Role of self-assembled molecules’anchoring groups for surface defect passivation and dipole modulation in inverted perovskite solar cells

Inverted perovskite solar cells have gained prominence in industrial advancement due to their easy fabrication,low hysteresis effects,and high stability.Despite these advantages,their efficiency is currently limited by excessive defects and poor carrier transport at the perovskite-electrode interface,particularly at the buried interface between the perovskite and transparent conductive oxide(TCO).Recent efforts in the perovskite community have focused on designing novel self-assembled molecules(SAMs)to improve the quality of the buried interface.However,a notable gap remains in understanding the regulation of atomic-scale interfacial properties of SAMs between the perovskite and TCO interfaces.This understanding is crucial,particularly in terms of identifying chemically active anchoring groups.In this study,we used the star SAM([2-(9H-carbazol-9-yl)ethyl]phosphonic acid)as the base structure to investigate the defect passivation effects of eight common anchoring groups at the perovskite-TCO interface.Our findings indicate that the phosphonic and boric acid groups exhibit notable advantages.These groups fulfill three key criteria:they provide the greatest potential for defect passivation,exhibit stable adsorption with defects,and exert significant regulatory effects on interface dipoles.Ionized anchoring groups exhibit enhanced passivation capabilities for defect energy levels due to their superior Lewis base properties,which effectively neutralize local charges near defects.Among various defect types,iodine vacancies are the easiest to passivate,whereas iodine-substituted lead defects are the most challenging to passivate.Our study provides comprehensive theoretical insights and inspiration for the design of anchoring groups in SAMs,contributing to the ongoing development of more efficient inverted perovskite solar cells.

Fast and Balanced Charge Transport Enabled by Solution-Processed Metal Oxide Layers for Efficient and Stable Inverted Perovskite Solar Cells

Metal oxide charge transport materials are preferable for realizing long-term stable and potentially low-cost perovskite solar cells(PSCs).However,due to some technical difficulties(e.g.,intricate fabrication protocols,high-temperature heating process,incompatible solvents,etc.),it is still challenging to achieve efficient and reliable all-metal-oxide-based devices.Here,we developed efficient inverted PSCs(IPSCs)based on solution-processed nickel oxide(NiO_(x))and tin oxide(SnO_(2))nanoparticles,working as hole and electron transport materials respectively,enabling a fast and balanced charge transfer for photogenerated charge carriers.Through further understanding and optimizing the perovskite/metal oxide interfaces,we have realized an outstanding power conversion efficiency(PCE)of 23.5%(the bandgap of the perovskite is 1.62 eV),which is the highest efficiency among IPSCs based on all-metal-oxide charge transport materials.Thanks to these stable metal oxides and improved interface properties,ambient stability(retaining 95%of initial PCE after 1 month),thermal stability(retaining 80%of initial PCE after 2 weeks)and light stability(retaining 90%of initial PCE after 1000 hours aging)of resultant devices are enhanced significantly.In addition,owing to the low-temperature fabrication procedures of the entire device,we have obtained a PCE of over 21%for flexible IPSCs with enhanced operational stability.

Chlorine-Substituent Regulation in Dopant-Free Small-Molecule Hole-Transport Materials Improves the Effi ciency and Stability of Inverted Perovskite Solar Cells

Although doped hole-transport materials(HTMs)off er an effi ciency benefi t for perovskite solar cells(PSCs),they inevi-tably diminish the stability.Here,we describe the use of various chlorinated small molecules,specifi cally fl uorenone-triphenylamine(FO-TPA)-x-Cl[x=para,meta,and ortho(p,m,and o)],with diff erent chlorine-substituent positions,as dopant-free HTMs for PSCs.These chlorinated molecules feature a symmetrical donor-acceptor-donor structure and ideal intramolecular charge transfer properties,allowing for self-doping and the establishment of built-in potentials for improving charge extraction.Highly effi cient hole-transfer interfaces are constructed between perovskites and these HTMs by strategi-cally modifying the chlorine substitution.Thus,the chlorinated HTM-derived inverted PSCs exhibited superior effi ciencies and air stabilities.Importantly,the dopant-free HTM FO-TPA-o-Cl not only attains a power conversion effi ciency of 20.82% but also demonstrates exceptional stability,retaining 93.8%of its initial effi ciency even after a 30-day aging test conducted under ambient air conditions in PSCs without encapsulation.These fi ndings underscore the critical role of chlorine-substituent regulation in HTMs in ensuring the formation and maintenance of effi cient and stable PSCs.

