The immobilization of biomaterials on a carrier is the first step for many different applications in life science and medicine. The usage of surface-near electrostatic forces is one possible approach to guide the char...The immobilization of biomaterials on a carrier is the first step for many different applications in life science and medicine. The usage of surface-near electrostatic forces is one possible approach to guide the charged biomaterials to a specific location on the carrier. In this study, we investigate the effect of intrinsic defects on the surface potential of silicon carriers in the dark and under illumination by means of Kelvin probe force microscopy. The intrinsic defects were introduced into the carrier by local, stripe-patterned ion implantation of silicon ions with a fluence of 3 × 10<sup>13</sup> Si ions/cm<sup>2</sup> and 3 × 10<sup>15</sup> Si ions/cm<sup>2</sup> into a p-type silicon wafer with a dopant concentration of 9 × 10<sup>15</sup> B/cm<sup>3</sup>. The patterned implantation allows a direct comparison between the surface potential of the silicon host against the surface potential of implanted stripes. The depth of the implanted silicon ions in the target and the concentration of displaced silicon atoms was simulated using the Stopping and Range of Ions in Matter (SRIM) software. The low fluence implantation shows a negligible effect on the measured Kelvin bias in the dark, whereas the large fluence implantation leads to an increased Kelvin bias, i.e. to a smaller surface work function according to the contact potential difference model. Illumination causes a reduced surface band bending and surface potential in the non-implanted regions. The change of the Kelvin bias in the implanted regions under illumination provides insight into the mobility and lifetime of photo-generated electron-hole pairs. Finally, the effect of annealing on the intrinsic defect density is discussed and compared with atomic force microscopy measurements on the 2<sup>nd</sup> harmonic. In addition, by using the Baumgart, Helm, Schmidt interpretation of the measured Kelvin bias, the dopant concentration after implantation is estimated.展开更多
With the depletion of fossil fuels and environmental pollution, energy storage and conversion have become the focus of current research. Water splitting and fuel cell technologies have made outstanding contributions t...With the depletion of fossil fuels and environmental pollution, energy storage and conversion have become the focus of current research. Water splitting and fuel cell technologies have made outstanding contributions to energy conversion. However, the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) have slow kinetics, which limit the capacity of fuel cells. It is of great significance to develop catalysts for the OER and ORR and continuously improve their catalytic performance. Many studies have shown that intrinsic defects, especially vacancies (anion and cation vacancies), can effectively improve the efficiency of electrochemical energy storage and conversion. The introduction of intrinsic defects can generally expose more active sites, enhance conductivity, adjust the electronic state, and promote ion diffusion, thereby enhancing the catalytic performance. This review comprehensively summarizes the latest developments regarding the effects of intrinsic defects on the performance of non-noble metal electrocatalysts. According to the type of intrinsic defect, this article reviews in detail the regulation mechanism, preparation methods and advanced characterization techniques of intrinsic defects in different materials (oxides, non-oxides, etc.). Then, the current difficulties and future development of intrinsic defect regulation are analyzed and discussed thoroughly. Finally, the prospect of intrinsic defects in the field of electrochemical energy storage is further explored.展开更多
Over the years,the fact that the quaternary diamond-like thermoelectric materials show much lower carrier mobilities than ternary compounds remains mysterious.In this work,by adopting first-principles defect chemistry...Over the years,the fact that the quaternary diamond-like thermoelectric materials show much lower carrier mobilities than ternary compounds remains mysterious.In this work,by adopting first-principles defect chemistry and electrical transport calculations,the fundamental origin of the difference on carrier mobility between quaternary and ternary diamond-like compounds is addressed,exemplified by Cd_(2)Cu_(3)In_(3)Te_(8).The results of defect chemistry show that the main intrinsic defects in quaternary compound Cd_(2)Cu_(3)In_(3)Te_(8) are substitutional defects,i.e.,CdIn and CdCu,differing from the copper vacancy defect in ternary Cu-based compound such as CuInTe_(2).The low defect formation energies in Cd_(2)Cu_(3)In_(3)Te_(8) result in high defect concentrations,which is caused by the similar atomic radii and electronegativities between CdeIn and CdeCu.Further calculations show that the low-energy defects are mainly located around the valence band maximum in Cd_(2)Cu_(3)In_(3)Te_(8).The electrical transport calculations,considering both the acoustic phonon scattering and ionized impurity scattering,demonstrate that mainly due to the higher concentration of the ionized defects,the mobility of the quaternary Cd_(2)Cu_(3)In_(3)Te_(8) is much lower than that of ternary CuInTe2.Our work sheds light on the intrinsic defects in quaternary diamond-like compounds and their influence on charge transport.展开更多
