Photo-and Electrocatalytic CO_(2)Reduction Based on Stable Lead-Free Perovskite Cs2PdBr6

All-inorganic lead-free palladium(Pd)halogen perovskites with prominent optoelectronic properties provide admirable potential for selective photo-and electroreduction of CO_(2).But it remains unachieved for effectively converting the CO_(2)to CO with high selectivity on Pd-based perovskites driven by solar light or electricity.Herein,high-quality Cs_(2)PdBr_(6)microcrystals and nanocrystals were synthesized through a facile antisolvent method.Among all the reported pure-phase perovskites,the Cs_(2)PdBr_(6)nanocrystals synthesized at 50℃performed the highest effectiveness on CO_(2)to CO conversion generating 73.8μmol g^(-1)of CO yield with 100%selectivity under visible light illumination(λ>420 nm)for 3 h.Meanwhile,for the first time,we report a new application of lead-free perovskites,in which they are applied to electrocatalysis of CO_(2)reduction reaction.Noticeably,they showed significant electrocatalytic activity(Faradaic yield:78%for CO)and operation stability(10 h).And the surface reaction intermediates were dynamically monitored and precisely unraveled according to the in situ diffuse reflectance infrared Fourier transform spectra investigation.In combination with the density functional theory calculation,the reaction mechanism and pathways were revealed.This work not only provides significant strategies to enhance the photocatalytic performance of perovskites,but also shows excellent potential for their application in electrocatalysis.

Efficient Environment-friendly Lead-free Tin Perovskite Solar Cells Enabled by Incorporating 4-Fluorobenzylammonium Iodide Additives

Development of tin(Sn)-based perovskite solar cells(PSCs)largely lags behind that of lead counterparts due to fast crystallization process of Sn perovskite and numerous defects in both bulk and surface of Sn perovskite films.Herein,this work reports a facile strategy of introducing 4-fluorobenzylammonium iodide(FBZAI)as additives into Sn perovskite precursor to synergistically modulate the roles of benzylamine and fluorine in Sn-based PSCs.Incorporation of FBZAI can increase crystallinity,passivate defects,and inhibit the oxidation of Sn^(2+),leading to suppression of nonradiative recombination and enhancement of charge transport and collection in devices.As a result,the best-performing Sn-based PSC with the FBZAI additive achieves the maximum PCE of 13.85%with the enhanced fill factor of 77.8%and open-circuit voltage of 0.778 V.Our unencapsulated device exhibits good stability by maintaining 95%of its initial PCE after 160 days of storage.

Air-Stable,Eco-Friendly RRAMs Based on Lead-Free Cs_(3)Bi_(2)Br_(9)Perovskite Quantum Dots for High-Performance Information Storage

Development of lead-free halide perovskites that are innocuous and stable has become an attractive trend in resistive random access memory(RRAM)fields.However,their inferior memory properties compared with the lead-based analogs hinder their commercialization.Herein,the lead-free Cs_(3)Bi_(2)Br_(9)perovskite quantum dot(PQD)-based RRAMs are reported with outstanding memory performance,where Cs_(3)Bi_(2)Br_(9)quantum dots(QDs)are synthesized via a modified ligand-assisted recrystallization process.This is the first report of applying Cs_(3)Bi_(2)Br_(9)QDs as the switching layer for RRAM device.The Cs_(3)Bi_(2)Br_(9)QD device demonstrates nonvolatile resistive switching(RS)effect with large ON/OFF ratio of 105,low set voltage of-0.45 V,as well as good reliability,reproducibility,and flexibility.Concurrently,the device exhibits the notable tolerance toward moisture,heat and light illumination,and long-term stability of 200 days.More impressively,the device shows the reliable light-modulated RS behavior,and therefrom the logic gate operations including"AND"and"OR"are implemented,foreboding its prospect in logic circuits integrated with storage and computation.Such multifunctionality of device could be derived from the unique 2D layered crystal structure,small particle size,quantum confinement effect,and photoresponse of Cs_(3)Bi_(2)Br_(9)QDs.This work provides the strategy toward the high-performance RRAMs based on stable and eco-friendly perovskites for future applications.

