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
The maximum velocity of a mobile vortex in movement is generally limited by the phenomenon of flux-flow instability(FFI),which necessitates weak vortex pinning and fast heat removal from non-equilibrium electrons.We h...The maximum velocity of a mobile vortex in movement is generally limited by the phenomenon of flux-flow instability(FFI),which necessitates weak vortex pinning and fast heat removal from non-equilibrium electrons.We here demonstrate exfoliations and nano-fabrications of Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrips,which possess a rather weak pinning volume of vortices,relatively low resistivity,and large normal electron diffusion coefficient.The deduced vortex velocity in Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrips can be up to 300 km/s near the superconducting transition temperature,well above the speed of sound.The observed vortex velocity is an order of magnitude faster than that of conventional superconducting systems,representing a perfect platform for exploration of ultra-fast vortex matter and a good candidate for fabrications of superconducting nanowire single photon detectors or superconducting THz modulator.展开更多
In the traditional process, m-phenylenediamine reacts with fuming sulfuric acid at high temperature to get intermediates, and then after dehydration occurs intramolecular rearrangement to get 2,4-diaminobenzenesulfoni...In the traditional process, m-phenylenediamine reacts with fuming sulfuric acid at high temperature to get intermediates, and then after dehydration occurs intramolecular rearrangement to get 2,4-diaminobenzenesulfonic acid. Traditional methods need to consume a lot of fuming sulfuric acid or concentrated sulfuric acid, resulting in high industrial large-scale production cost, more waste, and posing a serious environmental pollution risk. In this thesis, three different sulfonation reagents were used for the sulfonation reaction of m-phenylenediamine, and the reaction mechanisms and crystal structures of the three pathways were investigated. The three routes are: 1) one-step synthesis of monosulfonated compound 1 from raw material and sulfur trioxide (SO<sub>3</sub>);2) rapid reaction of raw material and chlorosulfonic acid to synthesize bisulfonated compound 2;3) direct eutectic crystallization of raw material and ordinary sulfuric acid to obtain compound 3. The crystal structure of the compounds synthesized by three paths was analyzed by X-ray single crystal diffraction, and compound 1 was characterized by NMR, Fourier infrared spectra, UV-visible spectrum and Mass spectrometry. The one-step synthesis of SO<sub>3</sub> as a sulfonation reagent has the advantages of mild reaction conditions, simple operation and low cost.展开更多
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).
基金supporting high quality of post growth treatment Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ)single crystalssupported by the National Key Research and Development Program of China(Grant No.2017YFA0304000)+4 种基金the National Natural Science Foundation of China(Grant Nos.61971408 and 61827823)Shanghai Municipal Science and Technology Major Project(Grant No.2019SHZDZX01)Shanghai Rising-Star Program(Grant No.20QA1410900)the Youth Innovation Promotion Association of Chinese Academy of Sciences(Grant Nos.2020241 and 2021230)the Natural Science Foundation of Shanghai(Grant No.19ZR1467400)。
文摘The maximum velocity of a mobile vortex in movement is generally limited by the phenomenon of flux-flow instability(FFI),which necessitates weak vortex pinning and fast heat removal from non-equilibrium electrons.We here demonstrate exfoliations and nano-fabrications of Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrips,which possess a rather weak pinning volume of vortices,relatively low resistivity,and large normal electron diffusion coefficient.The deduced vortex velocity in Bi_(2)Sr_(2)Ca_(2)Cu_(3)O_(10+δ) crystalline nanostrips can be up to 300 km/s near the superconducting transition temperature,well above the speed of sound.The observed vortex velocity is an order of magnitude faster than that of conventional superconducting systems,representing a perfect platform for exploration of ultra-fast vortex matter and a good candidate for fabrications of superconducting nanowire single photon detectors or superconducting THz modulator.
文摘In the traditional process, m-phenylenediamine reacts with fuming sulfuric acid at high temperature to get intermediates, and then after dehydration occurs intramolecular rearrangement to get 2,4-diaminobenzenesulfonic acid. Traditional methods need to consume a lot of fuming sulfuric acid or concentrated sulfuric acid, resulting in high industrial large-scale production cost, more waste, and posing a serious environmental pollution risk. In this thesis, three different sulfonation reagents were used for the sulfonation reaction of m-phenylenediamine, and the reaction mechanisms and crystal structures of the three pathways were investigated. The three routes are: 1) one-step synthesis of monosulfonated compound 1 from raw material and sulfur trioxide (SO<sub>3</sub>);2) rapid reaction of raw material and chlorosulfonic acid to synthesize bisulfonated compound 2;3) direct eutectic crystallization of raw material and ordinary sulfuric acid to obtain compound 3. The crystal structure of the compounds synthesized by three paths was analyzed by X-ray single crystal diffraction, and compound 1 was characterized by NMR, Fourier infrared spectra, UV-visible spectrum and Mass spectrometry. The one-step synthesis of SO<sub>3</sub> as a sulfonation reagent has the advantages of mild reaction conditions, simple operation and low cost.