High-Performance and Large-Area Inverted Perovskite Solar Cells Based on NiO_(x) Films Enabled with A Novel Microstructure-Control Technology

The improvement in the efficiency of inverted perovskite solar cells(PSCs)is significantly limited by undesirable contact at the NiO_(x)/perovskite interface.In this study,a novel microstructure-control technology is proposed for fabrication of porous NiO_(x)films using Pluronic P123 as the structure-directing agent and acetylacetone(AcAc)as the coordination agent.The synthesized porous NiO_(x)films enhanced the hole extraction efficiency and reduced recombination defects at the NiO_(x)/perovskite interface.Consequently,without any modification,the power conversion efficiency(PCE)of the PSC with MAPbl_(3)as the absorber layer improved from 16.50%to 19.08%.Moreover,the PCE of the device composed of perovskite Cs0.05(MA_(0.15)FA_(0.85))_(0.95)Pb(I_(0.85)Br_(0.15))_(3)improved from 17.49%to 21.42%.Furthermore,the application of the fabricated porous NiO_(x)on fluorine-doped tin oxide(FTO)substrates enabled the fabrication of large-area PSCs(1.2 cm^(2))with a PCE of 19.63%.This study provides a novel strategy for improving the contact at the NiO_(x)/perovskite interface for the fabrication of high-performance large-area perovskite solar cells.

Thermally Evaporated ZnSe for Efficient and Stable Regular/Inverted Perovskite Solar Cells by Enhanced Electron Extraction

Electron transport layers(ETLs)are crucial for achieving efficient and stable planar perovskite solar cells(PSCs).Reports on versatile inorganic ETLs using a simple film fabrication method and applicability for both low-cost planar regular and inverted PSCs with excellent efficiencies(>22%)and high stability are very limited.Herein,we employ a novel inorganic ZnSe as ETL for both regular and inverted PSCs to improve the efficiency and stability using a simple thermal evaporation method.The TiO_(2)-ZnSe-FAPbl_(3)heterojunction could be formed,resulting in an improved charge collection and a decreased carrier recombination further proved through theoretical calculations.The optimized regular PSCs based on TiO_(2)/ZnSe have achieved 23.25%efficiency with negligible hysteresis.In addition,the ZnSe ETL can also effectively replace the unstable bathocuproine(BCP)in inverted PSCs.Consequently,the ZnSe-based inverted device realizes a champion efficiency of 22.54%.Moreover,the regular device comprising the TiO_(2)/ZnSe layers retains 92%of its initial PCE after 10:00 h under 1 Sun continuous illumination and the inverted device comprising the C_(60)/ZnSe layers maintains over 85%of its initial PCE at 85℃for 10:00 h.This highlights one of the best results among universal ETLs in both regular and inverted perovskite photovoltaics.

Ecofriendly Hydroxyalkyl Cellulose Additives for Efficient and Stable MAPbI_(3)-Based Inverted Perovskite Solar Cells

Perovskite solar cells(PSCs)have been demonstrated to be one of the most promising technologies in the field of renewable energy.However,the presence of the defects in the perovskite films greatly limits the efficiency and the stability of the PSCs.The additive engineering is one of the most effective approaches to overcome this problem.Most of the successful additives are extracted from the petroleum-based materials,while the research on the biomass-based additives is still lagging behind.In this paper,two ecofriendly hydroxyalkyl cellulose additives,i.e.,hydroxyethyl cellulose(HEC)and hydroxylpropyl cellulose(HPC),are investigated on the performance of the MAPbl_(3)-based inverted PSCs.Due to the strong interaction between the hydroxyl groups of the cellulose and the divalent cations of the perovskite,these additives enhance the crystal grain orientation and significantly repair the defects of the perovskite films.Working as the additives,these two cellulose derivatives show a strong passivation ability,which significantly reduces the trap density and improves the optoelectronic feature of the PSCs.Compared with the average power conversion efficiency(PCE)of the control device(19.19%),an enhancement of~10%is achieved after the addition of HEC.The optimized device(PCE=21.25%)with a long-term stability(10:80 h,PCE=20.93%)is achieved by the incorporation of the HEC additives into the precursor solution.It is the best performance among the PSCs with the cellulose additives up to now.This research provides a novel choice to develop a cost-effective and renewable additive for the PSCs with high efficiency and excellent long-term stability.