First Principle Study of Cesium-based Lead-free Halide Double Perovskites

Inorganic halide double perovskites A_(2)B'B"X_(6) have gained significant interests for their diverse composition,stable physicochemical properties,and potential for photoelectric applications.The influences of trivalent and monovalent cations on the formation energy,decomposition energy,electronic structure and optical properties of cesium-based lead-free Cs^(+)_(2)B'B"Br_(6) (B'=Na^(+),In^(+)Cu^(+),or Ag^(+);B"=Bi^(3),Sb^(3+),In^(3+)) are systematically studied.In view of the analysis and results of the selected double perovskites,for the double perovskites with different B-site trivalent cation,the band gap increases in the order of Cs_(2)AgInBr_(6),Cs_(2)AgSbBr_(6) and Cs_(2)AgBiBr_(6),with Cs_(2)AgBiBr_(6) possessing the highest thermodynamic stability.Therefore,the Bi-based perovskites are further studied to elucidate the effect of monovalent cation on their stability and electronics.Results show that the thermodynamic stability rises in the sequence of Cs_(2)NaBiBr_(6),Cs_(2)InBiBr_(6),Cs_(2)AgBiBr_(6) and Cs_(2)CuBiBr_(6).Notably,Cs_(2)CuBiBr_(6) exhibits a relatively narrow and appropriate band gap of 1.4634 eV,together with the highest absorption coefficient than other compounds,suggesting that Cs_(2)CuBiBr_(6) is a promising light absorbing material that can be further explored experimentally and be applied to optoelectronic devices.Our research offers theoretical backing for the potential optoelectronic application of cesium-based lead-free halide double perovskites in solar energy conversion.

Ligand modulation of active center to promote lead-free Cs_(2)AgInCl_(6)photocatalytic CO_(2)reduction

Metal halide perovskites(MHP)are potential candidates for the photocatalytic reduction of CO_(2)due to their long photogenerated carrier lifetime and charge diffusion length.However,the conventional long-chain ligand impedes the adsorption and activation of CO_(2)molecules in practical applications.Here,a ligand modulation technology is employed to enhance the photocatalytic CO_(2)reduction activity of lead-free Cs_(2)AgInCl_(6)microcrystals(MCs).The Cs_(2)AgInCl_(6)MCs passivated by Oleic acid(OLA)and Octanoic acid(OCA)are used for photocatalytic CO_(2)reduction.The results show that the surface defects and electronic properties of Cs_(2)AgInCl_(6)MCs can be adjusted through ligand modulation.Compared with the OLA-Cs_(2)AgInCl_(6),the OCA-Cs_(2)AgInCl_(6)catalyst demonstrated a significant improvement in the catalytic yield of CO and CH_(4).The CO and CH_(4)catalytic yields of OCA-Cs_(2)AgInCl_(6)reached 171.88 and34.15μmol g^(-1)h^(-1)which were 2.03 and 12.98 times higher than those of OLA-Cs_(2)AgInCl_(6),and the total electron consumption rate of OCA-Cs_(2)AgInCl_(6)was 615.2μmol g^(-1)h^(-1)which was 3.25 times higher than that of OLA-Cs_(2)AgInCl_(6).Furthermore,in situ diffuse reflectance infrared Fourier transform spectra revealed the enhancement of photocatalytic activity in Cs_(2)AgInCl_(6)MCs induced by ligand modulation.This study illustrates the potential of lead-free Cs_(2)AgInCl_(6)MCs for efficient photocatalytic CO_(2)reduction and provides a ligand modulation strategy for the active promotion of MHP photocatalysts.

Ultrasensitive and stable X-ray detection using zero-dimensional lead-free perovskites

Sensitive and reliable X-ray detectors are essential for medical radiography,industrial inspection and security screening.Lowering the radiation dose allows reduced health risks and increased frequency and fidelity of diagnostic technologies for earlier detection of disease and its recurrence.Three-dimensional(3 D)organic-inorganic hybrid lead halide perovskites are promising for direct X-ray detection-they show improved sensitivity compared to conventional X-ray detectors.However,their high and unstable dark current,caused by ion migration and high dark carrier concentration in the 3 D hybrid perovskites,limits their performance and long-term operation stability.Here we report ultrasensitive,stable X-ray detectors made using zero-dimensional(0 D)methylammonium bismuth iodide perovskite(MA3Bi2I9)single crystals.The 0 D crystal structure leads to a high activation energy(Ea)for ion migration(0.46 e V)and is also accompanied by a low dark carrier concentration(~10^6 cm^-3).The X-ray detectors exhibit sensitivity of 10,620μC Gy-1 air cm-2,a limit of detection(Lo D)of 0.62 nG yairs-1,and stable operation even under high applied biases;no deterioration in detection performance was observed following sensing of an integrated X-ray irradiation dose of^23,800 m Gyair,equivalent to>200,000 times the dose required for a single commercial X-ray chest radiograph.Regulating the ion migration channels and decreasing the dark carrier concentration in perovskites provide routes for stable and ultrasensitive X-ray detectors.