Electrocatalytic carbon dioxide(CO2)reduction(ECR)has become one of the main methods to close the broken carbon cycle and temporarily store renewable energy,but there are still some problems such as poor stability,low...Electrocatalytic carbon dioxide(CO2)reduction(ECR)has become one of the main methods to close the broken carbon cycle and temporarily store renewable energy,but there are still some problems such as poor stability,low activity,and selectivity.While the most promising strategy to improve ECR activity is to develop electrocatalysts with low cost,high activity,and long-term stability.Recently,defective carbon-based nanomaterials have attracted extensive attention due to the unbalanced electron distribution and electronic structural distortion caused by the defects on the carbon materials.Here,the present review mainly summarizes the latest research progress of the construction of the diverse types of defects(intrinsic carbon defects,heteroatom doping defects,metal atomic sites,and edges detects)for carbon materials in ECR,and unveil the structure-activity relationship and its catalytic mechanism.The current challenges and opportunities faced by high-performance carbon materials in ECR are discussed,as well as possible future solutions.It can be believed that this review can provide some inspiration for the future of development of high-performance ECR catalysts.展开更多
Annealing was carried out at 950 and 1120℃ under various As pressure for undoped (ND) semi-insulating (SI) LECGaAs. The effects of annealing on native defects and electrical propefties were investigated. Experime...Annealing was carried out at 950 and 1120℃ under various As pressure for undoped (ND) semi-insulating (SI) LECGaAs. The effects of annealing on native defects and electrical propefties were investigated. Experimental re- sults indicate that, after an annealing at 950℃ for 14h under low As pressure, the Hall mobility decreases and the resis- tivity increases dramatically for the samples. These changes in electrical properties are due to the generation of intrinsic acceptor defects, and the generation of the intrinsic acceptor defects originates from the outdiffusion of As interstitial at high temperature. The generation of the intrinsic defects and these changes in electrical properties can be suppressed by increasing the applied As pressure during annealing. The concentration of the main donor defect E12 (AsGaVGa) can be decreased by about one order of magnitude by an evacuated annaling at 1120℃ for 2-8 h followed by a fast cooling. The decrease in E12 concentration can also be suppressed by increasing the As pressure during annealing.展开更多
The commercialization of lithium-sulfur(Li-S)batteries faces several bottlenecks,and the major two of which are the shuttle effect of polysulfides and the wild growth of Li dendrites,responsible for fast capacity deca...The commercialization of lithium-sulfur(Li-S)batteries faces several bottlenecks,and the major two of which are the shuttle effect of polysulfides and the wild growth of Li dendrites,responsible for fast capacity decay and severe safety issues.As an essential component of Li-S batteries,the structure and properties of the separators are closely related to the above problems,and the exploration of multifunctional separators is highly sought-after.Herein,an integrated separator composited of defective graphene and polyimide(DG-PI)was innovatively fabricated by electrospinning combined with the laser-induced carbonization strategy.The all-in-one compact architecture with well-interconnected channels shows superior mechanical and thermal stability and wettability.More importantly,the PI nanofibers containing N–/O–functional groups can induce the uniform deposition of lithium on the anode surface,while the DG framework with abundant pentagonal/heptagonal rings and vacancies can strongly trap polysulfides and accelerate polysulfide transformation on the cathode side.The strong chemical interaction between the insulative PI layer and the conductive DG layer modulates the surface charge distribution of each other,leading to more prominent contributions to restraining lithium dendrites and shuttle effect.Therefore,the Li-S batteries based on the integrated DG-PI separators afford an excellent performance in protecting lithium anode(stable cycles of 200 h at 5 mA·cm^(−2))and good cycling stability with a low capacity decay of 0.05%per cycle after 700 cycles at 1 C.This work offers a new design concept of multifunctional Li-S battery separators and broadens the application scope of laser micro-nano fabrication technology.展开更多