Hole‑Transport Management Enables 23%‑Efficient and Stable Inverted Perovskite Solar Cells with 84%Fill Factor

NiO_(x)-based inverted perovskite solar cells(PSCs)havepresented great potential toward low-cost,highly efficient and stablenext-generation photovoltaics.However,the presence of energy-levelmismatch and contact-interface defects between hole-selective contacts(HSCs)and perovskite-active layer(PAL)still limits device efficiencyimprovement.Here,we report a graded configuration based on bothinterface-cascaded structures and p-type molecule-doped compositeswith two-/three-dimensional formamidinium-based triple-halideperovskites.We find that the interface defects-induced non-radiativerecombination presented at HSCs/PAL interfaces is remarkably suppressedbecause of efficient hole extraction and transport.Moreover,astrong chemical interaction,halogen bonding and coordination bondingare found in the molecule-doped perovskite composites,whichsignificantly suppress the formation of halide vacancy and parasitic metallic lead.As a result,NiO_(x)-based inverted PSCs present a power-conversion-efficiency over 23%with a high fill factor of 0.84 and open-circuit voltage of 1.162 V,which are comparable to the best reported around 1.56-electron volt bandgap perovskites.Furthermore,devices with encapsulation present high operational stability over 1,200 h during T_(90) lifetime measurement(the time as a function of PCE decreases to 90%of its initial value)under 1-sun illumination in ambient-air conditions.

Tin dioxide buffer layer-assisted efficiency and stability of wide-bandgap inverted perovskite solar cells

Inverted perovskite solar cells(IPSCs) have attracted tremendous research interest in recent years due to their applications in perovskite/silicon tandem solar cells. However, further performance improvements and long-term stability issues are the main obstacles that deeply hinder the development of devices. Herein, we demonstrate a facile atomic layer deposition(ALD) processed tin dioxide(SnO2) as an additional buffer layer for efficient and stable wide-bandgap IPSCs. The additional buffer layer increases the shunt resistance and reduces the reverse current saturation density, resulting in the enhancement of efficiency from 19.23% to 21.13%. The target device with a bandgap of 1.63 eV obtains open-circuit voltage of 1.19 V, short circuit current density of 21.86 mA/cm^(2), and fill factor of 81.07%. More importantly, the compact and stable SnO_(2) film invests the IPSCs with superhydrophobicity, thus significantly enhancing the moisture resistance. Eventually, the target device can maintain 90% of its initial efficiency after 600 h storage in ambient conditions with relative humidity of 20%–40% without encapsulation. The ALD-processed SnO_(2) provides a promising way to boost the efficiency and stability of IPSCs, and a great potential for perovskite-based tandem solar cells in the near future.

Multiple methoxy-substituted hole transporter for inverted perovskite solar cells

Inverted organic-inorganic hybrid perovskite solar cells(i-PSC)with low temperature processed interlayers and weak hysteresis behaviors have shown great potential for commercialization[1-5].However,their relatively lower power conversion efficiency(PCE)and inferior reproducibility than conventional PSCs limit further developments.These problems are largely determined by the hole transporting layer(HTL)and the quality of the upper perovskite film[6-8];in particular,the latter is considerably influenced by the surface property of the underlying HTL.

Recent advances of interface engineering in inverted perovskite solar cells

Perovskite solar cells(PSCs)have witnessed great achievement in the past decade.Most of previous researches focus on the n-i-p structure of PSCs with ultra-high efficiency.While the n-i-p devices usually used the unstable charge transport layers,such as the hygroscopic doped spiro-OMe TAD,which affect the long-term stability.The inverted device with the p-i-n structure owns better stability when using stable undoped organic molecular or metal oxide materials.There are significant progresses in inverted PSCs,most of them related to charge transport or interface engineering.In this review,we will mainly summarize the inverted PSCs progresses related to the interface engineering.After that,we prospect the future direction on inverted PSCs.

