Dynamic adsorption processes of reaction intermediates for alkaline hydrogen evolution(HER)catalysts are still confusing to understand.Here,we report a series of A-site ordered quadruple perovskite ruthenium-based ele...Dynamic adsorption processes of reaction intermediates for alkaline hydrogen evolution(HER)catalysts are still confusing to understand.Here,we report a series of A-site ordered quadruple perovskite ruthenium-based electrocatalysts ACu_(3)Ru_(4)O_(12)(A=Na,Ca,Nd,and La),with the target sample SrCu_(3)Ru_(4)O_(12)exhibiting a very low overpotential(46 mV@10 mA·cm^(-2))and excellent catalytic stability with little decays after 48-h durability test.Precise tuning A-site cations can change the average valence state of Cu and Ru,thus the plot of HER activity versus the average Ru valence number shows a volcano-type relationship.Density functional theory indicates that the Ru 4d orbitals of SrCu3Ru4O12possesses the most suitable d-band center position among the five samples,which might be the key parameter to determine the catalytic performance.Our work provides further insight into the discovering advanced,efficient hydrogen evolution catalysts through designing precise descriptor.展开更多
The next-generation hot-carrier solar cells,which can overcome the Shockley-Queisser limit by harvesting excessenergy from hot carriers,are receiving increasing attention.Lead halide perovskite(LHP)materials are consi...The next-generation hot-carrier solar cells,which can overcome the Shockley-Queisser limit by harvesting excessenergy from hot carriers,are receiving increasing attention.Lead halide perovskite(LHP)materials are considered aspromising candidates due to their exceptional photovoltaic properties,good stability and low cost.The cooling rate of hotcarriers is a key parameter influencing the performance of hot-carrier solar cells.In this work,we successfully detected hotcarrier dynamics in operando LHP devices using the two-pulse photovoltage correlation technique.To enhance the signalto-noise ratio,we applied the delay-time modulation method instead of the traditional power modulation.This advancementallowed us to detect the intraband hot carrier cooling time for the organic LHP CH_(3)NH_(3)PbBr_(3),which is as short as 0.21 ps.In comparison,the inorganic Cs-based LHP CsPbBr_(3)exhibited a longer cooling time of around 0.59 ps due to differentphonon contributions.These results provide us new insights into the optimal design of hot-carrier solar cells and highlightthe potential of LHP materials in advancing solar cell technology.展开更多
While three-dimensional perovskites have high defect tolerance and an adjustable bandgap,their charges tend to be free rather than forming excitons,making them unsuitable for use in efficient light-emitting diodes(LED...While three-dimensional perovskites have high defect tolerance and an adjustable bandgap,their charges tend to be free rather than forming excitons,making them unsuitable for use in efficient light-emitting diodes(LEDs).Rather,quasi-two-dimensional(Q-2D)perovskites offer high photoluminescence quantum yield along with the advantages of bulk perovskites,making them ideal for high-performance LEDs.In Q-2D perovskites,the structure(which includes factors like crystal orientation,phase distribution,and layer thickness)directly influences how excitons and charge carriers behave within the material.Growth control techniques,such as varying the synthesis conditions or employing methods,allow for fine-tuning the structural characteristics of these materials,which in turn affect exciton dynamics and charge transport.This review starts with a description of the basic properties of Q-2D perovskites,examines crystal growth in solution,explains how structure affects energy transfer behavior,and concludes with future directions for Q-2D perovskite LEDs.By understanding and optimizing the structure-dependent behavior,researchers can better control exciton dynamics and charge transport,which are crucial for enhancing the performance of optoelectronic devices like solar cells and LEDs.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
Energy supply dominated by fossil energy has been and remains the main cause of carbon dioxide emissions,the major greenhouse gas leading to the current grave climate change challenges.Many technical pathways have bee...Energy supply dominated by fossil energy has been and remains the main cause of carbon dioxide emissions,the major greenhouse gas leading to the current grave climate change challenges.Many technical pathways have been proposed to address the challenges.Carbon capture and utilization(CCU) represents one of the approaches and thermochemical CO_(2) splitting driven by thermal energy is a subset of the CCU,which converts the captured CO_(2) into CO and makes it possible to achieve closed-loop carbon recirculation.Redox-active catalysts are among the most critical components of the thermochemical splitting cycles and perovskites are regarded as the most promising catalysts.Here we review the latest advancements in thermochemical cycles based on perovskites,covering thermodynamic principles,material modifications,reaction kinetics,oxygen pressure control,circular strategies,and demonstrations to provide a comprehensive overview of the topical area.Thermochemical cycles based on such materials require the consideration of trade-off between cost and efficiency,which is related to actual material used,operation mode,oxygen removal,and heat recovery.Lots of efforts have been made towards improving reaction rates,conversion efficiency and cycling stability,materials related research has been lacking-a key aspect affecting the performance across all above aspects.Double perovskites and composite perovskites arise recently as a potentially promising addition to material candidates.For such materials,more effective oxygen removal would be needed to enhance the overall efficiency,for which thermochemical or electrochemical oxygen pumps could contribute to efficient oxygen removal as well as serve as means for inert gas regeneration.The integration of thermochemical CO_(2) splitting process with downstream fuel production and other processes could reduce costs and increase efficiency of the technology.This represents one of the directions for the future research.展开更多
Wide-bandgap(WBG)perovskite solar cells(PSCs)play a fundamental role in perovskite-based tandem solar cells.However,the efficiency of WBG PSCs is limited by significant open-circuit voltage losses,which are primarily ...Wide-bandgap(WBG)perovskite solar cells(PSCs)play a fundamental role in perovskite-based tandem solar cells.However,the efficiency of WBG PSCs is limited by significant open-circuit voltage losses,which are primarily caused by surface defects.In this study,we present a novel method for modifying surfaces using the multifunctional S-ethylisothiourea hydrobromide(SEBr),which can passivate both Pb^(-1)and FA^(-1)terminated surfaces,Moreover,the SEBr upshifted the Fermi level at the perovskite interface,thereby promoting carrier collection.This proposed method was effective for both 1.67 and 1.77 eV WBG PSCs,achieving power conversion efficiencies(PCEs)of 22.47%and 19.90%,respectively,with V_(OC)values of 1.28 and 1.33 V,along with improved film and device stability.With this advancement,we were able to fabricate monolithic all-perovskite tandem solar cells with a champion PCE of 27.10%,This research offers valuable insights for passivating the surface trap states of WBG perovskite through rational multifunctional molecular engineering.展开更多