Research progress in lead-less or lead-free three-dimensional perovskite absorber materials for solar cells

The trend toward lead-free or lead-less perovskite solar cells(PSCs) has attracted increasing attention over the past few years because the toxicity of lead(Pb) is one of the substantial restrictions for large-scale applications. Researchers have investigated the viability of substituting Pb with other elements(group 14 elements, group 2 elements, transition-metal elements, and group 13 and 15 elements) in the three-dimensional(3 D) perovskites by theoretical calculations and experimental explorations. In this paper, recent research progress in Pb-less and Pb-free PSCs on the perovskite compositions, deposition methods, and device structures are summarized and the main problems that hinder the enhancement of device efficiency and stability are discussed in detail. To date, the fully Sn-based PSCs have shown a power conversion efficiency(PCE) of 8.12% and poor device stability. However, lead-less PSCs have shown higher PCE and a better stability. In addition, the introduction of double-perovskite materials also draws researchers' attention. We believe that the engineering of elemental composition, perovskite deposition methods, and interfacial modification are critical for the future development of Pb-less and Pb-free PSCs.

Self-template-oriented synthesis of lead-free perovskite Cs_(3)Bi_(2)I_(9) nanosheets for boosting photocatalysis of CO_(2) reduction over Z-scheme heterojunction Cs_(3)Bi_(2)I_(9)/CeO_(2)

Lead halide perovskite (LHP) nanocrystals have been intensely studied as photocatalysts for artificial photosynthesis in recent years.However,the toxicity of lead in LHP seriously limits their potential for widespread applications.Herein,we first present the synthesis of 2D lead-free halide perovskite (Cs_(3)Bi_(2)I_(9)) nanosheets with self-template-oriented method,in which BiOI/Bi_(2)O_(2) nanosheets were used as the template and Bi ion source simultaneously.Through facile electrostatic self-assembly strategy,a Z-scheme heterojunction composed of Cs_(3)Bi_(2)I_(9)nanosheets and CeO_(2) nanosheets (Cs_(3)Bi_(2)I_(9)/CeO_(2)-3:1) was constructed as photocatalyst for the photo-reduction of CO_(2) coupled with the oxidation of H_(2)O.Due to the matching energy levels and the close interfacial contact between Cs_(3)Bi_(2)I_(9)and CeO_(2) nanosheets,the separation efficiency of the photogenerated carriers in Cs_(3)Bi_(2)I_(9)/CeO_(2)-3:1 composite was significantly improved.Consequently,the environment-friendly halide perovskite heterojunction Cs_(3)Bi_(2)I_(9)/CeO_(2)-3:1presents impressive photocatalytic activity for the reduction of CO_(2)to CH_(4)and CO with an electron consumption yield of 877.04μmol g^(-1),which is over 7 and 15 times higher than those of pristine Cs_(3)Bi_(2)I_(9)and CeO_(2)nanosheets,exceeding the yield of other reported bismuth-based perovskite for photocatalytic CO_(2)reduction.

Defects and doping engineering towards high performance lead-free or lead-less perovskite solar cells

Up to now, perovskite solar cells(PSCs) have reached a certified 25.5% efficiency. As a promising photo-electric material, the metal halide perovskite possesses many outstanding properties such as tunable bandgap, long diffusion length, high absorption coefficient and carrier mobility. In spite of these remarkable properties, defects are inevitable during the solution processing. Therefore, many efforts have been made to reduce defects in perovskite films and thus improve the performance of devices. Among them,substitution or doping engineering is one of the most studied methods. Meanwhile, due to the poor stability of the organic-inorganic hybrid perovskite and the toxicity of Pb-based perovskite materials, all inorganic perovskite and lead-less or lead-free perovskite have emerged as promising materials. Here,we focus on the defect engineering especially substitutions on different sites in an ABX_(3) structure. The particular attention is devoted towards lead-less or lead-free perovskites, and we discuss several common elements or groups used to partially replace Pb^(2+). It is noted that proper elemental doping at different sites is an important guarantee for obtaining high-performance lead-less or lead-free PSCs.