文摘The immobilization of biomaterials on a carrier is the first step for many different applications in life science and medicine. The usage of surface-near electrostatic forces is one possible approach to guide the charged biomaterials to a specific location on the carrier. In this study, we investigate the effect of intrinsic defects on the surface potential of silicon carriers in the dark and under illumination by means of Kelvin probe force microscopy. The intrinsic defects were introduced into the carrier by local, stripe-patterned ion implantation of silicon ions with a fluence of 3 × 10<sup>13</sup> Si ions/cm<sup>2</sup> and 3 × 10<sup>15</sup> Si ions/cm<sup>2</sup> into a p-type silicon wafer with a dopant concentration of 9 × 10<sup>15</sup> B/cm<sup>3</sup>. The patterned implantation allows a direct comparison between the surface potential of the silicon host against the surface potential of implanted stripes. The depth of the implanted silicon ions in the target and the concentration of displaced silicon atoms was simulated using the Stopping and Range of Ions in Matter (SRIM) software. The low fluence implantation shows a negligible effect on the measured Kelvin bias in the dark, whereas the large fluence implantation leads to an increased Kelvin bias, i.e. to a smaller surface work function according to the contact potential difference model. Illumination causes a reduced surface band bending and surface potential in the non-implanted regions. The change of the Kelvin bias in the implanted regions under illumination provides insight into the mobility and lifetime of photo-generated electron-hole pairs. Finally, the effect of annealing on the intrinsic defect density is discussed and compared with atomic force microscopy measurements on the 2<sup>nd</sup> harmonic. In addition, by using the Baumgart, Helm, Schmidt interpretation of the measured Kelvin bias, the dopant concentration after implantation is estimated.
基金This work was financially supported by the National Natu-ral Science Foundation of China(12025503,U1867215,11875211,U1932134,12105208)Hubei Provincial Natural Science Foundation(2019CFA036)+1 种基金the Fundamental Research Funds for the Central Universities(2042021kf0068)China Postdoctoral Science Foundation(No.2020M682469).
文摘With the depletion of fossil fuels and environmental pollution, energy storage and conversion have become the focus of current research. Water splitting and fuel cell technologies have made outstanding contributions to energy conversion. However, the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) have slow kinetics, which limit the capacity of fuel cells. It is of great significance to develop catalysts for the OER and ORR and continuously improve their catalytic performance. Many studies have shown that intrinsic defects, especially vacancies (anion and cation vacancies), can effectively improve the efficiency of electrochemical energy storage and conversion. The introduction of intrinsic defects can generally expose more active sites, enhance conductivity, adjust the electronic state, and promote ion diffusion, thereby enhancing the catalytic performance. This review comprehensively summarizes the latest developments regarding the effects of intrinsic defects on the performance of non-noble metal electrocatalysts. According to the type of intrinsic defect, this article reviews in detail the regulation mechanism, preparation methods and advanced characterization techniques of intrinsic defects in different materials (oxides, non-oxides, etc.). Then, the current difficulties and future development of intrinsic defect regulation are analyzed and discussed thoroughly. Finally, the prospect of intrinsic defects in the field of electrochemical energy storage is further explored.
基金supported by the National Key Research and Development Program of China(No.2018YFB0703600)Key Research Project of Zhejiang Laboratory(No.2021PE0AC02)+1 种基金the Natural Science Foundation of China(Grant Nos.52172216 and 92163212)the 111 Project D16002.
文摘Over the years,the fact that the quaternary diamond-like thermoelectric materials show much lower carrier mobilities than ternary compounds remains mysterious.In this work,by adopting first-principles defect chemistry and electrical transport calculations,the fundamental origin of the difference on carrier mobility between quaternary and ternary diamond-like compounds is addressed,exemplified by Cd_(2)Cu_(3)In_(3)Te_(8).The results of defect chemistry show that the main intrinsic defects in quaternary compound Cd_(2)Cu_(3)In_(3)Te_(8) are substitutional defects,i.e.,CdIn and CdCu,differing from the copper vacancy defect in ternary Cu-based compound such as CuInTe_(2).The low defect formation energies in Cd_(2)Cu_(3)In_(3)Te_(8) result in high defect concentrations,which is caused by the similar atomic radii and electronegativities between CdeIn and CdeCu.Further calculations show that the low-energy defects are mainly located around the valence band maximum in Cd_(2)Cu_(3)In_(3)Te_(8).The electrical transport calculations,considering both the acoustic phonon scattering and ionized impurity scattering,demonstrate that mainly due to the higher concentration of the ionized defects,the mobility of the quaternary Cd_(2)Cu_(3)In_(3)Te_(8) is much lower than that of ternary CuInTe2.Our work sheds light on the intrinsic defects in quaternary diamond-like compounds and their influence on charge transport.