CsPbI_(2)Br perovskite solar cell has been extensively studied due to its exceptional thermal stability and relatively stable perovskite phase structure.However,the presence of bromine leads to a rapid crystallization...CsPbI_(2)Br perovskite solar cell has been extensively studied due to its exceptional thermal stability and relatively stable perovskite phase structure.However,the presence of bromine leads to a rapid crystallization rate of CsPbI_(2)Br films,resulting in small grain size and high defect density.Additionally,CsPbI_(2)Br demonstrates poor light absorption due to its wide bandgap.Therefore,it is crucial to control the crystallization rate and increase the film thickness to reduce defect density,enhance light absorption,and improve photovoltaic performance.In this study,we utilized a PbAc_(2)-incorporated twice spincoating(PTS) process to address these issues.Initially,PbAc_(2) was added to the CsPbI_(2)Br precursor solution to form a CsPbI_(2)Br film,which was then coated with the CsPbI_(2)Br precursor solution to produce the PTS film,Ac^(-)can delay the perovskite crystallization,leading to the formation of thicker and denser CsPbI_(2)Br films.Moreover,lone-pair electrons of the oxygen atom provided by Ac^(-)formed coordination bonds with under-coordinated Pb~(2+) ions to fill halogen ion vacancies,thereby reducing the defect density.Ultimately,the PTS CsPbI_(2)Br device achieved a peak power conversion efficiency(PCE) of 16.19% and maintained 96.7% of its initial PCE over 1500 h at room temperature under 25% relative humidity without any encapsulation.展开更多
The progress made by the scientific community in emerging photovoltaic technologies over the past two decades has been outstanding. Numerous methods have been developed for the preparation of hybrid organic–inorganic...The progress made by the scientific community in emerging photovoltaic technologies over the past two decades has been outstanding. Numerous methods have been developed for the preparation of hybrid organic–inorganic perovskite solar cells. The power conversion efficiency has been up to 14% by a one-step vacuum deposition technique. A serious concern is the toxicity of the materials. In this review, several methods aimed at resolving these problems to some extent have been compiled, including eco-friendly synthesis. Further efficiency enhancements are expected following optimization, and a better fundamental understanding of the internal electron charge transfer, electron–hole diffusion to the corresponding layers, flexibility, and stability-dependent bandgaps is reported. This paper explores the green synthesis of organic–inorganic perovskites for industrialization. Concerning the above facts, a simple low-cost model called‘‘dispersed photovoltaic cells' ' is presented.展开更多
Two-dimensional(2D) layered perovskites have emerged as potential alternates to traditional three-dimensional(3D)analogs to solve the stability issue of perovskite solar cells. In recent years, many efforts have been ...Two-dimensional(2D) layered perovskites have emerged as potential alternates to traditional three-dimensional(3D)analogs to solve the stability issue of perovskite solar cells. In recent years, many efforts have been spent on manipulating the interlayer organic spacing cation to improve the photovoltaic properties of Dion–Jacobson(DJ) perovskites. In this work, a serious of cycloalkane(CA) molecules were selected as the organic spacing cation in 2D DJ perovskites, which can widely manipulate the optoelectronic properties of the DJ perovskites. The underlying relationship between the CA interlayer molecules and the crystal structures, thermodynamic stabilities, and electronic properties of 58 DJ perovskites has been investigated by using automatic high-throughput workflow cooperated with density-functional(DFT) calculations.We found that these CA-based DJ perovskites are all thermodynamic stable. The sizes of the cycloalkane molecules can influence the degree of inorganic framework distortion and further tune the bandgaps with a wide range of 0.9–2.1 eV.These findings indicate the cycloalkane molecules are suitable as spacing cation in 2D DJ perovskites and provide a useful guidance in designing novel 2D DJ perovskites for optoelectronic applications.展开更多
Metal halide perovskites are crystalline materials originally developed out of scientific curiosity. They have shown great potential as active materials in optoelectronic applications. In the last 6 years, their certi...Metal halide perovskites are crystalline materials originally developed out of scientific curiosity. They have shown great potential as active materials in optoelectronic applications. In the last 6 years, their certified photovoltaic efficiencies have reached 22.1%. Compared to bulk halide perovskites, low-dimensional ones exhibited novel physical properties. The photoluminescence quantum yields of perovskite quantum dots are close to 100%. The external quantum efficiencies and current efficiencies of perovskite quantum dot light-emitting diodes have reached 8% and 43 cd A^(-1),respectively, and their nanowire lasers show ultralow-threshold room-temperature lasing with emission tunability and ease of synthesis. Perovskite nanowire photodetectors reached a responsivity of 10 A W^(-1)and a specific normalized detectivity of the order of 10^(12 )Jones. Different from most reported reviews focusing on photovoltaic applications, we summarize the rapid progress in the study of low-dimensional perovskite materials, as well as their promising applications in optoelectronic devices. In particular, we review the wide tunability of fabrication methods and the state-of-the-art research outputs of low-dimensional perovskite optoelectronic devices. Finally, the anticipated challenges and potential for this exciting research are proposed.展开更多
With only a few deep-level defect states having a high formation energy and dominance of shallow carrier non-trapping defects,the defect-tolerant electronic and optical properties of lead halide perovskites have made ...With only a few deep-level defect states having a high formation energy and dominance of shallow carrier non-trapping defects,the defect-tolerant electronic and optical properties of lead halide perovskites have made them appealing materials for high-efficiency,low-cost,solar cells and light-emitting devices.As such,recent observations of apparently deep-level and highly luminescent states in low-dimensional perovskites have attracted enormous attention as well as intensive debates.The observed green emission in 2D CsPb2Br5 and 0 D Cs4PbBr6 poses an enigma over whether it is originated from intrinsic point defects or simply from highly luminescent CsPbBr3 nanocrystals embedded in the otherwise transparent wide band gap semiconductors.The nature of deep-level edge emission in 2D Ruddlesden–Popper perovskites is also not well understood.In this mini review,the experimental evidences that support the opposing interpretations are analyzed,and challenges and root causes forthe controversy are discussed.Shortcomings in the current density functional theory approaches to modeling of properties and intrinsic point defects in lead halide perovskites are also noted.Selected experimental approaches are suggested to better correlate property with structure of a material and help resolve the controversies.Understanding and identification of the origin of luminescent centers will help design and engineer perovskites for wide device applications.展开更多