Stability and optoelectronic property of lead-free halide double perovskite Cs_(2)B′BiI_(6)(B′=Li,Na and K)

Although lead-based perovskite solar cells have achieved more than 25%power conversion efficiency,the toxicity of lead and instability are still urgent problems faced in industrial application.Lead-free halide double perovskite(DP)materials are promising candidates to resolve these issues.Based on the density functional theory,we explore the geometric stability,thermodynamic stability,mechanical stability,electronic structures,and optical properties of theCs_(2)B 0BiI_(6)(B 0=Li,Na and K)DP materials.By analyzing the tolerance factor and octahedral factor,we find the geometric stabilities ofCs_(2)NaBiI_(6) andCs_(2)KBiI_(6) DPs are better thanCs_(2)LiBiI_(6).By calculating the total energy,formation energy and decomposition energy,we propose that the most favorable structure ofCs_(2)B 0BiI_(6) is the orthorhombic phase,andCs_(2)LiBiI_(6) is less stable relative to the other two counterparts from an energetic viewpoint.Mechanical stability evaluations reveal that the orthorhombicCs_(2)LiBiI_(6) material is less stable relative to the isostructuralCs_(2)NaBiI_(6) andCs_(2)KBiI_(6) DPs.The mechanical property calculations indicate that theCs_(2)B 0BiI_(6) DPs possess good ductility,which can be used as flexible materials.Electronic structures and optical property calculations show that the orthorhombicCs_(2)B 0BiI_(6) DPs have suitable band gap values,weaker exciton binding energies,and excellent optical absorption performance in the visible-light range.Based on the above comprehensive assessments,we can conclude that the orthorhombic Cs_(2)NaBiI_(6) and Cs_(2)KBiI_(6) DPs with good stability are promising candidates for solar cell applications.

Heterogeneous FASnI3 Absorber with Enhanced Electric Field for High-Performance Lead-Free Perovskite Solar Cells

Lead-free tin perovskite solar cells(PSCs)have undergone rapid development in recent years and are regarded as a promising ecofriendly photovoltaic technology.However,a strategy to suppress charge recombination via a built-in electric field inside a tin perovskite crystal is still lacking.In the present study,a formamidinium tin iodide(FASnI;)perovskite absorber with a vertical Sn;gradient was fabricated using a Lewis base-assisted recrystallization method to enhance the built-in electric field and minimize the bulk recombination loss inside the tin perovskites.Depth-dependent X-ray photoelectron spectroscopy revealed that the Fermi level upshifts with an increase in Sn;content from the bottom to the top in this heterogeneous FASnI;film,which generates an additional electric field to prevent the trapping of photo-induced electrons and holes.Consequently,the Sn;-gradient FASnI;absorber exhibits a promising efficiency of 13.82%for inverted tin PSCs with an open-circuit voltage increase of 130 mV,and the optimized cell maintains over 13%efficiency after continuous operation under 1-sun illumination for 1,000 h.

Stability,electronic structure,and optical properties of lead-free perovskite monolayer Cs3B2X9(B=Sb,Bi;X=Cl,Br,I)and bilayer vertical heterostructure Cs_(3)B_(2)X_(9)/Cs3B’2X9(B,B’=Sb,Bi;X=Cl,Br,I)

The lead-free perovskites Cs_(3)B_(2)X_(9)(B=Sb,Bi;X=Cl,Br,I)as the popular photoelectric materials have excellent optical properties with lower toxicity.In this study,we systematically investigate the stable monolayer Cs_(3)B_(2)X_(9)and bilayer vertical heterostructure Cs_(3)B_(2)X_(9)/Cs3B02X9(B,B0=Sb,Bi;X=Cl,Br,I)via first-principles simulations.By exploring the electrical structures and band edge positions,we find the band gap reduction and the band type transition in the heterostructure Cs_(3)B_(2)X_(9)/Cs3B02X9 due to the charge transfer between layers.Furthermore,the results of optical properties reveal light absorption from the visible light to UV region,especially monolayer Cs3Sb2I9 and heterostructure Cs3Sb2I9/Cs3Bi2I9,which have absorption peaks in the visible light region,leading to the possibility of photocatalytic water splitting.These results provide insights for more two-dimensional semiconductors applied in the optoelectronic and photocatalytic fields.

