Environmental stability is a major bottleneck of perovskite solar cells.Only a handful of studies are investigating the effect of moisture on the structural degradation of the absorber.They mostly rely on ex situ expe...Environmental stability is a major bottleneck of perovskite solar cells.Only a handful of studies are investigating the effect of moisture on the structural degradation of the absorber.They mostly rely on ex situ experiments and on completely degraded samples,which restrict the assessment on initial and final stage.By combining in situ X-ray diffraction under controlled 85%relative humidity,and live observations of the water-induced degradation using liquid-cell transmission electron microscopy,we reveal two competitive degradation paths leading on one hand to the decomposition of state-of-theart mixed cation/anion(Cs_(0.05)(MA_(0.17)FA_(0.83))_(0.95)Pb(Br_(0.17)I_(0.83))_(3)(CsMAFA)into PbI_(2) through a dissolution/recrystallization mechanism and,on the other hand,to a non-equilibrium phase segregation leading to CsPb_(2)Br_(5) and a Cesium-poor/iodide-rich Cs_(0.05)-x(MA_(0.17)FA_(0.83))_(0.95)Pb(Br_(0.17-2y)I_(0.83)+2y)_(3) perovskite.This degradation mechanism is corroborated at atomic-scale resolution through solid-state ^(1)H and ^(133)Cs NMR analysis.Exposure to moisture leads to a film containing important heterogeneities in terms of morphology,photoluminescence intensities,and lifetimes.Our results provide new insights and consensus that complex perovskite compositions,though very performant as champion devices,are comparatively metastable,a trait that limits the chances to achieve long-term stability.展开更多
Inhomogeneous Pb/Sn elemental distribution and the resulted phase segregation in mixed Pb-Sn halide perovskites would result in energy disorder(band structure and phase distribution disorder),which greatly limits thei...Inhomogeneous Pb/Sn elemental distribution and the resulted phase segregation in mixed Pb-Sn halide perovskites would result in energy disorder(band structure and phase distribution disorder),which greatly limits their photovoltaic performance.Here,Pb S quantum dot has been synthesized and demonstrated as seeds for modulation crystallization dynamics of the mixed Pb-Sn inorganic perovskites,allowing an enhanced film quality and significantly suppressing phase segregation.With this additive power conversion efficiency of 8%and 6%is obtained under irradiation of full sunlight in planar and mesoporous structured solar cells in combination with CsPb_(0.5) Sn_(0.5)I_(2)Br inorganic perovskite,respectively.Our finding reveals exploring the actual Pb/Sn atoms location in perovskite structure and its influence on developing efficient and stable low-bandgap perovskite solar cells.展开更多
Proton exchange membranes （PEMs） are a key material for proton exchange membrane fuel cells （PEM-FCs）, Non-fluorinated hydrocarbon PEMs are low-cost alternatives to Nation, but limited by the low pro-ton conductiv...Proton exchange membranes （PEMs） are a key material for proton exchange membrane fuel cells （PEM-FCs）, Non-fluorinated hydrocarbon PEMs are low-cost alternatives to Nation, but limited by the low pro-ton conductivity, because of the weak phase segregation structure and narrow ion-transport channels.Various efforts have been taken to improve the performance of hydrocarbon PEMs, but mostly with com-plex methodologies. Here we demonstrate a simple, yet very efficient method to create phase segrega-tion structure inside a typical hydrocarbon PEM, sulfonated poly（ether ether ketone） （SPEEK）. By sim-ply adding appropriate amounts of water into the DMF solvent, the resulting SPEEK membrane exhibitswidened ion-transport channels, with the phase size of 2.7 nm, as indicated by both molecular dynamic（MD） simulations and transmission electron microscope （TEM） observations, and the proton conductivityis thus improved by 200%. These findings not only further our fundamental understanding of hydrocarbonPEMs, but are also valuable to the development of low-cost and practical fuel cell technologies.展开更多
Mixed cation strategy greatly benefits the enhancement of device performance and chemical stability.However,adverse impact also accompanies the mixed cation system simultaneously.It brings the compositional instabilit...Mixed cation strategy greatly benefits the enhancement of device performance and chemical stability.However,adverse impact also accompanies the mixed cation system simultaneously.It brings the compositional instability,wherein the homogeneous film is likely to segregate into multi-phases during the fabrication and ageing process,thus resulting in the efficiency reduction of perovskite solar cells(PSCs)devices.This review focuses on the cation induced phase segregation,and elucidates the segregation mechanisms from the perspectives of film formation and ageing process,respectively.Furthermore,the influence of cation segregation on device performance and operational stability are discussed.And based on these understandings,viable strategies are proposed for the design of phase-stable mixed composition halide perovskites and for suppressing segregation to benefit its development towards commercial applications.展开更多
Wide-bandgap(WB)mixed-halide perovskite solar cells(PSCs)play a crucial role in perovskite-based tandem solar cells(TSCs),enabling them to exceed the Shockley-Queisser limits of single-junction solar cells.Nonetheless...Wide-bandgap(WB)mixed-halide perovskite solar cells(PSCs)play a crucial role in perovskite-based tandem solar cells(TSCs),enabling them to exceed the Shockley-Queisser limits of single-junction solar cells.Nonetheless,the lack of stability in WB perovskite films due to photoinduced phase segregation undermines the stability of WB PSCs and their TSCs,thus impeding the commercialization of perovskite-based TSCs.Many efforts have been made to suppress photoinduced phase segregation in WB perovskite films and significant progresses have been obtained.In this review,we elaborate the mechanisms behind photoinduced phase segregation and its impact on the photovoltaic performance and stability of devices.The importance role of advanced characterization techniques in confirming the photoinduced phase segregation are comprehensively summarized.Beyond that,the effective strategies to alleviate photoinduced phase segregation in WB mixed halide PSCs are systematically assessed.Finally,the prospects for developing highly efficient and stable WB PSCs in tandem application are also presented.展开更多