The performance of La2-x M x CuO4 perovskites （where M=Ce,Ca or Sr） as catalysts for the water-gas shift reaction was investigated at 290℃ and 360℃.The catalysts were characterized by EDS,XRD,N2 adsorption-desorpt...The performance of La2-x M x CuO4 perovskites （where M=Ce,Ca or Sr） as catalysts for the water-gas shift reaction was investigated at 290℃ and 360℃.The catalysts were characterized by EDS,XRD,N2 adsorption-desorption,XPS and XANES.The XRD results showed that all the perovskites exhibited a single phase （the presence of perovskite structure）,suggesting the incorporation of metals in the perovskite structure.The XPS and XANES results showed the presence of Cu2＋ on the surface.The perovskites that exhibited the best catalytic performance were La 2 x Ce x CuO 4 perovskites,with CO conversions of 85% 90%.Moreover,these perovskites have higher surface areas and larger amounts of Cu on the surface.And Ce has a higher filled energy level than the other metals,increasing the energy of the valence band of Ce and providing more electrons for the reaction.Besides,the La1.80Ca0.20CuO4 perovskite showed a good catalytic performance.展开更多
The newly emerging metal halide perovskites have attracted considerable attention due to their exceptional optoelectronic properties. This upsurge was initially driven when the power conversion efficiency of perovskit...The newly emerging metal halide perovskites have attracted considerable attention due to their exceptional optoelectronic properties. This upsurge was initially driven when the power conversion efficiency of perovskite-based photovoltaic devices exceeded 23%. Due to their optoelectronic properties, perovskite materials have also been used in light-emitting diodes, photodetectors, lasers, and memory devices. This study comprehensively discusses the recent progress of allinorganic perovskite-based photodetectors, focusing on their structures, morphologies of their constituent materials, and diverse device architectures that improve the performance metrics of these photodetectors. A brief outlook, highlighting the main existing problems, possible solutions to these problems, and future development directions, is also provided herein.展开更多
Energetic molecular perovskites have attracted widespread attention in the fields of energy materials due to their high detonation performance.In this work,we reported the effect of MgCo_(2)O_(4) nanosheets on the the...Energetic molecular perovskites have attracted widespread attention in the fields of energy materials due to their high detonation performance.In this work,we reported the effect of MgCo_(2)O_(4) nanosheets on the thermal decomposition of ammonium perchlorate(NH_(4)ClO_(4),AP)-based energetic molecular perovskites(AP-based energetic molecular perovskites).The morphology and structure of the MgCo_(2)O_(4) nanosheets were characterized.And their catalytic effect on the thermal decomposition of AP-based energetic molecular perovskites(H_2pz)[NH_(4)(ClO_(4))_(3)](PAP-4),(H_2dabco)[NH_(4)(ClO_(4))_(3)](DAP-4),(H_2mpz)[NH_(4)(ClO_(4))_(3)](PAP-M_(4)),and (H_2hpz)[NH_(4)(ClO_(4))_(3)](PAP-H_(4)) was analyzed.The results showed that MgCo_(2)O_(4) nanosheets had excellent intrinsically catalytic performance towards enhancing the thermal decomposition of AP-based energetic molecular perovskites.After adding MgCo_(2)O_(4) nanosheets,the thermal decomposition peak temperatures of PAP-4,DAP-4,PAP-M_(4),and PAP-H_(4) had been reduced by35.7℃,48.4℃,37.9℃,and 43.6℃,respectively.And the activation energy(Ea)of the thermal decomposition of AP-based energetic molecular perovskites had been reduced,the Eaof PAP-H_(4) decreased by 46.4 kJ/mol at most among them.The catalytic mechanism of MgCo_(2)O_(4) nanosheets for AP-based energetic molecular perovskites is analyzed.This work provides a reference for the future application of AP-based energetic molecular perovskites.展开更多
Using time-dependent terahertz spectroscopy, we investigate the role of mixed-cation and mixed-halide on the ultrafast photoconductivity dynamics of two different methylammonium(MA) lead-iodide perovskite thin films. ...Using time-dependent terahertz spectroscopy, we investigate the role of mixed-cation and mixed-halide on the ultrafast photoconductivity dynamics of two different methylammonium(MA) lead-iodide perovskite thin films. It is found that the dynamics of conductivity after photoexcitation reveals significant correlation on the microscopy crystalline features of the samples. Our results show that mixed-cation and lead mixed-halide affect the charge carrier dynamics of the lead-iodide perovskites. In the(5-AVA)_(0.05)(MA)_(0.95) PbI_(2.95) Cl_(0.05)/spiro thin film, we observe a much weaker saturation trend of the initial photoconductivity with high excitation fluence, which is attributed to the combined effect of sequential charge carrier generation, transfer, cooling and polaron formation.展开更多
Dion-Jacobson phase two-dimensional(DJ 2D)perovskites,recently attracting considerable interests,exhibit excellent environmental stability and structural tunability,but their solar cells still offer unsatisfactory pow...Dion-Jacobson phase two-dimensional(DJ 2D)perovskites,recently attracting considerable interests,exhibit excellent environmental stability and structural tunability,but their solar cells still offer unsatisfactory power conversion efficiencies(PCEs).Herein,we develop DJ 2D perovskites employing formamidinium(FA+)as a ternary cation in the perovskite cages((PDA)(FA)x(MA)3-xPb4 I13,χ=0,0.15,0.3 and 0.6,PDA=1,3-propanediammonium)for highly efficient and stable perovskite solar cells(PSCs).We found that the DJ 2D perovskite with a 10%FA+fraction presents improved crystallinity,preferred vertical orientation,and longer charge carrier lifetime compared to that without FA+doping.As a result,the FAdoped DJ 2D PSCs exhibit a champion PCE of 14.74%with superior device stability.The unencapsulated devices sustain over 92%of its initial PCE after storage at a constant relative humidity(RH)of 65%for 6000 h,90%by heat at 85℃in air for 800 h,and 94%under 1-sun illumination for 5000 h.These findings demonstrate that the incorporation of FA cation into the DJ 2D perovskite is a promising strategy to develop highly efficient and stable DJ 2D PSCs.展开更多