Non-destructive buffer enabling near-infrared-transparent inverted inorganic perovskite solar cells toward 1400 h light-soaking stable perovskite/Cu(In,Ga)Se_(2) tandem solar cells

Near-infrared(NIR)transparent inverted all-inorganic perovskite solar cells(PSCs)are excellent top cell candidates in tandem applications.An essential challenge is the replacement of metal contacts with transparent conductive oxide(TCO)electrodes,which requires the introduction of a buffer layer to prevent sputtering damage.In this study,we show that the conventional buffers(i.e.,small organic molecules and atomic layer deposited metal oxides)used for organic-inorganic hybrid perovskites are not applicable to all-inorganic perovskites,due to non-uniform coverage of the vulnerable layers underneath,deterioration upon ion bombardment and moisture induced perovskite phase transition,A thin film of metal oxide nanoparticles by the spin-coating method serves as a non-destructive buffer layer for inorganic PSCs.All-inorganic inverted near-infrared-transparent PSCs deliver a PCE of 17.46%and an average transmittance of 73.7%between 780 and 1200 nm.In combination with an 18.56%Cu(In,Ga)Se_(2) bottom cell,we further demonstrate the first all-inorganic perovskite/CIGS 4-T tandem solar cell with a PCE of 24.75%,which exhibits excellent illumination stability by maintaining 86.7%of its initial efficiency after 1400 h.The non-destructive buffer lays the foundation for efficient and stable NIR-transparent inverted inorganic perovskite solar cells and perovskite-based tandems.

Efficient and Stable Inverted Perovskite Solar Modules Enabled by Solid-Liquid Two-Step Film Formation

A considerable efficiency gap exists between large-area perovskite solar modules and small-area perovskite solar cells.The control of forming uniform and large-area film and perovskite crystallization is still the main obstacle restricting the efficiency of PSMs.In this work,we adopted a solid-liquid two-step film formation technique,which involved the evaporation of a lead iodide film and blade coating of an organic ammonium halide solution to prepare perovskite films.This method possesses the advantages of integrating vapor deposition and solution methods,which could apply to substrates with different roughness and avoid using toxic solvents to achieve a more uniform,large-area perovskite film.Furthermore,modification of the NiO_(x)/perovskite buried interface and introduction of Urea additives were utilized to reduce interface recombination and regulate perovskite crystallization.As a result,a large-area perovskite film possessing larger grains,fewer pinholes,and reduced defects could be achieved.The inverted PSM with an active area of 61.56 cm^(2)(10×10 cm^(2)substrate)achieved a champion power conversion efficiency of 20.56%and significantly improved stability.This method suggests an innovative approach to resolving the uniformity issue associated with large-area film fabrication.

Multifunctional anchoring of O-ligands for high-performance and stable inverted perovskite solar cells

Functional additives have recently been regarded as emerging candidates to improve the performance and stability of perovskite solar cells(PSCs).Herein,nicotinamide(N),2-chloronicotinamide(2Cl),and 6-chloronicotinamide(6Cl)were employed as O-ligands to facilitate the deposition of MAPbI_(3)(MA=methylammonium)and MA-free FA_(0.88)Cs_(0.12)PbI_(2.64)Br_(0.36)(FA=formamidinium)perovskite films by multifunctional anchoring.By density functional theory(DFT)calculations and ultraviolet photoelectron spectroscopy(UPS)measurements,it is identified that the highest occupied molecular orbital(HOMO)level for additive modified MAPbI_(3)perovskite could reduce the voltage deficit for hole extraction.Moreover,due to the most favorable charge distribution and significant improvements in charge mobility and defect passivation,the power conversion efficiency(PCE)of 2Cl-MAPbI_(3)PSCs was significantly improved from 19.32%to 21.12%.More importantly,the two-dimensional grazing-incidence wide-angle X-ray scattering(GIWAXS)analysis showed that PbI_(2) defects were effectively suppressed and femtosecond transient absorption(TA)spectroscopy demonstrated that the trap-assisted recombination at grain boundaries was effectively inhibited in the 2Cl-MA-free film.As a result,the thermally stable 2Cl-MA-free PSCs achieved a remarkable PCE of 23.13%with an open-circuit voltage(V_(oc))of 1.164 V and an ultrahigh fill factor(FF)of 85.7%.Our work offers a practical strategy for further commercializing stable and efficient PSCs.

