3) SCFs and the mechanism has been explored in depth using in-situ techniques. Furthermore, we report the first instance of a CsPbCl_(3) SCF UV photodiode, which exhibits a record-breaking on/off ratio of 3.32 × 10^(7) and a detectivity of up to 1.15 × 10^(14) Jones under 0 V bias. It demonstrates excellent response even under weak light conditions of 10 nW·cm^(−2) and maintains outstanding stability with almost no performance degradation after 15 months. This study provides a novel approach for the synthesis of perovskite single crystals and holds significant potential for advancing the development of high-performance optoelectronic devices.
基金the financially support of the National Natural Science Foundation of China(12164051)the Joint Foundation of Provincial Science and Technology Department-Double First-class Construction of Yunnan University(2019FY003016)+4 种基金the Young Top Talent Project of Yunnan Province(YNWR-QNBJ-2018-229)the financially support by Yunnan Major Scientific and Technological Projects(202202AG050016)Advanced Analysis and Measurement Center of Yunnan University for the sample characterization service and the Postgraduate Research and Innovation Foundation of Yunnan University(2021Y036)the financially support of the National Natural Science Foundation of China(62064013)the Application Basic Research Project of Yunnan Province[2019FB130]。
文摘Low-dimensional halide perovskites have become the most promising candidates for X-ray imaging,yet the issues of the poor chemical stability of hybrid halide perovskite,the high poisonousness of lead halides and the relatively low detectivity of the lead-free halide perovskites which seriously restrain its commercialization.Here,we developed a solution inverse temperature crystal growth(ITCG)method to bring-up high quality Cs_(3)Cu_(2)I_(5)crystals with large size of centimeter order,in which the oleic acid(OA)is introduced as an antioxidative ligand to inhibit the oxidation of cuprous ions effieiently,as well as to decelerate the crystallization rate remarkalby.Based on these fine crystals,the vapor deposition technique is empolyed to prepare high quality Cs_(3)Cu_(2)I_(5)films for efficient X-ray imaging.Smooth surface morphology,high light yields and short decay time endow the Cs_(3)Cu_(2)I_(5)films with strong radioluminescence,high resolution(12 lp/mm),low detection limits(53 nGyair/s)and desirable stability.Subsequently,the Cs_(3)Cu_(2)I_(5)films have been applied to the practical radiography which exhibit superior X-ray imaging performance.Our work provides a paradigm to fabricate nonpoisonous and chemically stable inorganic halide perovskite for X-ray imaging.
基金supported by the National Natural Science Foundation of China (21878143)the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)。
文摘Adding Na_(2)CO_(3) to the NaHCO_(3) cooling crystallizer, using the common ion effect to promote crystallization and improve product morphology, is a new process recently proposed in the literature. However, the mechanism of the impact of Na_(2)CO_(3)on the crystal morphology is still indeterminate. In this work, the crystallization of NaHCO_(3)in water and Na_(2)CO_(3)–NaHCO_(3) aqueous solution was investigated by experiments and molecular dynamics simulations(MD). The crystallization results demonstrate that the morphology of NaHCO_(3) crystal changed gradually from needle-like to flake structure with the addition of Na_(2)CO_(3). The simulation results indicate that the layer docking model and the modified attachment energy formula without considering the roughness of crystal surface can obtain the crystal morphology in agreement with the experimental results, but the lower molecules of the crystal layer have to be fixed during MD. Thermodynamic calculation of the NaHCO_(3) crystallization process verifies that the common ion effect from Na^(+)and the ionization equilibrium transformation from CO_(3)^(2-) jointly promote the precipitation of NaHCO_(3) crystal. The radial distribution function analysis indicates that the oxygen atoms of Na_(2)CO_(3) formed strong hydrogen bonds with the hydrogen atoms of the(0 1 1) face, which weakened the hydration of water molecules at the crystal surface, resulting in a significant change in the attachment energy of this crystal surface. In addition, Na+and CO_(3)^(2-) are more likely to accumulate on the(011) face,resulting in the fastest growth rate on this crystal surface, which eventually leads to a change in crystal morphology from needle-like to flake-like.
基金the National Natural Science Foundation of China(No.51974168)the Science and Technology Major Project of Inner Mongolia Autonomous Region in China(Nos.2019ZD023 and 2021ZD0028)the State Key Laboratory of Silicate Materials for Architectures(Wuhan University of Technology)(No.SYSJJ2020-08)。
文摘The effect of substitution La_(2)O_(3)and YF_(3)as network modifiers respectively for Y_(2)O_(3),and ZnO as intermediate oxide for Al_(2)O_(3)on crystallization and viscous behavior of Y_(2)O_(3)-Al_(2)O_(3)-SiO_(2)glass was studied.La_(2)O_(3)and YF_(3)substitution for Y_(2)O_(3)decreases the melting temperature of studied glass from 1402 to 1346 and 1379℃,and the activation energy of viscous flow decreases from 340 to 250 and 265 kJ/mol.Meanwhile,ZnO substitution for Al_(2)O_(3)decreases the melting temperature to 1379℃while increases the activation energy of viscous flow to 542 kJ/mol,due to their different role in glass structure.Substitution ZnO for Al_(2)O_(3)refines and homogenizes the crystals size and lowers crystallinity because the nucleation and crystal growth are depressed by higher activation energy of crystallization and change of crystallization mechanism from bulk crystallization to surface crystallization.Replacement of Y_(2)O_(3)by La_(2)O_(3)and YF_(3)respectively also decreases the crystallinity of Y_(2)O_(3)-Al_(2)O_(3)-SiO_(2)glass ceramic due to competitive and hindering effect on the rearranged atoms,structural units and groups required by precipitated two crystals.Besides,y-Y2Si2O7,precipitation of Y4.67(SiO4)3O,ZnAl_(2)O_(4),and Y3Si3O10F were observed respectively due to incorporation of La_(2)O_(3),ZnO,and YF_(3).