Thiocyanate-anion(SCN−)two-dimensional(2D)layered perovskite with internal stress-controlled nano phase segregation has been firstly demonstrated as a promising material system for luminescence applications.An interes...Thiocyanate-anion(SCN−)two-dimensional(2D)layered perovskite with internal stress-controlled nano phase segregation has been firstly demonstrated as a promising material system for luminescence applications.An interesting energy band structure is found as well as charge transfer process caused by nano phase segregation,which provide an alternative route to overcome the indirect-bandgap luminescence limit of SCN layered perovskites.It is revealed that,within the SCN layered framework,the segregated nano phases exist in a quantum well form,possessing much higher carrier localization and second-order radiative recombination abilities.With the help of internal stress modulation,these advantages can be significantly enhanced and finally contribute to high luminescence performances in visible-red regions.This work provides more potential opportunities for 2D layered perovskite materials in the future optoelectronic applications.展开更多
Wide-bandgap(>1.7 eV)perovskites suffer from severe light-induced phase segregation due to high bromine content,causing irreversible damage to devices stability.However,the strategies of suppressing photoinduced ph...Wide-bandgap(>1.7 eV)perovskites suffer from severe light-induced phase segregation due to high bromine content,causing irreversible damage to devices stability.However,the strategies of suppressing photoinduced phase segregation and related mechanisms have not been fully disclosed.Here,we report a new passivation agent 4-aminotetrahydrothiopyran hydrochloride(4-ATpHCl)with multifunctional groups for the interface treatment of a 1.77-eV wide-bandgap perovskite film.4-ATpH^(+)impeded halogen ion migration by anchoring on the perovskite surface,leading to the inhibition of phase segregation and thus the passivation of defects,which is ascribed to the interaction of 4-ATpH^(+)with perovskite and the formation of low-dimensional perovskites.Finally,the champion device achieved an efficiency of 19.32%with an open-circuit voltage(V_(OC))of 1.314 V and a fill factor of 83.32%.Moreover,4-ATpHCl modified device exhibited significant improved stability as compared with control one.The target device maintained 80%of its initial efficiency after 519 h of maximum power output(MPP)tracking under 1 sun illumination,however,the control device showed a rapid decrease in efficiency after 267 h.Finally,an efficiency of 27.38%of the champion 4-terminal all-perovskite tandem solar cell was achieved by mechanically stacking this wide-bandgap top subcell with a 1.25-eV low-bandgap perovskite bottom subcell.展开更多
Mixed halide perovskites with the ability to tune bandgaps exhibit attractive applications in tandem solar cells,building integrated photovoltaic and wavelength-tunable light-emitting devices.However,halide demixing u...Mixed halide perovskites with the ability to tune bandgaps exhibit attractive applications in tandem solar cells,building integrated photovoltaic and wavelength-tunable light-emitting devices.However,halide demixing under illumination or in the dark with a charge-carrier injection in both hybrid and inorganic perovskites results in bandgap instability and current-density-voltage(J-V)hysteresis,which can significantly hamper their application.Here,we demonstrate that halide segregation and J-V hysteresis in mixed halide inorganic CsPbIBr_(2)solar cells can be effectively mitigated by introducing an intermediate phase-enhanced Ostwald ripening through the control of the chemical composition in the CsPbIBr_(2)precursor solution.Excess amounts of either PbBr_(2)or CsI are incorporated into originally even molar amounts of PbBr_(2)and CsI precursor solutions.With the PbBr_(2)-excess,we observed an enlarged perovskite grain size,no detectable halide phase segregation at the grain boundaries nor the perovskite/TiO2 interface,an increased minority carrier lifetime,a reduced J-V hysteresis,and an improved solar-cell performance.However,different CsI:PbBr_(2)stoichiometric ratios were found to have different effects on the performance of the perovskite solar cell.The excessive lead phase is reactive with the dimethyl sulfoxide(DMSO)in the precursor solution to form the Pb(I,Br)2·DMSO complex and the quasi-twodimensional(2D)CsPb_(2)(I,Br)5,which are conducive to Ostwald maturation and defect extinction.Finally,the CsPbIBr_(2)solar cell with a PbBr_(2)-excess precursor composition reaches a power conversion efficiency(PCE)of 9.37%(stabilized PCE of 8.48%)and a maximum external quantum efficiency of over 90%.展开更多
Polycrystalline La0.67Ba0.33MnO3 bulk samples were annealed in flowing 95%Ar：5%H2 （AH） mixed gas at 973 K for different time respectively. The influence of the annealing time on the current-voltage properties was s...Polycrystalline La0.67Ba0.33MnO3 bulk samples were annealed in flowing 95%Ar：5%H2 （AH） mixed gas at 973 K for different time respectively. The influence of the annealing time on the current-voltage properties was systematically investigated. Linear current-voltage characteristics were observed in the as-prepared and the 10 h annealed samples, and nonlinear current-voltage characteristics was found in the 100 h annealed sample. At the same time, segregation of impurity phase and micro-cracks were found on the surfaces of the 100 h annealed samples, which was testified to be Ba ion impurity. Analysis showed that the changes of electronic properties were caused by barium ion im-purities and micro-cracks in the 100 h annealed sample.展开更多