Oxide double perovskites A2 B’B"O6 are a class of emerging materials in the fields of optoelectronics and catalysis.Due to the chemical flexibilities of perovskite structures,there are multiple elemental combina...Oxide double perovskites A2 B’B"O6 are a class of emerging materials in the fields of optoelectronics and catalysis.Due to the chemical flexibilities of perovskite structures,there are multiple elemental combinations of cations A,B’,and B",which leading to tremendous candidates.In this study,we comprehensively screened stable oxide double perovskite A2 B’B"O6 from a pool of 2,018 perovskite candidates using a high-throughput computational approach.By considering a tolerance factor(t)-octahedral factor(μ) phase diagram,138 candidates with Fm 3 m, P21/c,and R3 c phases were selected and systematically studied via first-principles calculations based on density functional theory.The screening procedure finally predicted the existence of 21 stable perovskites,and 14 among them have never been reported.Verification with existing experimental results demonstrates that the prediction accuracy for perovskite formability is approximately 90%.The predicted oxide double perovskites exhibit quasi-direct bandgaps ranging from 0 to 4.4 eV with a significantly small direct-indirect bandgap difference,balanced electron and hole effective masses,and strong optical absorptions.The newly predicted oxide double perovskites may enlarge the pool of material candidates for applications in optoelectronics and photocatalysis.This study provides a route for computational screening of novel perovskites for functional applications.展开更多
Quasi-two-dimensional(quasi-2D)perovskites with high stability usually suffers from poor device efficiency.Chemical tuning of the spacer cations has been an effective strategy to achieve efficient and stable quasi-2D ...Quasi-two-dimensional(quasi-2D)perovskites with high stability usually suffers from poor device efficiency.Chemical tuning of the spacer cations has been an effective strategy to achieve efficient and stable quasi-2D perovskite solar cells.Here,we demonstrate that 3-halogon-substituted benzylammonium iodide(3X-BAI,X=F,Cl,Br,I)can significantly affect the orientation of low-dimensional perovskites and charge transport from perovskite to hole extraction layer,as well as device performance.With 3Br-BAI,we achieve the highest device efficiency of 13.21%for quasi-2D perovskites with a nominal n=3 average composition.Our work provides a facile approach to regulate vertical crystal orientation and charge transport via tuning the molecular structure of organic spacer toward high performance quasi-2D perovskite solar cells.展开更多
The structural,elastic,mechanical,electronic,and optical properties of KPaO_3 and RbPaO_3 compounds are investigated from first-principles calculations by using the WIEN2 k code in the frame of local density approxima...The structural,elastic,mechanical,electronic,and optical properties of KPaO_3 and RbPaO_3 compounds are investigated from first-principles calculations by using the WIEN2 k code in the frame of local density approximation（LDA） and generalized gradient approximation（GGA）.The calculated ground state quantities,such as lattice constant（α_0）,ground state energy（E）,bulk modulus（S）,and their pressure derivative（B_p） are in reasonable agreement with the present analytical and previous theoretical results and available experimental data.Based on several elastic and mechanical parameters,the structural stability,hardness,stiffness and the brittle and ductile behaviors are discussed,which reveal that protactiniumbased oxide series of perovskites is mechanically stable and possesses weak resistance to shear deformation compared with resistance to unidirectional compression while flexible and covalent behaviors are dominated in them.The analysis of band profile through Trans-Blaha modified Becke-Johnson（TB-mBJ） potential highlights the underestimation of bandgap with traditional density functional theory（DFT） approximation.Specific contribution of electronic states is investigated by means of total and partial density of states and it can be evaluated that both compounds are（Γ-Γ） direct bandgap semiconductors.All fundamental optical properties are analyzed while attention is paid to absorption and reflection spectra to explore extensive absorptions and reflections of these compounds in high frequency regions.The present method represents an influential approach to calculating the whole set of elastic,mechanical,and opto-electronic parameters,which would conduce to the understanding of various physical phenomena and empower the device engineers to implement these materials in flexible opto-electronic applications.展开更多
Crystallographic stability is an important factor that affects the stability of perovskites.The stability dictates the commercial applications of lead-based organometal halide perovskites.The tolerance factor(t)and oc...Crystallographic stability is an important factor that affects the stability of perovskites.The stability dictates the commercial applications of lead-based organometal halide perovskites.The tolerance factor(t)and octahedral factor(μ)form the state-of-the-art criteria used to evaluate the perovskite crystallographic stability.We studied the crystallographic stabilities of halide and chalcogenide perovskites by exploring an effective alternative descriptor,the global instability index(GII)that was used as an indicator of the stability of perovskite oxides.We particularly focused on determining crystallographic reliability by calculating GII.We analyzed the bond valence models of the 243 halide and chalcogenide perovskites that occupied the lowest-energy cubic-phase structures determined by conducting the first-principles-based total energy minimization calculations.The decomposition energy(ΔHD)reflects the thermodynamic stability of the system and is considered as the benchmark that helps assess the effectiveness of GII in evaluating the crystallographic stability of the systems under study.The results indicated that the accuracy of predicting thermodynamic stability was significantly higher when GII(73.6%)was analyzed compared to the cases when t(55%)andμ(39.1%)were analyzed to determine the stability.The results obtained from the machine learning-based data mining method further indicate that GII is an important descriptor of the stability of the perovskite family.展开更多
基金Project supported financially by the National Key Research and Development Program of China(Grant No.2023YFA1406000)the National Natural Science Foundation of China(Grant Nos.22171283 and 12474002)+3 种基金the Fundamental Research Funds for the Central Universities(Grant Nos.2023ZCJH03 and 2021XD-A041)the Fund of State Key Laboratory of Information Photonics and Optical Communications(Beijing University of Posts and Telecommunications,China)the Teaching Reform Projects at BUPT(Grant No.2022CXCYB03)the BUPT Excellent Ph.D.Students Foundation(Grant No.CX2023108)。
文摘Dynamic adsorption processes of reaction intermediates for alkaline hydrogen evolution(HER)catalysts are still confusing to understand.Here,we report a series of A-site ordered quadruple perovskite ruthenium-based electrocatalysts ACu_(3)Ru_(4)O_(12)(A=Na,Ca,Nd,and La),with the target sample SrCu_(3)Ru_(4)O_(12)exhibiting a very low overpotential(46 mV@10 mA·cm^(-2))and excellent catalytic stability with little decays after 48-h durability test.Precise tuning A-site cations can change the average valence state of Cu and Ru,thus the plot of HER activity versus the average Ru valence number shows a volcano-type relationship.Density functional theory indicates that the Ru 4d orbitals of SrCu3Ru4O12possesses the most suitable d-band center position among the five samples,which might be the key parameter to determine the catalytic performance.Our work provides further insight into the discovering advanced,efficient hydrogen evolution catalysts through designing precise descriptor.
