Enhancing performance of low-temperature processed CsPbI2Br all-inorganic perovskite solar cells using polyethylene oxide-modified TiO_(2)

CsPbX_(3)-based(X=I,Br,Cl)inorganic perovskite solar cells(PSCs)prepared by low-temperature process have attracted much attention because of their low cost and excellent thermal stability.However,the high trap state density and serious charge recombination between low-temperature processed TiO_(2)film and inorganic perovskite layer interface seriously restrict the performance of all-inorganic PSCs.Here a thin polyethylene oxide(PEO)layer is employed to modify TiO_(2)film to passivate traps and promote carrier collection.The impacts of PEO layer on microstructure and photoelectric characteristics of TiO_(2)film and related devices are systematically studied.Characterization results suggest that PEO modification can reduce the surface roughness of TiO_(2)film,decrease its average surface potential,and passivate trap states.At optimal conditions,the champion efficiency of CsPbI_(2)Br PSCs with PEO-modified TiO_(2)(PEO-PSCs)has been improved to 11.24%from 9.03%of reference PSCs.Moreover,the hysteresis behavior and charge recombination have been suppressed in PEO-PSCs.

Efficient and stable planar all-inorganic perovskite solar cells based on high-quality CsPbBr3 films with controllable morphology

All-inorganic cesium lead bromide(CsPbBr3)perovskite is attracting growing interest as functional materials in photovoltaics and other optoelectronic devices due to its superb stability.However,the fabrication of high-quality CsPbBr3 films still remains a big challenge by solution-process because of the low solubility of the cesium precursor in common solvents.Herein,we report a facile solution-processed approach to prepare high-quality CsPbBr3 perovskite films via a two-step spin-coating method,in which the Cs Br methanol/H2 O mixed solvent solution is spin-coated onto the lead bromide films,followed by an isopropanol-assisted post-treatment to regulate the crystallization process and to control the film morphology.In this fashion,dense and uniform CsPbBr3 films are obtained consisting of large crystalline domains with sizes up to microns and low defect density.The effectiveness of the resulting CsPbBr3 films is further examined in perovskite solar cells(PSCs)with a simplified planar architecture of fluorine–doped tin oxide/compact Ti O2/CsPbBr3/carbon,which deliver a maximum power conversion efficiency of 8.11%together with excellent thermal and humidity stability.The present work offers a simple and effective strategy in fabrication of high-quality CsPbBr3 films for efficient and stable PSCs as well as other optoelectronic devices.

Tri-functionalized TiOxCl4-2x accessory layer to boost efficiency of hole-free, all-inorganic perovskite solar cells

Tin dioxide(SnO2) is generally regarded as a promising electron-transporting layer(ETL) for state-of-theart perovskite solar cells(PSCs), however, the ubiquitous oxygen-vacancy-related defects at SnO2 surface and the large energy difference between conduction band of SnO2 and perovskite layer undoubtedly cause severe charge carrier recombination, resulting in sluggish charge extraction efficiency and non-negligible open-circuit voltage(Voc) loss. Herein, a chlorine-containing TiOxCl4-2x accessory layer is fabricated by immersing SnO2 layer into the TiCl4 aqueous solution to passivate the surface oxygen-vacancy-related defects of SnO2 layer and to set an intermediate energy level at ETL/perovskite interface in all-inorganic cesium lead tri-bromine(CsPbBr3) PSCs. Furthermore, the TiOxCl4-2x layer also improves the infiltration of SnO2 layer surface toward perovskite precursor for high-quality perovskite film. Finally, the hole-free, allinorganic CsPbBr3PSC with a structure of FTO/SnO2/TiOxCl4-2x/Cs0.91Rb0.09PbBr3/carbon achieves a champion efficiency of 10.44% with a Vocas high as 1.629 V in comparison to 8.31% for control device. Moreover, the optimized solar cell presents good stability in 80% humidity in air.

Organic additives in all-inorganic perovskite solar cells and modules:from moisture endurance to enhanced efficiency and operational stability

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.