In a recent online publication of Science,Professor Peter Strasser of the Technical University of Berlin,Germany,and his collaborators reported element-specific anisotropic growth of Pt and Ni in shaped Pt alloy synth...In a recent online publication of Science,Professor Peter Strasser of the Technical University of Berlin,Germany,and his collaborators reported element-specific anisotropic growth of Pt and Ni in shaped Pt alloy synthesis[1].They showed that the surface steps in the Pt3Ni concave hexapod alloy formed in the initial stage of the synthesis were crucial in the segregation of an M-rich(M=Ni,Co,展开更多
The segregation of Mg to phase interfaces in a nickel base superalloy IN 100 has been investi- gated using EPT(Electron Microprobe Technique).AES(Auger Electron Spectroscopy) and EDS analyses on thin TEM film.The resu...The segregation of Mg to phase interfaces in a nickel base superalloy IN 100 has been investi- gated using EPT(Electron Microprobe Technique).AES(Auger Electron Spectroscopy) and EDS analyses on thin TEM film.The results show that Mg segregates to the phase inter- faces of MC/γ and γ′/γ.The segregation concentration and layer thickness of Mg on MC/γ phase interface are larger than that on γ′/γ phase interface.Mg is not only a grain boundary segregation element,but also a phase interface segregation one.展开更多
The rapid rise in the power conversion efficiency(PCE)of CsPbBr_(2)I-based perovskite solar cells(PSCs),from 4.7%in 2016 to 11.08%in 2020,render it a promising material for use in photovoltaic devices.However,the phas...The rapid rise in the power conversion efficiency(PCE)of CsPbBr_(2)I-based perovskite solar cells(PSCs),from 4.7%in 2016 to 11.08%in 2020,render it a promising material for use in photovoltaic devices.However,the phase stability and current hysteresis caused by photo-induced phase segregation in CsPbBr_(2)I represent major obstacles to further improvements in the PCE for such devices.In this review,we describe the basic structure and optical properties of CsPbBr_(2)I,and systematically elaborate on the mechanism of the phase transition.We then discuss the strategies in progress to suppress phase transition in CsPbBr_(2)I,and their potential application in the photovoltaic field.Finally,challenges and application prospects for CsPbBr2I PSCs are summarized in the final section of this article.展开更多
This paper describes the design of a FeWOx-based oxygen carrier for the chemical partial oxidation of methane(CLPOM).Thermodynamic screening and kinetic analyses both forecast the FeWOx-based oxygen carrier as a promi...This paper describes the design of a FeWOx-based oxygen carrier for the chemical partial oxidation of methane(CLPOM).Thermodynamic screening and kinetic analyses both forecast the FeWOx-based oxygen carrier as a promising candidate for the production of syngas.The total methane conversion and syngas yield can be dramatically increased with this catalyst compared to the case with the unmodified WO3/SiO2,thereby enabling CLPOM with 62%methane conversion,93%CO gas-phase selectivity,94%H2 selectivity,and a 2.4 H2/CO ratio.The catalyst has the advantages of high availability of lattice oxygen to oxidize carbonaceous intermediates in time,together with the formation of an Fe-W alloy to promote the surface reaction.Consequently,it demonstrates excellent catalytic performance with no catalyst deactivation at 900°C and 1 atm.The excellent structural stability plays an essential role in CLPOM.As revealed via XPS and ICP,the phase segregation has not been observed due to the strong interaction between Fe and W,which resulted in the formation of the Fe-W alloy during the reduction processes and the match between the ion oxidation rates of the Fe and W ions in the oxidation stage.The results provide fundamental information on the reaction mechanism of FeWOx/SiO2,and present it as a promising candidate for CLPOM.展开更多
Mixed-halide lead perovskites(MHLPs) are semiconductor materials with bandgaps that are tunable across the visible spectrum and have seen promising applications in photovoltaics and optoelectronics.However, their segr...Mixed-halide lead perovskites(MHLPs) are semiconductor materials with bandgaps that are tunable across the visible spectrum and have seen promising applications in photovoltaics and optoelectronics.However, their segregation into phases with enriched halide components, under resonant light illumination and/or electric field, have hindered their practical applications. Herein, we demonstrate the stabilization of the MHLP photoluminescence(PL) peak as a function of their excitation intensities.This effect is associated with the phase segregation of MHLPs and their subsequent remixing by photothermal heating. We conclude that the balance between these opposing processes dictates the equilibrium PL peak of the MHLPs. The findings in this work could serve as a potential approach to obtain MHLP with stable emission peaks under operating conditions.展开更多