基金supported by the National Key R&D Program of China(Grant No.2021YFA1400500)New Cornerstone Science Foundation through the New Cornerstone Investigator Program,and the XPLORER Prize.
文摘The next-generation hot-carrier solar cells,which can overcome the Shockley-Queisser limit by harvesting excessenergy from hot carriers,are receiving increasing attention.Lead halide perovskite(LHP)materials are considered aspromising candidates due to their exceptional photovoltaic properties,good stability and low cost.The cooling rate of hotcarriers is a key parameter influencing the performance of hot-carrier solar cells.In this work,we successfully detected hotcarrier dynamics in operando LHP devices using the two-pulse photovoltage correlation technique.To enhance the signalto-noise ratio,we applied the delay-time modulation method instead of the traditional power modulation.This advancementallowed us to detect the intraband hot carrier cooling time for the organic LHP CH_(3)NH_(3)PbBr_(3),which is as short as 0.21 ps.In comparison,the inorganic Cs-based LHP CsPbBr_(3)exhibited a longer cooling time of around 0.59 ps due to differentphonon contributions.These results provide us new insights into the optimal design of hot-carrier solar cells and highlightthe potential of LHP materials in advancing solar cell technology.
文摘While three-dimensional perovskites have high defect tolerance and an adjustable bandgap,their charges tend to be free rather than forming excitons,making them unsuitable for use in efficient light-emitting diodes(LEDs).Rather,quasi-two-dimensional(Q-2D)perovskites offer high photoluminescence quantum yield along with the advantages of bulk perovskites,making them ideal for high-performance LEDs.In Q-2D perovskites,the structure(which includes factors like crystal orientation,phase distribution,and layer thickness)directly influences how excitons and charge carriers behave within the material.Growth control techniques,such as varying the synthesis conditions or employing methods,allow for fine-tuning the structural characteristics of these materials,which in turn affect exciton dynamics and charge transport.This review starts with a description of the basic properties of Q-2D perovskites,examines crystal growth in solution,explains how structure affects energy transfer behavior,and concludes with future directions for Q-2D perovskite LEDs.By understanding and optimizing the structure-dependent behavior,researchers can better control exciton dynamics and charge transport,which are crucial for enhancing the performance of optoelectronic devices like solar cells and LEDs.
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.
文摘Energy supply dominated by fossil energy has been and remains the main cause of carbon dioxide emissions,the major greenhouse gas leading to the current grave climate change challenges.Many technical pathways have been proposed to address the challenges.Carbon capture and utilization(CCU) represents one of the approaches and thermochemical CO_(2) splitting driven by thermal energy is a subset of the CCU,which converts the captured CO_(2) into CO and makes it possible to achieve closed-loop carbon recirculation.Redox-active catalysts are among the most critical components of the thermochemical splitting cycles and perovskites are regarded as the most promising catalysts.Here we review the latest advancements in thermochemical cycles based on perovskites,covering thermodynamic principles,material modifications,reaction kinetics,oxygen pressure control,circular strategies,and demonstrations to provide a comprehensive overview of the topical area.Thermochemical cycles based on such materials require the consideration of trade-off between cost and efficiency,which is related to actual material used,operation mode,oxygen removal,and heat recovery.Lots of efforts have been made towards improving reaction rates,conversion efficiency and cycling stability,materials related research has been lacking-a key aspect affecting the performance across all above aspects.Double perovskites and composite perovskites arise recently as a potentially promising addition to material candidates.For such materials,more effective oxygen removal would be needed to enhance the overall efficiency,for which thermochemical or electrochemical oxygen pumps could contribute to efficient oxygen removal as well as serve as means for inert gas regeneration.The integration of thermochemical CO_(2) splitting process with downstream fuel production and other processes could reduce costs and increase efficiency of the technology.This represents one of the directions for the future research.
基金financially supported by the National Natural Science Foundation of China(52330004)the Fundamental Research Funds for the Central Universities(WUT:2023IVA075 and 2023IVB009)+3 种基金the financial support from RISE project Grant(Q-CDBK)Start-up Fund for RAPs under the Strategic Hiring Scheme(PoluU)(1-BD1H)PRI Strategic Grant(1-CD7X)RI-iWEAR Strategic Supporting Scheme(1-CD94)。
文摘Wide-bandgap(WBG)perovskite solar cells(PSCs)play a fundamental role in perovskite-based tandem solar cells.However,the efficiency of WBG PSCs is limited by significant open-circuit voltage losses,which are primarily caused by surface defects.In this study,we present a novel method for modifying surfaces using the multifunctional S-ethylisothiourea hydrobromide(SEBr),which can passivate both Pb^(-1)and FA^(-1)terminated surfaces,Moreover,the SEBr upshifted the Fermi level at the perovskite interface,thereby promoting carrier collection.This proposed method was effective for both 1.67 and 1.77 eV WBG PSCs,achieving power conversion efficiencies(PCEs)of 22.47%and 19.90%,respectively,with V_(OC)values of 1.28 and 1.33 V,along with improved film and device stability.With this advancement,we were able to fabricate monolithic all-perovskite tandem solar cells with a champion PCE of 27.10%,This research offers valuable insights for passivating the surface trap states of WBG perovskite through rational multifunctional molecular engineering.