Antimony doped CsPbI_(2)Br for high-stability all-inorganic perovskite solar cells

All-inorganic perovskites,adopting cesium(Cs+)cation to completely replace the organic component of A-sites of hybrid organic–inorganic halide perovskites,have attracted much attention owing to the excellent thermal stability.However,all-inorganic iodine-based perovskites generally exhibit poor phase stability in ambient conditions.Herein,we propose an efficient strategy to introduce antimony(Sb^(3+))into the crystalline lattices of CsPbI_(2)Br perovskite,which can effectively regulate the growth of perovskite crystals to obtain a more stable perovskite phase.Due to the much smaller ionic radius and lower electronegativity of trivalent Sb^(3+)than those of Pb^(2+),the Sb^(3+)doping can decrease surface defects and suppress charge recombination,resulting in longer carrier lifetime and negligible hysteresis.As a result,the all-inorganic perovskite solar cells(PSCs)based on 0.25%Sb^(3+)doped CsPbI_(2)Br light absorber and screen-printable nanocarbon counter electrode achieved a power conversion efficiency of 11.06%,which is 16%higher than that of the control devices without Sb^(3+)doping.Moreover,the Sb^(3+)doped all-inorganic PSCs also exhibited greatly improved endurance against heat and moisture.Due to the use of low-cost and easy-to-process nanocarbon counter electrodes,the manufacturing process of the all-inorganic PSCs is very convenient and highly repeatable,and the manufacturing cost can be greatly reduced.This work offers a promising approach to constructing high-stability all-inorganic PSCs by introducing appropriate lattice doping.

Precursor engineering enables high-performance all-inorganic CsPbIBr_(2) perovskite solar cells with a record efficiency approaching 13%

All-inorganic CsPbIBr_(2) perovskite has attracted widespread attention in photovoltaic and other optoelectronic devices because of its superior thermal stability.However,the deposition of high-quality solutionprocessed CsPbIBr_(2) perovskite films with large thicknesses remains challenging.Here,we develop a triple-component precursor(TCP) by employing lead bromide,lead iodide,and cesium bromide,to replace the most commonly used double-component precursor(DCP) consisting of lead bromide and cesium iodide.Remarkably,the TCP system significantly increases the solution concentration to 1.3 M,leading to a larger film thickness(~390 nm) and enhanced light absorption.The resultant CsPbIBr_(2) films were evaluated in planar n-i-p structured solar cells,which exhibit a considerably higher optimal photocurrent density of 11.50 mA cm^(-2) in comparison to that of DCP-based devices(10.69 mA cm^(-2)).By adopting an organic surface passivator,the maximum device efficiency using TCP is further boosted to a record efficiency of 12.8% for CsPbIBr_(2) perovskite solar cells.

Synchronous defect passivation of all-inorganic perovskite solar cells enabled by fullerene interlayer

All-inorganic CsPbI_(3-x)Br_(x)perovskite solar cells(PSCs)are advantageous in terms of high thermal stability,while its efficiency lags behind those of organic-inorganic hybrid perovskite counterparts.Defect passivations have been extensively applied for enhancing efficiency of all-inorganic PSCs,which are mainly based on univocal defect passivation of perovskite layer.Herein,we incorporated a bis-dimethylamino-functionalized fullerene derivative(abbreviated as PCBDMAM)as an interlayer between ZnO electron transport layer(ETL)and all-inorganic CsPbI_(2.25)Br_(0.75)perovskite layer,accomplishing synchronous defect passivations of both layers and consequently dramatic enhancements of efficiency and thermal stability of PSC devices.Upon spin-coating PCBDMAM onto ZnO ETL,the surface defects of ZnO especially oxygen vacancies can be effectively passivated due to the formation of Zn−N ionic bonds.In addition,PCBDMAM incorporation affords effective passivation of Pb_(I)and I_(Pb)antisite defects within the atop perovskite layer as well via coordination bonding with Pb^(2+).As a result,the regular-structure planar CsPbI_(2.25)Br_(0.75)PSC device delivers a champion power conversion efficiency(PCE)of 17.04%,which surpasses that of the control device(15.44%).Moreover,the PCBDMAM-incorporated PSC device maintains~80%of its initial PCE after 600 h heating at 85°C hot plate in N2 atmosphere,whereas PCE of the control device degrades rapidly to~62%after 460 h heating under identical conditions.Hence,PCBDMAM incorporation benefited dramatic improvement of the thermal stability of PSC device.