Power conversion efficiency(PCE) of perovskite solar cells(PSC) has been skyrocketed to certified 25.5% owing to their improved and tunable optoelectronic properties. Although, various strategies have been adopted to ...Power conversion efficiency(PCE) of perovskite solar cells(PSC) has been skyrocketed to certified 25.5% owing to their improved and tunable optoelectronic properties. Although, various strategies have been adopted to date regarding PCE and stability enhancement within PSC technology, certain instability factors(moisture, heat, light) are hindering their commercial placement. Recently, all-inorganic PSCs got hype in the photovoltaic research community after they attained PCE > 20% and due to their significant endurance against heat and light mishmashes, but there only left moisture sensitivity as the only roadblock for their industrial integration. Here, we review the recent progress of additive inclusion into allinorganic(CsPbX_(3)) PSCs to stabilize their intrinsic structure and to withstand the performance limiting factors. We start with the detailed description of chemical instability of different perovskite compositions, phase segregation, and how organic molecules and dyes help to repair the structural defects to improve the overall PCE and stability of PSCs. Moisture endurance as a result of chemical passivation through organic additives, low-dimensional inorganic PSCs to enhance device stability and scalable fabrication of CsPbX_(3) PSCs are also reviewed. The challenges of module degradation and design implications with proposed strategies and outlook are interpreted in the ending phrases of this review.展开更多
The effect of doping additional Bi on the magnetoresistance （MR） of La2/3Ca1/3BxMn1-x O3 was investigated. It is found that traditional colossal magnetoresistance （CMR） peak can only be observed in the x〈0.05 sam...The effect of doping additional Bi on the magnetoresistance （MR） of La2/3Ca1/3BxMn1-x O3 was investigated. It is found that traditional colossal magnetoresistance （CMR） peak can only be observed in the x〈0.05 samples and the peak value decreases with the increase of x, but the x≥0.05 samples show a magnetoresistance plateau above 200 K because of the presence of additional （La,Ca,Bi）-O layers. Moreover, this MR plateau is enhanced for the segregation of the La, Ca, and Bi elements.展开更多
The crystal growth of a nickel-based single crystal superalloy DD3 was researched via controlled directional solidification under the action of a DC electric field. The cellular or dendrite spacing of the single cryst...The crystal growth of a nickel-based single crystal superalloy DD3 was researched via controlled directional solidification under the action of a DC electric field. The cellular or dendrite spacing of the single crystal superalloy is refined and microsegregation of alloying elements Al, Ti, Mo and W, is reduced by the electric field. The electric field decreases the interface stability and reduces the critical growth rate of the ceUular-dendritic translation because of Thomson effect and Joule heating. The precipitation of the γ＇ phase is more uniform and the size of the γ＇ phase is smaller with the electric field than that without the electric field.展开更多
The mechanical behavior of LC 4 alloy in the semisolid state at high volume fractions of solid has been studied through unconstrictive compressing test. The results show that peak stress mainly depends on grain bound...The mechanical behavior of LC 4 alloy in the semisolid state at high volume fractions of solid has been studied through unconstrictive compressing test. The results show that peak stress mainly depends on grain boundary’s cohesion and instantaneous strain rate sensitivity in the semisolid state, which is similar to that in the solid state. Analyses on microstructures and status of compressive stress of specimen demonstrate that segregation of liquid solid phase is mainly affected by strain rate and deformation temperature. There are mainly two kinds of flow in liquid phase: either from the region with relatively large hydrostatic compressive stress to the region with relatively small hydrostatic compressive stress or from the grain boundaries perpendicular to the compression axis to the grain boundaries with a certain directional angle to the compression direction. Based on the above results, compressive deformation mechanism mainly depends on deformation temperature, strain rate and stress state.展开更多
Graphene-like, ternary system B-C-N atomic layer materials promise highly tunable electronic properties and a plethora of potential applications. However, thus far, experimental synthesis of the B-C-N atomic layers no...Graphene-like, ternary system B-C-N atomic layer materials promise highly tunable electronic properties and a plethora of potential applications. However, thus far, experimental synthesis of the B-C-N atomic layers normally yields a microscopic phase-segregated structure consisting of pure C and BN domains. Further, growing the truly ternary B-C-N phase layers with homogenous atomic arrangements has proven to be very challenging. Here, in designing a better- controlled process for the chemical vapor deposition （CVD） growth of B-C-N atomic layer films with the minimized C and BN phase segregation, we selected trimethyl borane （TMB）, a gaseous organoboron compound with pre-existing B--C bonds, as the molecular precursor to react with ammonia （NH3） gas that serves as the nitrification agent. The use of this unique B-C delivery precursor allows for the successful synthesis of high-quality and large-area B-C-N atomic layer films. Moreover, the TMB/NH3 reactant combination can offer a high level of tunability and control of the overall chemical composition of B-C-N atomic layers by regulating the relative partial pressure of two gaseous reactants. Electrical transport measurements show that a finite energy gap can be opened in the as-grown B-C-N atomic layers and its tunability is essentially dependent on the relative C to BN atomic compositions. On the basis of carefully controlled experiments, we show that the pre-existing B-C bonds in the TMB molecular precursor have played a crucial role in effectively reducing the C and BN phase segregation problem, thereby facilitating the formation of truly ternary B-C-N phase atomic layers.展开更多
基金financial support from Region Hauts-de-France,FEDER,and Electricité de France(EDF)through PEROVSTAB programfinancial support from the IR-RMN-THC FR-3050 CNRS France for conducting solid-state NMR measurements.P.R.and G.N.M.R+1 种基金financial support from University of Lille and région Hauts-de-France.F.S“IMPRESSIVE”project which received funding from the European Union’s Horizon 2020 Research and Innovation Program under grant agreement number 826013.