Ligand Engineering in Tin-Based Perovskite Solar Cells

Perovskite solar cells(PSCs)have attracted aggressive attention in the photovoltaic field in light of the rapid increasing power conversion efficiency.However,their large-scale application and commercialization are limited by the toxicity issue of lead(Pb).Among all the lead-free perovskites,tin(Sn)-based perovskites have shown potential due to their low toxicity,ideal bandgap structure,high carrier mobility,and long hot carrier lifetime.Great progress of Sn-based PSCs has been realized in recent years,and the certified efficiency has now reached over 14%.Nevertheless,this record still falls far behind the theoretical calculations.This is likely due to the uncontrolled nucleation states and pronounced Sn(Ⅳ)vacancies.With insights into the methodologies resolving both issues,ligand engineering-assisted perovskite film fabrication dictates the state-of-the-art Sn-based PSCs.Herein,we summarize the role of ligand engineering during each state of film fabrication,ranging from the starting precursors to the ending fabricated bulks.The incorporation of ligands to suppress Sn~(2+)oxidation,passivate bulk defects,optimize crystal orientation,and improve stability is discussed,respectively.Finally,the remained challenges and perspectives toward advancing the performance of Sn-based PSCs are presented.We expect this review can draw a clear roadmap to facilitate Sn-based PSCs via ligand engineering.

Preparation of nanometer perovskite-type oxide La_(0.8)Sr_(0.2)MnO_3 by organic solvent sol-gel method and capability testing

A perovskite-type oxide, La0.8Sr0.2MnO3, was synthesized by the organic solvent sol-gel method. The desired metal cations were chelated in a solution by using citric acid as the chelating agent and absolute ethanol as the solvent. The thermal decomposition of the metal carboxylate precursor gels was studied by thermogravimetric/differential thermal analyzer （TG/DTA） and the products derived from calcining the gels were characterized by X-ray diffraction （XRD） and transmission electronic microscope （TEM）. The polarization curves were acquired on an electrochemical workstation （LK98） and the discharge curves were acquired on a testing instrument of batteries （DC-5）, with a constant current discharge, less than 120 mA/cm^2. The results revealed that the nanometer perovskite-type powder with lesser particle size could be achieved with an organic solvent and had a better catalytic activity.

Sb^(3+)and Sm^(3+)co-doped lead-free Cs_(2)NaInCl_(6)double perovskite nanocrystals for single-component cold white emitter

Metal halide perovskites exhibit promising prospect in light-emitting diodes,solar cells,photodetectors and bioimaging.However,the workhorse of metal halide perovskites relies on toxicity lead element,which severely damages human body and environment.Among lead-free perovskites,Cs_(2)NaInCl_(6)double perovskite is one of the most promising candidates because of its great stability and easy synthesis,but suffers inadequate optical performance.Here,we doped Sb^(3+)and Sm^(3+)into Cs_(2)NaInCl_(6)nanocrystals by a hot injection method.Cs_(2)NaInCl_(6):Sb^(3+)exhibits blue emission at 447 nm.Cs_(2)NaInCl_(6):Sm^(3+),Sb^(3+)nanocrystals simultaneously generate the blue emission of Sb^(3+)and the multiple emissions of Sm^(3+)at 565,602,650 and 710 nm.With the increase of Sm^(3+)feed ratio,the emission color of Cs_(2)NaInCl_(6):Sm^(3+),Sb^(3+)gradually moves to cold white region at(0.27,0.28)in CIE chromaticity diagram and correlated color temperature of 11840 K.This work shows the potential application of Cs_(2)NaInCl_(6):Sm^(3+),Sb^(3+)nanocrystals as a single-component cold white emitter.

Lead-free hybrid two-dimensional double perovskite with switchable dielectric phase transition

Molecular dielectric switches constitute a type of intelligent materials that are highly coveted for their distinctive advantages of switchable dielectric responses,lightweight,and mechanical flexibility.Twodimensional(2D)hybrid perovskites have demonstrated excellent promise for assembling dielectric switches,in which the dynamic motions of organic moieties afford driving force to trigger switchable dielectric phase transition.Here,we successfully assembled a new lead-free hybrid double perovskite,(CHA)4Cu Bi Br8(1,CHA=cyclohexylammonium),adopting a typical 2D structural motif,which shows dielectric anisotropy and bistable behaviors during the reversible phase transition near T_(c)=378 K(the Curie temperature).That is,its dielectric constants could be switched and tuned between high-dielectric and low-dielectric states.Structure analyses reveal that the ordered-disordered transformation of the organic CHA+moiety and distortion of inorganic framework account for its phase transition.This result will stimulate further exploration of molecular dielectric switches in this 2D environmentally friendly family.