Enhanced charge extraction for all-inorganic perovskite solar cells by graphene oxide quantum dots modified TiO_(2)layer

All-inorganic cesium lead bromide(CsPbBr_(3))perovskite solar cells have been attracting growing interest due to superior performance stability and low cost.However,low light absorbance and large charge recombination at TiO_(2)/CsPbBr_(3)interface or within CsPbBr_(3)film still prevent further performance improvement.Herein,we report devices with high power conversion efficiency(9.16%)by introducing graphene oxide quantum dots(GOQDs)between TiO_(2)and perovskite layers.The recombination of interfacial radiation can be effectively restrained due to enhanced charge transfer capability.GOQDs with C-rich active sites can involve in crystallization and fill within the CsPbBr_(3)perovskite film as functional semiconductor additives.This work provides a promising strategy to optimize the crystallization process and boost charge extraction at the surface/interface optoelectronic properties of perovskites for high efficient and low-cost solar cells.

A short overview of the lead iodide residue impact and regulation strategies in perovskite solar cells

Lead iodide(PbI2) is a vital raw material for preparing perovskite solar cells(PSCs),and it not only takes part in forming the light absorption layer but also remains in the grain boundary as a passivator.In other words,the PbI2 content in the precursor and as formed film will affect the efficiency and stability of the PSCs.With moderate residual PbI2,it passivates the bulk/surface defects of perovskite,reduces the interfacial recombination,promotes the perovskite stability,minimizes the device hysteresis,and so on.Deficient PbI2 residue will reduce the interfacial passivation effect and device performance.In addition to facilitating the non-radiative recombination,over PbI2 residue can also lead to electronic insulation in the grain boundary and deteriorate the device performance.However,the impact and regulation of PbI2 residue on the device performance and stability is still not fully understood.Herein,a comprehensive and detailed review is presented by discussing the PbI2 residue impact and its regulation strategies(i.e., elimination,facilitation and conversion of the residue PbI2) to manipulate the PbI2 content,distribution and forms.Finally,we also show future outlooks in this field,with an aim to help further the progression of high-efficiency and stable PSCs.

Stabilizing perovskite precursors with the reductive natural amino acid for printable mesoscopic perovskite solar cells

Solution processability significantly advances the development of highly-efficient perovskite solar cells.However,the precursor solution tends to undergo irreversible degradation reactions,impairing the device performance and reproducibility.Here,we utilize a reductive natural amino acid,Nacetylcysteine(NALC),to stabilize the precursor solution for printable carbon-based hole-conductorfree mesoscopic perovskite solar cells.We find that I_(2) can be generated in the aged solution containing methylammonium iodide(MI) in an inert atmosphere and speed up the MA-FA^(+)(formamidinium) reaction which produces large-size cations and hinders the formation of perovskite phase.NALC effectively stabilizes the precursor via its sulfhydryl group which reduces I_(2) back to I^(-)and provides H^(+).The NALC-stabilized precursor which is aged for 1440 h leads to devices with a power conversion efficiency equivalent to 98% of that for devices prepared with the fresh precursor.Furthermore,NALC improves the device power conversion efficiency from 16.16% to 18.41% along with enhanced stability under atmospheric conditions by modifying grain boundaries in perovskite films and reducing associated defects.

Modeling the performance of perovskite solar cells with inserting porous insulating alumina nanoplates

Peng et al.[Science 379683(2023)]reported an effective method to improve the performance of perovskite solar cells by using thicker porous insulator contact(PIC)-alumina nanoplates.This method overcomes the trade-off between the open-circuit voltage and the fill factor through two mechanisms:reduced surface recombination velocity and increased bulk recombination lifetime due to better perovskite crystallinity.From arguments of drift-diffusion simulations,we find that an increase in mobility and carrier recombination lifetime in bulk are the key factors for minimizing the resistance-effect from thicker PICs and achieving a maximum power conversion efficiency(PCE)at approximately 25%reduced contact area.Furthermore,the partially replacement of perovskite films with thicker PICs would result in a reduction in short-current density,but the relative low refractive index of the PICs imbedded into the high refractive index perovskite creates light trapping structures that compensate for this loss.