文摘Environmental stability is a major bottleneck of perovskite solar cells.Only a handful of studies are investigating the effect of moisture on the structural degradation of the absorber.They mostly rely on ex situ experiments and on completely degraded samples,which restrict the assessment on initial and final stage.By combining in situ X-ray diffraction under controlled 85%relative humidity,and live observations of the water-induced degradation using liquid-cell transmission electron microscopy,we reveal two competitive degradation paths leading on one hand to the decomposition of state-of-theart mixed cation/anion(Cs_(0.05)(MA_(0.17)FA_(0.83))_(0.95)Pb(Br_(0.17)I_(0.83))_(3)(CsMAFA)into PbI_(2) through a dissolution/recrystallization mechanism and,on the other hand,to a non-equilibrium phase segregation leading to CsPb_(2)Br_(5) and a Cesium-poor/iodide-rich Cs_(0.05)-x(MA_(0.17)FA_(0.83))_(0.95)Pb(Br_(0.17-2y)I_(0.83)+2y)_(3) perovskite.This degradation mechanism is corroborated at atomic-scale resolution through solid-state ^(1)H and ^(133)Cs NMR analysis.Exposure to moisture leads to a film containing important heterogeneities in terms of morphology,photoluminescence intensities,and lifetimes.Our results provide new insights and consensus that complex perovskite compositions,though very performant as champion devices,are comparatively metastable,a trait that limits the chances to achieve long-term stability.
基金Financial support from the National Key Research and Development Program of China (2019YFE0101300, 2018YFB1502900)the National Natural Science Foundation of China (No. 21975088)+1 种基金the National Natural Science Foundation of China Major International (Regional) Joint Research Project (No. 51961165106)the double first-class research funding of China-EU Institute for Clean and Renewable Energy (3011187029)。
文摘Inhomogeneous Pb/Sn elemental distribution and the resulted phase segregation in mixed Pb-Sn halide perovskites would result in energy disorder(band structure and phase distribution disorder),which greatly limits their photovoltaic performance.Here,Pb S quantum dot has been synthesized and demonstrated as seeds for modulation crystallization dynamics of the mixed Pb-Sn inorganic perovskites,allowing an enhanced film quality and significantly suppressing phase segregation.With this additive power conversion efficiency of 8%and 6%is obtained under irradiation of full sunlight in planar and mesoporous structured solar cells in combination with CsPb_(0.5) Sn_(0.5)I_(2)Br inorganic perovskite,respectively.Our finding reveals exploring the actual Pb/Sn atoms location in perovskite structure and its influence on developing efficient and stable low-bandgap perovskite solar cells.
基金financially supported by the National Key Research and Development Program of China (2016YFB0101203)the National Natural Science Foundation of China (91545205,21633008)
文摘Proton exchange membranes （PEMs） are a key material for proton exchange membrane fuel cells （PEM-FCs）, Non-fluorinated hydrocarbon PEMs are low-cost alternatives to Nation, but limited by the low pro-ton conductivity, because of the weak phase segregation structure and narrow ion-transport channels.Various efforts have been taken to improve the performance of hydrocarbon PEMs, but mostly with com-plex methodologies. Here we demonstrate a simple, yet very efficient method to create phase segrega-tion structure inside a typical hydrocarbon PEM, sulfonated poly（ether ether ketone） （SPEEK）. By sim-ply adding appropriate amounts of water into the DMF solvent, the resulting SPEEK membrane exhibitswidened ion-transport channels, with the phase size of 2.7 nm, as indicated by both molecular dynamic（MD） simulations and transmission electron microscope （TEM） observations, and the proton conductivityis thus improved by 200%. These findings not only further our fundamental understanding of hydrocarbonPEMs, but are also valuable to the development of low-cost and practical fuel cell technologies.
基金National Natural Science Foundation of China(22109057,21805010,21975028,52172182,22011540377,22005035)Beijing Municipal Science and Technology Project(Z181100005118002)+2 种基金Beijing Municipal Natural Science Foundation(JQ19008)the China Postdoctoral Science Foundation(Grant No.2020TQ0043,2020M680012)Research Foundation of Jiangxi Educational Committee(GJJ200836).
文摘Mixed cation strategy greatly benefits the enhancement of device performance and chemical stability.However,adverse impact also accompanies the mixed cation system simultaneously.It brings the compositional instability,wherein the homogeneous film is likely to segregate into multi-phases during the fabrication and ageing process,thus resulting in the efficiency reduction of perovskite solar cells(PSCs)devices.This review focuses on the cation induced phase segregation,and elucidates the segregation mechanisms from the perspectives of film formation and ageing process,respectively.Furthermore,the influence of cation segregation on device performance and operational stability are discussed.And based on these understandings,viable strategies are proposed for the design of phase-stable mixed composition halide perovskites and for suppressing segregation to benefit its development towards commercial applications.
基金the National Natural Science Foundation of China(Grant No.62274018)the Xinjiang Construction Corps Key Areas of Science and Technology Research Project(Grant No.2023AB029)the Key Project of Chongqing Overseas Students Returning to China Entrepreneurship and Innovation Support Plan(Grant No.cx2023006).