Structure design of lead-free chiral-polar perovskites for sensitive self-powered X-ray detection

Metal halide perovskites have made significant progress in X-ray detection owing to their exceptional optoelec-tronic properties.However,most of these materials suffer from toxic element lead and require for high operating voltages.Hence,it is imperative to explore environmentally friendly perovskite crystals without external bias for X-ray detection.Herein,we strategically introduce chiral cations to synthesize a pair of lead-free chiral-polar hybrid perovskites(S-MPz)_(6)Bi_(3)I_(21)·6H_(2)O and(R-MPz)_(6)Bi_(3)I_(21)·6H_(2)O(1S and 1R,S/R-MPz=S/R-2-methylpipera-zinium),which exhibit strong circular dichroism(CD)signals with an anisotropic g-factor reaching approximately 0.017.Significantly,the chiral-polar feature gives rise to distinctive spontaneous polarization,which leads to a photovoltage of 1.1 V under X-ray illumination,endowing self-powered detection capabilities for X-ray.Further exploration of X-ray devices based on 1R single crystal(SC)demonstrates a high sensitivity of 5.2 pC Gy_(air)^(-1)cm^(-2)at zero bias.This study realizes passive X-ray detection depending on the intrinsic spontaneous polarization induced built-in electric field of chiral-polar perovskite,providing an effective approach to the chemical design of desired materials for high-performance"green"self-powered radiation detection.

X-ray-ultraviolet–visible-near-infrared photoresponsesrealized in a lead-free hybrid perovskite ferroelectricthrough light-induced ferro-pyro-phototronic effect

Due to the built-in electric field induced by spontaneous polarization in hybridperovskite (HP) ferroelectrics, the devices based on them exhibit excellent performancein self-powered photodetection. However, most of the self-poweredphotodetector are made of lead-based HP ferroelectrics and have a relativelynarrow photoresponse waveband. Although lead-free HPs solve the problem oflead toxicity, their optoelectronic performance is inferior to that of lead-basedHPs and photoresponse waveband is limited by its optical band gap, whichhinders their further application. To solve this problem, herein, a lead-free HPferroelectric (HDA)BiI5 (HDA is hexane-1,6-diammonium) with large spontaneouspolarization shows an enhanced photocurrent and achieves x-ray-ultraviolet–visible-near-infrared (x-ray-UV–Vis–NIR) photoresponse through theferro-pyro-phototronic (FPP) effect. The ferroelectric, pyroelectric, and photovoltaiccharacteristics coupled together in a single-phase (HDA)BiI5 ferroelectricis an effective way to improve the performance of the devices. What isparticularly attractive is that the FPP effect not only improves the optoelectronicperformance of (HDA)BiI_(5), but also achieves broadband photoresponsesbeyond its optical absorption range. Especially, the current boosting with anexceptional contrast of 1100% and 2400% under 520 and 637 nm, respectively,which is associated with FPP effect. Meanwhile, single crystal self-poweredphotodetector based on (HDA)BiI5 also exhibit significant FPP effects evenunder high-energy x-ray, which owns an outstanding sensitivity of 170.7 μCGy^(-1) cm^(-2) and a lower detection limit of 266 nGy s^(-1) at 0 V bias. Therefore, it is of great significance to study the coupling of multiple physical effects andimprove device performance based on lead-free HP ferroelectrics.

Lead‑Free Perovskite Materials for Solar Cells

The toxicity issue of lead hinders large-scale commercial production and photovoltaic field application of lead halide perovskites.Some novel non-or low-toxic perovskite materials have been explored for development of environmentally friendly lead-free perovskite solar cells(PSCs).This review studies the substitution of equivalent/heterovalent metals for Pb based on first-principles calculation,summarizes the theoretical basis of lead-free perovskites,and screens out some promising lead-free candidates with suitable bandgap,optical,and electrical properties.Then,it reports notable achievements for the experimental studies of lead-free perovskites to date,including the crystal structure and material bandgap for all of lead-free materials and photovoltaic performance and stability for corresponding devices.The review finally discusses challenges facing the successful development and commercialization of lead-free PSCs and predicts the prospect of lead-free PSCs in the future.

The Main Progress of Perovskite Solar Cells in 2020-2021

Perovskite solar cells(PSCs)emerging as a promising photovoltaic technology with high efficiency and low manufacturing cost have attracted the attention from all over the world.Both the efficiency and stability of PSCs have increased steadily in recent years,and the research on reducing lead leakage and developing eco-friendly lead-free perovskites pushes forward the commercialization of PSCs step by step.This review summarizes the main progress of PSCs in 2020 and 2021 from the aspects of efficiency,stability,perovskite-based tandem devices,and lead-free PSCs.Moreover,a brief discussion on the development of PSC modules and its challenges toward practical application is provided.