基金supported by the National Natural Science Foundation of China (U22A20142)the Fundamental Research Funds for the Central Universities (2023JC007)。
文摘CsPbI_(2)Br perovskite solar cell has been extensively studied due to its exceptional thermal stability and relatively stable perovskite phase structure.However,the presence of bromine leads to a rapid crystallization rate of CsPbI_(2)Br films,resulting in small grain size and high defect density.Additionally,CsPbI_(2)Br demonstrates poor light absorption due to its wide bandgap.Therefore,it is crucial to control the crystallization rate and increase the film thickness to reduce defect density,enhance light absorption,and improve photovoltaic performance.In this study,we utilized a PbAc_(2)-incorporated twice spincoating(PTS) process to address these issues.Initially,PbAc_(2) was added to the CsPbI_(2)Br precursor solution to form a CsPbI_(2)Br film,which was then coated with the CsPbI_(2)Br precursor solution to produce the PTS film,Ac^(-)can delay the perovskite crystallization,leading to the formation of thicker and denser CsPbI_(2)Br films.Moreover,lone-pair electrons of the oxygen atom provided by Ac^(-)formed coordination bonds with under-coordinated Pb~(2+) ions to fill halogen ion vacancies,thereby reducing the defect density.Ultimately,the PTS CsPbI_(2)Br device achieved a peak power conversion efficiency(PCE) of 16.19% and maintained 96.7% of its initial PCE over 1500 h at room temperature under 25% relative humidity without any encapsulation.
基金CONACYT for a postdoctoral research fellowship (Fellowship:24641)support by CONACYT (Grant: 240011)UANL-FCQ
文摘The progress made by the scientific community in emerging photovoltaic technologies over the past two decades has been outstanding. Numerous methods have been developed for the preparation of hybrid organic–inorganic perovskite solar cells. The power conversion efficiency has been up to 14% by a one-step vacuum deposition technique. A serious concern is the toxicity of the materials. In this review, several methods aimed at resolving these problems to some extent have been compiled, including eco-friendly synthesis. Further efficiency enhancements are expected following optimization, and a better fundamental understanding of the internal electron charge transfer, electron–hole diffusion to the corresponding layers, flexibility, and stability-dependent bandgaps is reported. This paper explores the green synthesis of organic–inorganic perovskites for industrialization. Concerning the above facts, a simple low-cost model called‘‘dispersed photovoltaic cells' ' is presented.
基金supported by the National Natural Science Foundation of China (Grant No. 62004080)the Postdoctoral Innovative Talents Supporting Program (Grant No. BX20190143)the China Postdoctoral Science Foundation (Grant No. 2020M670834)。
文摘Two-dimensional(2D) layered perovskites have emerged as potential alternates to traditional three-dimensional(3D)analogs to solve the stability issue of perovskite solar cells. In recent years, many efforts have been spent on manipulating the interlayer organic spacing cation to improve the photovoltaic properties of Dion–Jacobson(DJ) perovskites. In this work, a serious of cycloalkane(CA) molecules were selected as the organic spacing cation in 2D DJ perovskites, which can widely manipulate the optoelectronic properties of the DJ perovskites. The underlying relationship between the CA interlayer molecules and the crystal structures, thermodynamic stabilities, and electronic properties of 58 DJ perovskites has been investigated by using automatic high-throughput workflow cooperated with density-functional(DFT) calculations.We found that these CA-based DJ perovskites are all thermodynamic stable. The sizes of the cycloalkane molecules can influence the degree of inorganic framework distortion and further tune the bandgaps with a wide range of 0.9–2.1 eV.These findings indicate the cycloalkane molecules are suitable as spacing cation in 2D DJ perovskites and provide a useful guidance in designing novel 2D DJ perovskites for optoelectronic applications.
基金supported by the Doctoral Program of Higher Education(20130142120075)the Fundamental Research Funds for the Central Universities(HUST:2016YXMS032)National Key Research and Development Program of China(Grant No.2016YFB0700702)
文摘Metal halide perovskites are crystalline materials originally developed out of scientific curiosity. They have shown great potential as active materials in optoelectronic applications. In the last 6 years, their certified photovoltaic efficiencies have reached 22.1%. Compared to bulk halide perovskites, low-dimensional ones exhibited novel physical properties. The photoluminescence quantum yields of perovskite quantum dots are close to 100%. The external quantum efficiencies and current efficiencies of perovskite quantum dot light-emitting diodes have reached 8% and 43 cd A^(-1),respectively, and their nanowire lasers show ultralow-threshold room-temperature lasing with emission tunability and ease of synthesis. Perovskite nanowire photodetectors reached a responsivity of 10 A W^(-1)and a specific normalized detectivity of the order of 10^(12 )Jones. Different from most reported reviews focusing on photovoltaic applications, we summarize the rapid progress in the study of low-dimensional perovskite materials, as well as their promising applications in optoelectronic devices. In particular, we review the wide tunability of fabrication methods and the state-of-the-art research outputs of low-dimensional perovskite optoelectronic devices. Finally, the anticipated challenges and potential for this exciting research are proposed.