Recent progress of inverted organic-inorganic halide perovskite solar cells

In recent years,inverted perovskite solar cells(IPSCs)have attracted significant attention due to their low-temperature and cost-effective fabrication processes,hysteresis-free properties,excellent stability,and wide application.The efficiency gap between IPSCs and regular structures has shrunk to less than 1%.Over the past few years,IPSC research has mainly focused on optimizing power conversion efficiency to accelerate the development of IPSCs.This review provides an overview of recent improvements in the efficiency of IPSCs,including interface engineering and novel film production techniques to overcome critical obstacles.Tandem and integrated applications of IPSCs are also summarized.Furthermore,prospects for further development of IPSCs are discussed,including the development of new materials,methods,and device structures for novel IPSCs to meet the requirements of commercialization.

Electrodeposited transparent PEDOT for inverted perovskite solar cells:improved charge transport and catalytic performances

The acidic, corrosive effect of sodium polystyrene sulfonate(PSS) in poly 3,4-ethylenedioxythiophene:sodium polystyrene sulfonate(PEDOT:PSS) limits the stability of inverted perovskite solar cells(PSCs) based on the ITO/PEDOT:PSS/perovskite/PCBM/BCP/Ag structure. In this work, a poly 3,4-ethylenedioxythiophene(PEDOT) hole transport layer(HTL) with high hole mobility and good catalytic performance was prepared by electrochemical cyclic voltammetry(CV) method for inverted PSCs. By controlling the CV cycles(from 1 to 5 cycles) and EDOT monomer solution concentration(from0.5 to 2.0 mmol·L^(-1)) of electrochemical deposition, the thickness, morphology, optical and electrochemical properties of PEDOT could be accurately adjusted. The optimal photovoltaic performance with current density(J_(sc)) of 22.19 mA·cm^(-2), open circuit voltage(V_(oc)) of 0.94 V, fill factor(FF) of 0.65 and photoelectric conversion efficiency of 13.56% was obtained when deposition of PEDOT with 1 CV cycle and EDOT concentration of 0.5 mmol·L^(-1). At this point, the perovskite showed good crystallization,optimal optical, charge transport and recombination performance, resulting in better V_(oc)and photoelectric conversion efficiency(PCE) compared to the devices with higher CV cycle numbers and 3,4-ethylenedioxythiophene(EDOT) concentration. For comparison with spin-coated PEDOT:PSS, the device with electrodeposited PEDOT showed improved J_(sc)and comparable V_(oc), which may result from its better charge transport and catalytic ability.The device with spin-coated PEDOT:PSS showed photoelectric conversion efficiency of 12.25%, which was lower than that based on electrodeposited PEDOT(13.56%) with1 CV cycles and 0.5 mmol·L^(-1) EDOT concentration. And the device with electrodeposited PEDOT as HTLs showed more excellent air stability. In ambient air((32 ± 5) ℃ and RH: 70% ± 20%), it still maintained more than 80%of the initial photoelectric conversion efficiency after1000 h. In comparison, the photoelectric conversion efficiency of the device with PEDOT:PSS decreased to 20% of the initial value after storage for 500 h. From this study, a facial and low-cost way to prepare PEDOT HTL with high performances that better than the traditional PEDOT:PSS has been explored, which is expected to eliminate the acidic, corrosive effect of PSS in PEDOT:PSS.

Interfacial stabilization for inverted perovskite solar cells with long-term stability

Perovskite solar cells(PSCs)commonly exhibit significant performance degradation due to ion migration through the top charge transport layer and ultimately metal electrode corrosion.Here,we demonstrate an interfacial management strategy using a boron chloride subphthalocyanine(Cl_(6)SubPc)/fullerene electron-transport layer,which not only passivates the interfacial defects in the perovskite,but also suppresses halide diffusion as evidenced by multiple techniques,including visual element mapping by electron energy loss spectroscopy.As a result,we obtain inverted PSCs with an efficiency of 22.0%(21.3%certified),shelf life of 7000 h,T_(80) of 816 h under damp heat stress(compared to less than 20 h without Cl_(6)SubPc),and initial performance retention of 98%after 2000 h at 80℃in inert environment,90%after 2034 h of illumination and maximum power point tracking in ambient for encapsulated devices and 95%after 1272 h outdoor testing ISOS-O-1.Our strategy and results pave a new way to move PSCs forward to their potential commercialization solidly.