文摘Wide-bandgap(WB)mixed-halide perovskite solar cells(PSCs)play a crucial role in perovskite-based tandem solar cells(TSCs),enabling them to exceed the Shockley-Queisser limits of single-junction solar cells.Nonetheless,the lack of stability in WB perovskite films due to photoinduced phase segregation undermines the stability of WB PSCs and their TSCs,thus impeding the commercialization of perovskite-based TSCs.Many efforts have been made to suppress photoinduced phase segregation in WB perovskite films and significant progresses have been obtained.In this review,we elaborate the mechanisms behind photoinduced phase segregation and its impact on the photovoltaic performance and stability of devices.The importance role of advanced characterization techniques in confirming the photoinduced phase segregation are comprehensively summarized.Beyond that,the effective strategies to alleviate photoinduced phase segregation in WB mixed halide PSCs are systematically assessed.Finally,the prospects for developing highly efficient and stable WB PSCs in tandem application are also presented.
基金supported by the National Natural Science Foundation of China(Nos.52102332,11874402,51872321,52172260,52072402,and 51627803)Beijing Natural Science Foundation(No.2222082)the Ministry of Science and Technology of the People’s Republic of China(No.2021YFB3800103)。
文摘Thiocyanate-anion(SCN−)two-dimensional(2D)layered perovskite with internal stress-controlled nano phase segregation has been firstly demonstrated as a promising material system for luminescence applications.An interesting energy band structure is found as well as charge transfer process caused by nano phase segregation,which provide an alternative route to overcome the indirect-bandgap luminescence limit of SCN layered perovskites.It is revealed that,within the SCN layered framework,the segregated nano phases exist in a quantum well form,possessing much higher carrier localization and second-order radiative recombination abilities.With the help of internal stress modulation,these advantages can be significantly enhanced and finally contribute to high luminescence performances in visible-red regions.This work provides more potential opportunities for 2D layered perovskite materials in the future optoelectronic applications.
基金financially supported by the National Key R&D Program of China (2022YFB4200304)the National Natural Science Foundation of China (52303347)+3 种基金the Fundamental Research Funds for the Central Universities (YJ2021157)the Engineering Featured Team Fund of Sichuan University (2020SCUNG102)open foundation of Guangxi Key Laboratory of Processing for Non-Ferrous Metals and Featured Materials, Guangxi University (2022GXYSOF05)the support from the National Natural Science Foundation of China (E30853YM19)
文摘Wide-bandgap(>1.7 eV)perovskites suffer from severe light-induced phase segregation due to high bromine content,causing irreversible damage to devices stability.However,the strategies of suppressing photoinduced phase segregation and related mechanisms have not been fully disclosed.Here,we report a new passivation agent 4-aminotetrahydrothiopyran hydrochloride(4-ATpHCl)with multifunctional groups for the interface treatment of a 1.77-eV wide-bandgap perovskite film.4-ATpH^(+)impeded halogen ion migration by anchoring on the perovskite surface,leading to the inhibition of phase segregation and thus the passivation of defects,which is ascribed to the interaction of 4-ATpH^(+)with perovskite and the formation of low-dimensional perovskites.Finally,the champion device achieved an efficiency of 19.32%with an open-circuit voltage(V_(OC))of 1.314 V and a fill factor of 83.32%.Moreover,4-ATpHCl modified device exhibited significant improved stability as compared with control one.The target device maintained 80%of its initial efficiency after 519 h of maximum power output(MPP)tracking under 1 sun illumination,however,the control device showed a rapid decrease in efficiency after 267 h.Finally,an efficiency of 27.38%of the champion 4-terminal all-perovskite tandem solar cell was achieved by mechanically stacking this wide-bandgap top subcell with a 1.25-eV low-bandgap perovskite bottom subcell.
基金the National Natural Science Foundation of China(51802241 and 91963209)the Fundamental Research Funds for the Central Universities(WUT:2019IVB055 and 2019IVA066)+1 种基金ARC Discovery Grant DP150104483,ARC Centre of Excellence in Exciton Science(CE170100026)the Australian Government through the Australian Renewable Energy Agency(ARENA).
文摘Mixed halide perovskites with the ability to tune bandgaps exhibit attractive applications in tandem solar cells,building integrated photovoltaic and wavelength-tunable light-emitting devices.However,halide demixing under illumination or in the dark with a charge-carrier injection in both hybrid and inorganic perovskites results in bandgap instability and current-density-voltage(J-V)hysteresis,which can significantly hamper their application.Here,we demonstrate that halide segregation and J-V hysteresis in mixed halide inorganic CsPbIBr_(2)solar cells can be effectively mitigated by introducing an intermediate phase-enhanced Ostwald ripening through the control of the chemical composition in the CsPbIBr_(2)precursor solution.Excess amounts of either PbBr_(2)or CsI are incorporated into originally even molar amounts of PbBr_(2)and CsI precursor solutions.With the PbBr_(2)-excess,we observed an enlarged perovskite grain size,no detectable halide phase segregation at the grain boundaries nor the perovskite/TiO2 interface,an increased minority carrier lifetime,a reduced J-V hysteresis,and an improved solar-cell performance.However,different CsI:PbBr_(2)stoichiometric ratios were found to have different effects on the performance of the perovskite solar cell.The excessive lead phase is reactive with the dimethyl sulfoxide(DMSO)in the precursor solution to form the Pb(I,Br)2·DMSO complex and the quasi-twodimensional(2D)CsPb_(2)(I,Br)5,which are conducive to Ostwald maturation and defect extinction.Finally,the CsPbIBr_(2)solar cell with a PbBr_(2)-excess precursor composition reaches a power conversion efficiency(PCE)of 9.37%(stabilized PCE of 8.48%)and a maximum external quantum efficiency of over 90%.