基金the National Natural Science Foundation of China(No.21875221,21571157,U1604123,and 21773016)the Youth Talent Support Program of High-Level Talents Special Support Plan in Henan Province(ZYQR201810148)+1 种基金Creative talents in the Education Department of Henan Province(19HASTIT039)the project supported by State Key Laboratory of Advanced Technology for Materials Synthesis and Processing(Wuhan University of Technology)(2019-KF-13).
文摘Electrocatalytic carbon dioxide(CO2)reduction(ECR)has become one of the main methods to close the broken carbon cycle and temporarily store renewable energy,but there are still some problems such as poor stability,low activity,and selectivity.While the most promising strategy to improve ECR activity is to develop electrocatalysts with low cost,high activity,and long-term stability.Recently,defective carbon-based nanomaterials have attracted extensive attention due to the unbalanced electron distribution and electronic structural distortion caused by the defects on the carbon materials.Here,the present review mainly summarizes the latest research progress of the construction of the diverse types of defects(intrinsic carbon defects,heteroatom doping defects,metal atomic sites,and edges detects)for carbon materials in ECR,and unveil the structure-activity relationship and its catalytic mechanism.The current challenges and opportunities faced by high-performance carbon materials in ECR are discussed,as well as possible future solutions.It can be believed that this review can provide some inspiration for the future of development of high-performance ECR catalysts.
文摘Annealing was carried out at 950 and 1120℃ under various As pressure for undoped (ND) semi-insulating (SI) LECGaAs. The effects of annealing on native defects and electrical propefties were investigated. Experimental re- sults indicate that, after an annealing at 950℃ for 14h under low As pressure, the Hall mobility decreases and the resis- tivity increases dramatically for the samples. These changes in electrical properties are due to the generation of intrinsic acceptor defects, and the generation of the intrinsic acceptor defects originates from the outdiffusion of As interstitial at high temperature. The generation of the intrinsic defects and these changes in electrical properties can be suppressed by increasing the applied As pressure during annealing. The concentration of the main donor defect E12 (AsGaVGa) can be decreased by about one order of magnitude by an evacuated annaling at 1120℃ for 2-8 h followed by a fast cooling. The decrease in E12 concentration can also be suppressed by increasing the As pressure during annealing.
基金the National Natural Science Foundation of China(Nos.22005341 and 22138013)the Shandong Provincial Natural Science Foundation(Nos.ZR2020QB128 and ZR2020ZD08)+2 种基金the Taishan Scholar Project(No.tsqnz20221121)the Major Scientific and Technological Innovation Project of Shandong Province(No.2020CXGC010402)the Independent Innovation Research Project of China University of Petroleum(No.22CX06026A).
文摘The commercialization of lithium-sulfur(Li-S)batteries faces several bottlenecks,and the major two of which are the shuttle effect of polysulfides and the wild growth of Li dendrites,responsible for fast capacity decay and severe safety issues.As an essential component of Li-S batteries,the structure and properties of the separators are closely related to the above problems,and the exploration of multifunctional separators is highly sought-after.Herein,an integrated separator composited of defective graphene and polyimide(DG-PI)was innovatively fabricated by electrospinning combined with the laser-induced carbonization strategy.The all-in-one compact architecture with well-interconnected channels shows superior mechanical and thermal stability and wettability.More importantly,the PI nanofibers containing N–/O–functional groups can induce the uniform deposition of lithium on the anode surface,while the DG framework with abundant pentagonal/heptagonal rings and vacancies can strongly trap polysulfides and accelerate polysulfide transformation on the cathode side.The strong chemical interaction between the insulative PI layer and the conductive DG layer modulates the surface charge distribution of each other,leading to more prominent contributions to restraining lithium dendrites and shuttle effect.Therefore,the Li-S batteries based on the integrated DG-PI separators afford an excellent performance in protecting lithium anode(stable cycles of 200 h at 5 mA·cm^(−2))and good cycling stability with a low capacity decay of 0.05%per cycle after 700 cycles at 1 C.This work offers a new design concept of multifunctional Li-S battery separators and broadens the application scope of laser micro-nano fabrication technology.