Defect mediated losses and degradation of perovskite solar cells:Origin impacts and reliable characterization techniques

The rapid advancement of halide-based hybrid perovskite materials has garnered significant research attention,particularly in the domain of photovoltaic technology.Owing to their exceptional optoelec-tronic properties,they demonstrated power conversion efficiency(PcE)of over 25%in single junction solar cells.Despite the notable progress in PCE over the past decade,the inherent high defect density pre-senting in perovskite materials gives rise to several loss mechanisms and associated ion migration in per-ovskite solar cells(PsCs)during operational conditions.These factors collectively contribute to a significant stability challenge in PsCs,placing their longevity far behind for commercialization.While numerous reports have explored defects,ion migration,and their impacts on device performance,a com-prehensive correlation between the types of defects and the degradation kinetics of perovskite materials and PsCs has been lacking.In this context,this review aims to provide a comprehensive overview of the origins of defects and ion migration,emphasizing their correlation with the degradation kinetics of per-ovskite materials and PsCs,leveraging reliable characterization techniques.Furthermore,these charac-terization techniques are intended to comprehend loss mechanisms by different passivation approaches to enhance the durability and PCE of PSCs.

Surface-functionalized hole-selective monolayer for high efficiency single-junction wide-bandgap and monolithic tandem perovskite solar cells

Carbazole moiety-based 2PACz([2-(9H-carbazol-9-yl)ethyl]phosphonic acid)self-assembled monolayers(SAMs)are excellent hole-selective contact(HSC)materials with abilities to excel the charge-transferdynamics of perovskite solar cells(PSCs).Herein,we report a facile but powerful method to functionalize the surface of 2PACz-SAM,by which reproducible,highly stable,high-efficiency wide-bandgap PSCs can be obtained.The 2PACz surface treatment with various donor number solvents improves assembly of 2PACz-SAM and leave residual surface-bound solvent molecules on 2PACz-SAM,which increases perovskite grain size,retards halide segregation,and accelerates hole extraction.The surface functionalization achieves a high power conversion efficiency(PCE)of 17.62%for a single-junction wide-bandgap(~1.77 e V)PSC.We also demonstrate a monolithic all-perovskite tandem solar cell using surfaceengineered HSC,showing high PCE of 24.66%with large open-circuit voltage of 2.008 V and high fillfactor of 81.45%.Our results suggest this simple approach can further improve the tandem device,when coupled with a high-performance narrow-bandgap sub-cell.

Boosting MA-based two-dimensional Ruddlesden-Popper perovskite solar cells by incorporating a binary spacer

Two-dimensional Ruddlesden-Popper(2DRP)perovskite exhibits excellent stability in perovskite solar cells(PSCs)due to introducing hydrophobic long-chain organic spacers.However,the poor charge transporting property of bulky organic cation spacers limits the performance of 2DRP PSCs.Inspired by the Asite cation alloying strategy in 3D perovskites,2DRP perovskites with a binary spacer can promote charge transporting compared to the unary spacer counterparts.Herein,the superior MA-based 2DRP perovskite films with a binary spacer,including 3-guanidinopropanoic acid(GPA)and 4-fluorophenethylamine(FPEA)are realized.These films(GPA_(0.85)FPEA_(0.15))_(2)MA_(4)Pb_5I_(16)show good morphology,large grain size,decreased trap state density,and preferential orientation of the as-prepared film.Accordingly,the present 2DRP-based PSC with the binary spacer achieves a remarkable efficiency of 18.37%with a V_(OC)of1.15 V,a J_(SC)of 20.13 mA cm^(-2),and an FF of 79.23%.To our knowledge,the PCE value should be the highest for binary spacer MA-based 2DRP(n≤5)PSCs to date.Importantly,owing to the hydrophobic fluorine group of FPEA and the enhanced interlayer interaction by FPEA,the unencapsulated 2DRP PSCs based on binary spacers exhibit much excellent humidity stability and thermal stability than the unary spacer counterparts.