基金supported by the National Natural Science Foundation of China (10975103)
文摘Polycrystalline La0.67Ba0.33MnO3 bulk samples were annealed in flowing 95%Ar：5%H2 （AH） mixed gas at 973 K for different time respectively. The influence of the annealing time on the current-voltage properties was systematically investigated. Linear current-voltage characteristics were observed in the as-prepared and the 10 h annealed samples, and nonlinear current-voltage characteristics was found in the 100 h annealed sample. At the same time, segregation of impurity phase and micro-cracks were found on the surfaces of the 100 h annealed samples, which was testified to be Ba ion impurity. Analysis showed that the changes of electronic properties were caused by barium ion im-purities and micro-cracks in the 100 h annealed sample.
文摘In a recent online publication of Science,Professor Peter Strasser of the Technical University of Berlin,Germany,and his collaborators reported element-specific anisotropic growth of Pt and Ni in shaped Pt alloy synthesis[1].They showed that the surface steps in the Pt3Ni concave hexapod alloy formed in the initial stage of the synthesis were crucial in the segregation of an M-rich(M=Ni,Co,
文摘The segregation of Mg to phase interfaces in a nickel base superalloy IN 100 has been investi- gated using EPT(Electron Microprobe Technique).AES(Auger Electron Spectroscopy) and EDS analyses on thin TEM film.The results show that Mg segregates to the phase inter- faces of MC/γ and γ′/γ.The segregation concentration and layer thickness of Mg on MC/γ phase interface are larger than that on γ′/γ phase interface.Mg is not only a grain boundary segregation element,but also a phase interface segregation one.
基金the National Natural Science Foundation of China(52073131,51902148,61704099,61874166,U1832149,51801088 and 51802024)the Natural Science Foundation of Gansu Province(20JR5RA227,20JR5RA217,20JR5RA278)the Fundamental Research Funds for the Central Universities(lzujbky-2020-61,lzujbky-2019-88 and lzujbky-2020-kb06).
文摘The rapid rise in the power conversion efficiency(PCE)of CsPbBr_(2)I-based perovskite solar cells(PSCs),from 4.7%in 2016 to 11.08%in 2020,render it a promising material for use in photovoltaic devices.However,the phase stability and current hysteresis caused by photo-induced phase segregation in CsPbBr_(2)I represent major obstacles to further improvements in the PCE for such devices.In this review,we describe the basic structure and optical properties of CsPbBr_(2)I,and systematically elaborate on the mechanism of the phase transition.We then discuss the strategies in progress to suppress phase transition in CsPbBr_(2)I,and their potential application in the photovoltaic field.Finally,challenges and application prospects for CsPbBr2I PSCs are summarized in the final section of this article.
基金Financial supports from The National Natural Science Foundation of China(Nos.51625402,51790483,51801069 and U19A2084)are greatly acknowledgedPartial financial support came from The Science and Technology Devel-opment Program of Jilin Province(Nos.20190901010JC,20190103003JH,20200401025GX and 20200201002JC)The Changjiang Scholars Program(T2017035).
文摘This paper describes the design of a FeWOx-based oxygen carrier for the chemical partial oxidation of methane(CLPOM).Thermodynamic screening and kinetic analyses both forecast the FeWOx-based oxygen carrier as a promising candidate for the production of syngas.The total methane conversion and syngas yield can be dramatically increased with this catalyst compared to the case with the unmodified WO3/SiO2,thereby enabling CLPOM with 62%methane conversion,93%CO gas-phase selectivity,94%H2 selectivity,and a 2.4 H2/CO ratio.The catalyst has the advantages of high availability of lattice oxygen to oxidize carbonaceous intermediates in time,together with the formation of an Fe-W alloy to promote the surface reaction.Consequently,it demonstrates excellent catalytic performance with no catalyst deactivation at 900°C and 1 atm.The excellent structural stability plays an essential role in CLPOM.As revealed via XPS and ICP,the phase segregation has not been observed due to the strong interaction between Fe and W,which resulted in the formation of the Fe-W alloy during the reduction processes and the match between the ion oxidation rates of the Fe and W ions in the oxidation stage.The results provide fundamental information on the reaction mechanism of FeWOx/SiO2,and present it as a promising candidate for CLPOM.
基金Nanoscale and Quantum Phenomena Institute (NQPI)National Institutes of Health award number R15HG009972 for support in microscope building and maintenance。
文摘Mixed-halide lead perovskites(MHLPs) are semiconductor materials with bandgaps that are tunable across the visible spectrum and have seen promising applications in photovoltaics and optoelectronics.However, their segregation into phases with enriched halide components, under resonant light illumination and/or electric field, have hindered their practical applications. Herein, we demonstrate the stabilization of the MHLP photoluminescence(PL) peak as a function of their excitation intensities.This effect is associated with the phase segregation of MHLPs and their subsequent remixing by photothermal heating. We conclude that the balance between these opposing processes dictates the equilibrium PL peak of the MHLPs. The findings in this work could serve as a potential approach to obtain MHLP with stable emission peaks under operating conditions.