基金support from the Robert A.Welch Foundation(E-1728)National Science Foundation(EEC-1530753)supported by the State of Texas through the Texas Center for superconductivity at the University of Houston
文摘With only a few deep-level defect states having a high formation energy and dominance of shallow carrier non-trapping defects,the defect-tolerant electronic and optical properties of lead halide perovskites have made them appealing materials for high-efficiency,low-cost,solar cells and light-emitting devices.As such,recent observations of apparently deep-level and highly luminescent states in low-dimensional perovskites have attracted enormous attention as well as intensive debates.The observed green emission in 2D CsPb2Br5 and 0 D Cs4PbBr6 poses an enigma over whether it is originated from intrinsic point defects or simply from highly luminescent CsPbBr3 nanocrystals embedded in the otherwise transparent wide band gap semiconductors.The nature of deep-level edge emission in 2D Ruddlesden–Popper perovskites is also not well understood.In this mini review,the experimental evidences that support the opposing interpretations are analyzed,and challenges and root causes forthe controversy are discussed.Shortcomings in the current density functional theory approaches to modeling of properties and intrinsic point defects in lead halide perovskites are also noted.Selected experimental approaches are suggested to better correlate property with structure of a material and help resolve the controversies.Understanding and identification of the origin of luminescent centers will help design and engineer perovskites for wide device applications.
文摘The performance of La2-x M x CuO4 perovskites （where M=Ce,Ca or Sr） as catalysts for the water-gas shift reaction was investigated at 290℃ and 360℃.The catalysts were characterized by EDS,XRD,N2 adsorption-desorption,XPS and XANES.The XRD results showed that all the perovskites exhibited a single phase （the presence of perovskite structure）,suggesting the incorporation of metals in the perovskite structure.The XPS and XANES results showed the presence of Cu2＋ on the surface.The perovskites that exhibited the best catalytic performance were La 2 x Ce x CuO 4 perovskites,with CO conversions of 85% 90%.Moreover,these perovskites have higher surface areas and larger amounts of Cu on the surface.And Ce has a higher filled energy level than the other metals,increasing the energy of the valence band of Ce and providing more electrons for the reaction.Besides,the La1.80Ca0.20CuO4 perovskite showed a good catalytic performance.
基金Project supported by the National Science Foundation for Distinguished Young Scholars of China(Grant No.61425021)the National Natural Science Foundation of China(Grant Nos.U1604263,11774318,and 11604302)
文摘The newly emerging metal halide perovskites have attracted considerable attention due to their exceptional optoelectronic properties. This upsurge was initially driven when the power conversion efficiency of perovskite-based photovoltaic devices exceeded 23%. Due to their optoelectronic properties, perovskite materials have also been used in light-emitting diodes, photodetectors, lasers, and memory devices. This study comprehensively discusses the recent progress of allinorganic perovskite-based photodetectors, focusing on their structures, morphologies of their constituent materials, and diverse device architectures that improve the performance metrics of these photodetectors. A brief outlook, highlighting the main existing problems, possible solutions to these problems, and future development directions, is also provided herein.
基金the National Natural Science Foundation of China(Grant No.21975227)the Found of National defence Sci&Tech Laboratory(Grant No.6142602210306)。
文摘Energetic molecular perovskites have attracted widespread attention in the fields of energy materials due to their high detonation performance.In this work,we reported the effect of MgCo_(2)O_(4) nanosheets on the thermal decomposition of ammonium perchlorate(NH_(4)ClO_(4),AP)-based energetic molecular perovskites(AP-based energetic molecular perovskites).The morphology and structure of the MgCo_(2)O_(4) nanosheets were characterized.And their catalytic effect on the thermal decomposition of AP-based energetic molecular perovskites(H_2pz)[NH_(4)(ClO_(4))_(3)](PAP-4),(H_2dabco)[NH_(4)(ClO_(4))_(3)](DAP-4),(H_2mpz)[NH_(4)(ClO_(4))_(3)](PAP-M_(4)),and (H_2hpz)[NH_(4)(ClO_(4))_(3)](PAP-H_(4)) was analyzed.The results showed that MgCo_(2)O_(4) nanosheets had excellent intrinsically catalytic performance towards enhancing the thermal decomposition of AP-based energetic molecular perovskites.After adding MgCo_(2)O_(4) nanosheets,the thermal decomposition peak temperatures of PAP-4,DAP-4,PAP-M_(4),and PAP-H_(4) had been reduced by35.7℃,48.4℃,37.9℃,and 43.6℃,respectively.And the activation energy(Ea)of the thermal decomposition of AP-based energetic molecular perovskites had been reduced,the Eaof PAP-H_(4) decreased by 46.4 kJ/mol at most among them.The catalytic mechanism of MgCo_(2)O_(4) nanosheets for AP-based energetic molecular perovskites is analyzed.This work provides a reference for the future application of AP-based energetic molecular perovskites.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11604202,11674213,61735010 and 51603119the Young Eastern Scholar under Grant Nos QD2015020 and QD2016027+3 种基金the Shanghai Rising-Star Program under Grant No18QA1401700the ‘Chen Guang’ Project under Grant Nos 16CG45 and 16CG46the Shanghai Municipal Education Commissionthe Shanghai Education Development Foundation
文摘Using time-dependent terahertz spectroscopy, we investigate the role of mixed-cation and mixed-halide on the ultrafast photoconductivity dynamics of two different methylammonium(MA) lead-iodide perovskite thin films. It is found that the dynamics of conductivity after photoexcitation reveals significant correlation on the microscopy crystalline features of the samples. Our results show that mixed-cation and lead mixed-halide affect the charge carrier dynamics of the lead-iodide perovskites. In the(5-AVA)_(0.05)(MA)_(0.95) PbI_(2.95) Cl_(0.05)/spiro thin film, we observe a much weaker saturation trend of the initial photoconductivity with high excitation fluence, which is attributed to the combined effect of sequential charge carrier generation, transfer, cooling and polaron formation.
基金supported by the National Natural Science Foundation of China(No.51973223)the DICP&QIBEBT UN201705+1 种基金the Liaoning Revitalization Talents Program(XLYC1807231)the DICP(Grant No.DICP I202011)。
文摘Dion-Jacobson phase two-dimensional(DJ 2D)perovskites,recently attracting considerable interests,exhibit excellent environmental stability and structural tunability,but their solar cells still offer unsatisfactory power conversion efficiencies(PCEs).Herein,we develop DJ 2D perovskites employing formamidinium(FA+)as a ternary cation in the perovskite cages((PDA)(FA)x(MA)3-xPb4 I13,χ=0,0.15,0.3 and 0.6,PDA=1,3-propanediammonium)for highly efficient and stable perovskite solar cells(PSCs).We found that the DJ 2D perovskite with a 10%FA+fraction presents improved crystallinity,preferred vertical orientation,and longer charge carrier lifetime compared to that without FA+doping.As a result,the FAdoped DJ 2D PSCs exhibit a champion PCE of 14.74%with superior device stability.The unencapsulated devices sustain over 92%of its initial PCE after storage at a constant relative humidity(RH)of 65%for 6000 h,90%by heat at 85℃in air for 800 h,and 94%under 1-sun illumination for 5000 h.These findings demonstrate that the incorporation of FA cation into the DJ 2D perovskite is a promising strategy to develop highly efficient and stable DJ 2D PSCs.