Dimethylamine oxalate manipulating CsPbI_(3) perovskite film crystallization process for high efficiency carbon electrode based perovskite solar cells

Crystallization process determines the quality of perovskite films and the performances of resultant perovskite solar cells(PSCs).Dimethylamine oxalate has been proven as a multifunctional modulator,and is explored as an efficient additive in manipulating the crystallization process of CsPbI_(3) perovskite films.On one hand,oxalate serves as the precipitator that facilitates the nucleation process of intermediate.The larger size of intermediate is conductive to the larger size and smaller grain boundaries of resultant perovskite.On the other hand,in subsequent annealing process,the phase conversion and growth process of transient perovskite can be decelerated due to the strong interactions of oxalate with both dimethylamine cation(DMA^(+))and Pb^(2+).Due to the optimized crystallization kinetics,the morphology and quality of CsPbI_(3) perovskite films are comprehensively improved with lower defect concentrations,and charge recombination loss is effectively suppressed.Benefiting from the optimized crystal quality of perovskite films,the carbon electrode-based CsPbI_(3) PSCs exhibit a champion efficiency of 18.48%.This represents one of the highest levels among all hole transport layer-free inorganic perovskite solar cells.

Manipulating Crystal Growth and Secondary Phase PbI_(2)to Enable Efficient and Stable Perovskite Solar Cells with Natural Additives

In perovskite solar cells(PSCs),the inherent defects of perovskite film and the random distribution of excess lead iodide(PbI_(2))prevent the improvement of efficiency and stability.Herein,natural cellulose is used as the raw material to design a series of cellulose derivatives for perovskite crystallization engineering.The cationic cellulose derivative C-Im-CN with cyano-imidazolium(Im-CN)cation and chloride anion prominently promotes the crystallization process,grain growth,and directional orientation of perovskite.Meanwhile,excess PbI_(2)is transferred to the surface of perovskite grains or formed plate-like crystallites in local domains.These effects result in suppressing defect formation,decreasing grain boundaries,enhancing carrier extraction,inhibiting non-radiative recombination,and dramatically prolonging carrier lifetimes.Thus,the PSCs exhibit a high power conversion efficiency of 24.71%.Moreover,C-Im-CN has multiple interaction sites and polymer skeleton,so the unencapsulated PSCs maintain above 91.3%of their initial efficiencies after 3000 h of continuous operation in a conventional air atmosphere and have good stability under high humidity conditions.The utilization of biopolymers with excellent structure-designability to manage the perovskite opens a state-of-the-art avenue for manufacturing and improving PSCs.

High performance wide bandgap perovskite solar cell with low V_(OC) deficit less than 0.4 V

Wide bandgap perovskite solar cells(PSCs)have attracted significant attention because they can be applied to the top cells of tandem solar cells.However,high open-circuit voltage(V_(OC))deficit(>0.4 V)result from poor crystallization and high non-radiative recombination losses become a serious limitation in the pursuit of high performance.Here,the relevance between different Pbl_(2)proportions and performance parameters are revealed through analysis of surface morphology,residual stress,and photostability.The increase of Pbl_(2)proportion promotes crystal growth and reduces the work function of the perovskite film surface and promotes the energy level alignment with the carrier transport layer,which decreased the V_(OC)deficit.However,residual PbI_(2)exacerbated the stress level of perovskite film,and the resulting lattice disorder deteriorated the photostability of the device.Ultimately,after the synergistic passivation of residual PbI_(2)and PEAI,the V_(OC)achieves 1.266 V and V_(OC)deficit is less than 0.4 V,the record value in wide bandgap PSCs.