基金supported by the National Key Research and Development Program of China(2017YFA0206600)the National Natural Science Foundation of China(52173192)+1 种基金the Science and Technology Innovation Program of Hunan Province(2020RC4004)the Special Funding for the Construction of Innovative Provinces in Hunan Province(2020GK2024)。
文摘Power conversion efficiency(PCE) of perovskite solar cells(PSC) has been skyrocketed to certified 25.5% owing to their improved and tunable optoelectronic properties. Although, various strategies have been adopted to date regarding PCE and stability enhancement within PSC technology, certain instability factors(moisture, heat, light) are hindering their commercial placement. Recently, all-inorganic PSCs got hype in the photovoltaic research community after they attained PCE > 20% and due to their significant endurance against heat and light mishmashes, but there only left moisture sensitivity as the only roadblock for their industrial integration. Here, we review the recent progress of additive inclusion into allinorganic(CsPbX_(3)) PSCs to stabilize their intrinsic structure and to withstand the performance limiting factors. We start with the detailed description of chemical instability of different perovskite compositions, phase segregation, and how organic molecules and dyes help to repair the structural defects to improve the overall PCE and stability of PSCs. Moisture endurance as a result of chemical passivation through organic additives, low-dimensional inorganic PSCs to enhance device stability and scalable fabrication of CsPbX_(3) PSCs are also reviewed. The challenges of module degradation and design implications with proposed strategies and outlook are interpreted in the ending phrases of this review.
基金Funded by the Foundation for the Author of National Excellent Doctoral Dissertation of China (FANEDD) (No. 200233)
文摘The effect of doping additional Bi on the magnetoresistance （MR） of La2/3Ca1/3BxMn1-x O3 was investigated. It is found that traditional colossal magnetoresistance （CMR） peak can only be observed in the x〈0.05 samples and the peak value decreases with the increase of x, but the x≥0.05 samples show a magnetoresistance plateau above 200 K because of the presence of additional （La,Ca,Bi）-O layers. Moreover, this MR plateau is enhanced for the segregation of the La, Ca, and Bi elements.
基金supported by the National Natural Science Foundation of China(No.50374062)the Science and Technology Foundation of Liaoning(No.20032015).
文摘The crystal growth of a nickel-based single crystal superalloy DD3 was researched via controlled directional solidification under the action of a DC electric field. The cellular or dendrite spacing of the single crystal superalloy is refined and microsegregation of alloying elements Al, Ti, Mo and W, is reduced by the electric field. The electric field decreases the interface stability and reduces the critical growth rate of the ceUular-dendritic translation because of Thomson effect and Joule heating. The precipitation of the γ＇ phase is more uniform and the size of the γ＇ phase is smaller with the electric field than that without the electric field.
文摘The mechanical behavior of LC 4 alloy in the semisolid state at high volume fractions of solid has been studied through unconstrictive compressing test. The results show that peak stress mainly depends on grain boundary’s cohesion and instantaneous strain rate sensitivity in the semisolid state, which is similar to that in the solid state. Analyses on microstructures and status of compressive stress of specimen demonstrate that segregation of liquid solid phase is mainly affected by strain rate and deformation temperature. There are mainly two kinds of flow in liquid phase: either from the region with relatively large hydrostatic compressive stress to the region with relatively small hydrostatic compressive stress or from the grain boundaries perpendicular to the compression axis to the grain boundaries with a certain directional angle to the compression direction. Based on the above results, compressive deformation mechanism mainly depends on deformation temperature, strain rate and stress state.
基金Acknowledgements We acknowledge financial support from the National Natural Science Foundation of China （Nos. 21322304 and 51472267） and the National Basic Research Program of China （Nos. 2012CB933003 and 2013CB932603） and the Strategic Priority Research Program B of the Chinese Academy of Sciences （No. XDB07030100） of China.
文摘Graphene-like, ternary system B-C-N atomic layer materials promise highly tunable electronic properties and a plethora of potential applications. However, thus far, experimental synthesis of the B-C-N atomic layers normally yields a microscopic phase-segregated structure consisting of pure C and BN domains. Further, growing the truly ternary B-C-N phase layers with homogenous atomic arrangements has proven to be very challenging. Here, in designing a better- controlled process for the chemical vapor deposition （CVD） growth of B-C-N atomic layer films with the minimized C and BN phase segregation, we selected trimethyl borane （TMB）, a gaseous organoboron compound with pre-existing B--C bonds, as the molecular precursor to react with ammonia （NH3） gas that serves as the nitrification agent. The use of this unique B-C delivery precursor allows for the successful synthesis of high-quality and large-area B-C-N atomic layer films. Moreover, the TMB/NH3 reactant combination can offer a high level of tunability and control of the overall chemical composition of B-C-N atomic layers by regulating the relative partial pressure of two gaseous reactants. Electrical transport measurements show that a finite energy gap can be opened in the as-grown B-C-N atomic layers and its tunability is essentially dependent on the relative C to BN atomic compositions. On the basis of carefully controlled experiments, we show that the pre-existing B-C bonds in the TMB molecular precursor have played a crucial role in effectively reducing the C and BN phase segregation problem, thereby facilitating the formation of truly ternary B-C-N phase atomic layers.