基金the funding support from the National Key Research and Development Program of China(Grant 2016YFB0700700)National Natural Science Foundation of China(Grants 11674237,11974257)+1 种基金Priority Academic program Development of Jiangsu Higher Education Institutions(PAPD)Suzhou Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies,China。
文摘Oxide double perovskites A2 B’B"O6 are a class of emerging materials in the fields of optoelectronics and catalysis.Due to the chemical flexibilities of perovskite structures,there are multiple elemental combinations of cations A,B’,and B",which leading to tremendous candidates.In this study,we comprehensively screened stable oxide double perovskite A2 B’B"O6 from a pool of 2,018 perovskite candidates using a high-throughput computational approach.By considering a tolerance factor(t)-octahedral factor(μ) phase diagram,138 candidates with Fm 3 m, P21/c,and R3 c phases were selected and systematically studied via first-principles calculations based on density functional theory.The screening procedure finally predicted the existence of 21 stable perovskites,and 14 among them have never been reported.Verification with existing experimental results demonstrates that the prediction accuracy for perovskite formability is approximately 90%.The predicted oxide double perovskites exhibit quasi-direct bandgaps ranging from 0 to 4.4 eV with a significantly small direct-indirect bandgap difference,balanced electron and hole effective masses,and strong optical absorptions.The newly predicted oxide double perovskites may enlarge the pool of material candidates for applications in optoelectronics and photocatalysis.This study provides a route for computational screening of novel perovskites for functional applications.
基金supported financially by the National Natural Science Foundation of China(61974066,61961160733,62005223)the National Science Fund for Distinguished Young Scholars(61725502)+2 种基金the Major Program of Natural Science Research of Jiangsu Higher Education Institutions of China(18KJA510002)the Joint Research Funds of Department of Science&Technology of Shaanxi Province and Northwestern Polytechnical University(2020GXLH-Z-024)the Synergetic Innovation Center for Organic Electronics and Information Displays。
文摘Quasi-two-dimensional(quasi-2D)perovskites with high stability usually suffers from poor device efficiency.Chemical tuning of the spacer cations has been an effective strategy to achieve efficient and stable quasi-2D perovskite solar cells.Here,we demonstrate that 3-halogon-substituted benzylammonium iodide(3X-BAI,X=F,Cl,Br,I)can significantly affect the orientation of low-dimensional perovskites and charge transport from perovskite to hole extraction layer,as well as device performance.With 3Br-BAI,we achieve the highest device efficiency of 13.21%for quasi-2D perovskites with a nominal n=3 average composition.Our work provides a facile approach to regulate vertical crystal orientation and charge transport via tuning the molecular structure of organic spacer toward high performance quasi-2D perovskite solar cells.
文摘The structural,elastic,mechanical,electronic,and optical properties of KPaO_3 and RbPaO_3 compounds are investigated from first-principles calculations by using the WIEN2 k code in the frame of local density approximation（LDA） and generalized gradient approximation（GGA）.The calculated ground state quantities,such as lattice constant（α_0）,ground state energy（E）,bulk modulus（S）,and their pressure derivative（B_p） are in reasonable agreement with the present analytical and previous theoretical results and available experimental data.Based on several elastic and mechanical parameters,the structural stability,hardness,stiffness and the brittle and ductile behaviors are discussed,which reveal that protactiniumbased oxide series of perovskites is mechanically stable and possesses weak resistance to shear deformation compared with resistance to unidirectional compression while flexible and covalent behaviors are dominated in them.The analysis of band profile through Trans-Blaha modified Becke-Johnson（TB-mBJ） potential highlights the underestimation of bandgap with traditional density functional theory（DFT） approximation.Specific contribution of electronic states is investigated by means of total and partial density of states and it can be evaluated that both compounds are（Γ-Γ） direct bandgap semiconductors.All fundamental optical properties are analyzed while attention is paid to absorption and reflection spectra to explore extensive absorptions and reflections of these compounds in high frequency regions.The present method represents an influential approach to calculating the whole set of elastic,mechanical,and opto-electronic parameters,which would conduce to the understanding of various physical phenomena and empower the device engineers to implement these materials in flexible opto-electronic applications.
基金supported by the National Natural Science Foundation of China(62004080 and 92061113)the Postdoctoral Innovative Talents Supporting Program(BX20190143)the China Postdoctoral Science Foundation(2020M670834)。
文摘Crystallographic stability is an important factor that affects the stability of perovskites.The stability dictates the commercial applications of lead-based organometal halide perovskites.The tolerance factor(t)and octahedral factor(μ)form the state-of-the-art criteria used to evaluate the perovskite crystallographic stability.We studied the crystallographic stabilities of halide and chalcogenide perovskites by exploring an effective alternative descriptor,the global instability index(GII)that was used as an indicator of the stability of perovskite oxides.We particularly focused on determining crystallographic reliability by calculating GII.We analyzed the bond valence models of the 243 halide and chalcogenide perovskites that occupied the lowest-energy cubic-phase structures determined by conducting the first-principles-based total energy minimization calculations.The decomposition energy(ΔHD)reflects the thermodynamic stability of the system and is considered as the benchmark that helps assess the effectiveness of GII in evaluating the crystallographic stability of the systems under study.The results indicated that the accuracy of predicting thermodynamic stability was significantly higher when GII(73.6%)was analyzed compared to the cases when t(55%)andμ(39.1%)were analyzed to determine the stability.The results obtained from the machine learning-based data mining method further indicate that GII is an important descriptor of the stability of the perovskite family.