Interfacial modification using the cross-linkable tannic acid for highly-efficient perovskite solar cells with excellent stability

Although the performance of perovskite solar cells(PSCs)has been dramatically increased in recent years,stability is still the main obstacle preventing the PSCs from being commercial.PSC device instability can be caused by a variety of reasons,including ions diffusion,surface and grain boundary defects,etc.In this work,the cross-linkable tannic acid(TA)is introduced to modify perovskite film through post-treatment method.The numerous organic functional groups(–OH and C=O)in TA can interact with the uncoordinated Pb^(2+)and I^(-)ions in perovskite,thus passivating defects and inhibiting ions diffusion.In addition,the formed TA network can absorb a small amount of the residual moisture inside the device to protect the perovskite layer.Furthermore,TA modification regulates the energy level of perovskite,and reduces interfacial charge recombination.Ultimately,following TA treatment,the device efficiency is increased significantly from 21.31%to 23.11%,with a decreased hysteresis effect.Notably,the treated device shows excellent air,thermal,and operational stability.In light of this,the readily available,inexpensive TA has the potential to operate as a multipurpose interfacial modifier to increase device efficiency while also enhancing device stability.

Multifunctional interfacial molecular bridge enabled by an aggregation-induced emission strategy for enhancing efficiency and UV stability of perovskite solar cells

The interface defects between the electron transport layer(ETL)and the perovskite layer,as well as the low ultraviolet(UV)light utilization rate of the perovskite absorption layer,pose significant challenges for the commercialization of perovskite solar cells(PSCs).To address this issue,this paper proposes an innovative multifunctional interface modulation strategy by introducing aggregation-induced emission(AIE)molecule 5-[4-[1,2,2-tri[4-(3,5-dicarboxyphenyl)phenyl]ethylene]phenyl]benzene-1,3-dicarboxylic acid(H_(8)ETTB)at the SnO_(2)ETL/perovskite interface.Firstly,the interaction of H_(8)ETTB with the SnO_(2)surface,facilitated by its carboxyl groups,is effective in passivating surface defects caused by noncoord inated Sn and O vacancies.This interaction enhances the conductivity of the SnO_(2)film and adjusts energy levels,leading to enhanced charge carrier transport.Simultaneously,H_(8)ETTB can passivate noncoord inated Pb^(2+)ions at the perovskite interface,promoting perovskite crystallization and reducing the interface energy barrier,resulting in a perovskite film with low defects and high crystalline quality.More importantly,the H_(8)ETTB molecule,can convert UV light into light absorbable by the perovskite,thereby reducing damage caused by UV light and improving the device's utilization of UV.Consequently,the champion PSC based on SnO_(2)-H_(8)ETTB achieves an impressing efficiency of 23.32%and significantly improved photostability compared with the control device after continuous exposure to intense UV radiation.In addition,the Cs_(0.05)(FA_(0.95)MA_(0.05))_(0.95)Pb(I_(0.95)Br_(0.05))_(3)based device can achieve maximum efficiency of 24.01%,demonstrating the effectiveness and universality of this strategy.Overall,this innovative interface bridging strategy effectively tackles interface defects and low UV light utilization in PSCs,presenting a promising approach for achieving highly efficient and stable PSCs.

Minimizing interfacial energy losses in inverted perovskite solar cells by a dipolar stereochemical 2D perovskite interface

Inverted perovskite solar cells(PSCs) have attracted broad research and industrial interest owing to their suppressed hysteresis,cost-effectiveness,and easy-fabrication.However,the issue of non-radiative recombination losses at the n-type interface between the perovskite and fullerene has impeded further improvement of photovoltaic performance.Here,we modify the n-type interface of FAPbI_(3) perovskite films by constructing a stereochemical two-dimensional(2D) perovskite interlayer,in which the organic cations comprise both pyridine and ammonium groups.The pyridine N donor can create stable bonding with the surface-uncoordinated Pb on the perovskite,thereby passivating the shallow-level defects and enhancing the air stability of the film.Furthermore,the pyridine N donor also offers a positive polar interface to decrease the surface work function of the perovskite film,enabling n-type modification.Ultimately,we employ a p-i-n photovoltaic(PV) device with the positive dipole interlayer at perovskite/fullerene contact and achieve remarkable photoelectric conversion efficiency(PCE) of 22.0%.