Recent advances in developing high‑performance organic hole transporting materials for inverted perovskite solar cells

Inverted perovskite solar cells(PVSCs)have recently made exciting progress,showing high power conversion efciencies(PCEs)of 25%in single-junction devices and 30.5%in silicon/perovskite tandem devices.The hole transporting material(HTM)in an inverted PVSC plays an important role in determining the device performance,since it not only extracts/transports holes but also afects the growth and crystallization of perovskite flm.Currently,polymer and self-assembled monolayer(SAM)have been considered as two types of most promising HTM candidates for inverted PVSCs owing to their high PCEs,high stability and adaptability to large area devices.In this review,recent encouraging progress of high-performance polymer and SAM-based HTMs is systematically reviewed and summarized,including molecular design strategies and the correlation between molecular structure and device performance.We hope this review can inspire further innovative development of HTMs for wide applications in highly efcient and stable inverted PVSCs and the tandem devices.

Effective Surface Treatment for High‑Performance Inverted CsPbI2Br Perovskite Solar Cells with Efficiency of 15.92%

Developing high-efficiency and stable inverted CsPbI2Br perovskite solar cells is vitally urgent for their unique advantages of removing adverse dopants and compatible process with tandem cells in comparison with the regular.However,relatively low opening circuit voltage(Voc)and limited moisture stability have lagged their progress far from the regular.Here,we propose an effective surface treatment strategy with high-temperature FABr treatment to address these issues.The induced ions exchange can not only adjust energy level,but also gift effective passivation.Meanwhile,the gradient distribution of FA+can accelerate the carriers transport to further suppress bulk recombination.Besides,the Br-rich surface and FA+substitution can isolate moisture erosions.As a result,the optimized devices show champion efficiency of 15.92%with Voc of 1.223 V.In addition,the tolerance of humidity and operation get significant promotion:maintaining 91.7%efficiency after aged at RH 20%ambient condition for 1300 h and 81.8%via maximum power point tracking at 45°C for 500 h in N2.Furthermore,the unpackaged devices realize the rare reported air operational stability and,respectively,remain almost efficiency(98.9%)after operated under RH 35%for 600 min and 91.2%under RH 50%for 300 min.

Hydrogen-Bonded Dopant-Free Hole Transport Material Enables Efficient and Stable Inverted Perovskite Solar Cells

Although many dopant-free hole transport materials(HTMs)for perovskite solar cells(PSCs)have been investigated in the literature,novel and useful molecular designs for high-performance HTMs are still needed.In this work,a hydrogen-bonding association system(NH⋯CO)between amide and carbonyl is introduced into the pure HTM layer.

Efficient and stable inverted perovskite solar cells enabled by inhibition of self-aggregation of fullerene electron-transporting compounds

Fullerene-based electron-transporting layers(ETLs)significantly influence the defect passivation and device performance of inverted perovskite solar cells(PSCs).However,theπ-cage structures of fullerenes lead to a strong tendency to self-aggregate,which affects the long-term stability of the corresponding PSCs.Experimental results revealed that[6,6]-phenyl-C61-butyric acid methyl ester(PCBM)-based ETLs exhibit a certain degree of self-aggregation that affects the stability of the device,particularly under continuous irradiation stress.To modulate the aggregation behavior,we replaced a methyl hydrogen of PCBM with a phenyl group to yield[6,6]-phenyl-C61-butyric acid benzyl ester(PCBB).As verified through X-ray crystallography,this minor structural modification results in more non-covalent intermolecular interactions,which effectively enhanced the electron-transporting ability of the PCBB-based ETL and led to an efficiency approaching 20%.Notably,the enhanced intermolecular forces of PCBB suppressed its self-aggregation,and the corresponding device showed significantly improved stability,retaining approximately 90%of its initial efficiency after 600 h under one-sun irradiation with maximum power point tracking.These findings provide a viable approach for the design of new fullerene derivatives to tune their intermolecular interactions to suppress self-aggregation within the ETL for highperformance PSCs.