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.

Highly Efficient and Stable FAPbI_(3) Perovskite Solar Cells and Modules Based on Exposure of the(011)Facet

Perovskite crystal facets greatly impact the performance and stability of their corresponding photovoltaic devices.Compared to the(001)facet,the(011)facet yields better photoelectric properties,including higher conductivity and enhanced charge carrier mobility.Thus,achieving(011)facet-exposed films is a promising way to improve device performance.However,the growth of(011)facets is energetically unfavorable in FAPbI_(3) perovskites due to the influence of methylammonium chloride additive.Here,1-butyl-4-methylpyridinium chloride([4MBP]Cl)was used to expose(011)facets.The[4MBP]^(+)cation selectively decreases the surface energy of the(011)facet enabling the growth of the(011)plane.The[4MBP]^(+)cation causes the perovskite nuclei to rotate by 45°such that(011)crystal facets stack along the out-of-plane direction.The(011)facet has excellent charge transport properties and can achieve better-matched energy level alignment.In addition,[4MBP]Cl increases the activation energy barrier for ion migration,suppressing decomposition of the perovskite.As a result,a small-size device(0.06 cm2)and a module(29.0 cm2)based on exposure of the(011)facet achieved power conversion efficiencies of 25.24%and 21.12%,respectively.

Modulating J-V hysteresis of planar perovskite solar cells and mini-modules via work function engineering

Commercialization of perovskite solar cells(PSCs) requires the development of high-efficiency devices with none current density-voltage(J-V) hysteresis. Here, electron transport layers(ETLs) with gradual change in work function(WF) are successfully fabricated and employed as an ideal model to investigate the energy barriers, charge transfer and recombination kinetics at ETL/perovskite interface. The energy barrier for electron injection existing at ETL/perovskite is directly assessed by surface photovoltage microscopy, and the results demonstrate the tunable barriers have significant impact on the J-V hysteresis and performance of PSCs. By work function engineering of ETL, PSCs exhibit PCEs over 21% with negligible hysteresis. These results provide a critical understanding of the origin reason for hysteresis effect in planar PSCs, and clear reveal that the J-V hysteresis can be effectively suppressed by carefully tuning the interface features in PSCs. By extending this strategy to a modified formamidinium-cesium-rubidium(FA-Cs-Rb) perovskite system, the PCEs are further boosted to 24.18%. Moreover, 5 cm × 5 cm perovskite mini-modules are also fabricated with an impressive efficiency of 20.07%, demonstrating compatibility and effectiveness of our strategy on upscaled devices.

Enhanced performance of solution-processed carbon nanotube transparent electrodes in foldable perovskite solar cells through vertical separation of binders by using eco-friendly parylene substrate

The successful utilization of an eco-friendly and biocompatible parylene-C substrate for high-performance solution-processed double-walled carbon nanotube(CNT)electrode-based perovskite solar cells(PSCs)was demonstrated.Through the use of a novel inversion transfer technique,vertical separation of the binders from the CNTs was induced,rendering a stronger p-doping effect and thereby a higher conductivity of the CNTs.The resulting foldable devices exhibited a power conversion efficiency of 18.11%,which is the highest reported among CNT transparent electrode-based PSCs to date,and withstood more than 10,000 folding cycles at a radius of 0.5 mm,demonstrating unprecedented mechanical stability.Furthermore,solar modules were fabricated using entirely laser scribing processes to assess the potential of the solution-processable nanocarbon electrode.Notably,this is the only one to be processed entirely by the laser scribing process and to be biocompatible as well as eco-friendly among the previously reported nonindium tin oxide-based perovskite solar modules.

Solvent engineering towards scalable fabrication of high-quality perovskite films for efficient solar modules

Over the last decade,remarkable progress has been made in metal halide perovskite solar cells(PSCs),which have been a focus of emerging photovoltaic techniques and show great potential for commercialization.However,the upscaling of small-area PSCs to large-area solar modules to meet the demands of practical applications remains a significant challenge.The scalable production of high-quality perovskite films by a simple,reproducible process is crucial for resolving this issue.Furthermore,the crystallization behavior in the solution-processed fabrication of perovskite films can be strongly influenced by the physicochemical properties of the precursor inks,which are significantly affected by the employed solvents and their interactions with the solutes.Thus,a comprehensive understanding of solvent engineering for fabricating perovskite films over large areas is urgently required.In this paper,we first analyze the role of solvents in the solution-processed fabrication of large-area perovskite films based on the classical crystal nucleation and growth mechanism.Recent efforts in solvent engineering to improve the quality of perovskite films for solar modules are discussed.Finally,the basic principles and future challenges of solvent system design for scalable fabrication of high-quality perovskite films for efficient solar modules are proposed.

Crystallization and Orientation Modulation Enable Highly Efficient Doctor-Bladed Perovskite Solar Cells

With the rapid rise in perovskite solar cells(PSCs)performance,it is imperative to develop scalable fabrication techniques to accelerate potential commercialization.However,the power conversion efficiencies(PCEs)of PSCs fabricated via scalable two-step sequential deposition lag far behind the state-of-the-art spin-coated ones.Herein,the additive methylammonium chloride(MACl)is introduced to modulate the crystallization and orientation of a two-step sequential doctorbladed perovskite film in ambient conditions.MACl can significantly improve perovskite film quality and increase grain size and crystallinity,thus decreasing trap density and suppressing nonradiative recombination.Meanwhile,MACl also promotes the preferred face-up orientation of the(100)plane of perovskite film,which is more conducive to the transport and collection of carriers,thereby significantly improving the fill factor.As a result,a champion PCE of 23.14%and excellent longterm stability are achieved for PSCs based on the structure of ITO/SnO_(2)/FA_(1-x)MA_xPb(I_(1-y)Br_y)_3/Spiro-OMeTAD/Ag.The superior PCEs of 21.20%and 17.54%are achieved for 1.03 cm~2 PSC and 10.93 cm~2 mini-module,respectively.These results represent substantial progress in large-scale two-step sequential deposition of high-performance PSCs for practical applications.

Low-Temperature Soft-Cover-Assisted Hydrolysis Deposition of Large-Scale TiO_2 Layer for Efficient Perovskite Solar Modules

Perovskite solar cells with TiO_2 electron transport layers exhibit power conversion efficiency(PCE) as high as 22.7% in single cells. However, the preparation process of the TiO_2 layer is adopted by an unscalable method or requires high-temperature sintering, which precludes its potential use for mass production of flexible devices. In this study, a scalable low-temperature softcover-assisted hydrolysis(SAH) method is presented,where the precursor solution is sandwiched between a soft cover and preheated substrate to form a closed hydrolysis environment. Compact homogeneous TiO_2 films with a needle-like structure were obtained after the hydrolysis of a TiCl_4 aqueous solution. Moreover, by careful optimization of the TiO_2 fabrication conditions, a high PCE of 14.01% could be achieved for a solar module(4 × 4 cm^2) prepared using the SAH method. This method provides a novel approach for the efficient scale-up of the low-temperature TiO_2 film growth for industrial applications.

Sodium Diffuses from Glass Substrates through P1 Lines and Passivates Defects in Perovskite Solar Modules

Most thin-film photovoltaic modules are constructed on soda-lime glass(SLG)substrates containing alkali oxides,such as Na_(2)O.Na may diffuse from SLG into a module's active layers through P1 lines,an area between a module's constituent cells where the substrate-side charge transport layer(CTL)is in direct contact with SLG.Na diffusion from SLG is known to cause several important effects inⅡ-Ⅵand chalcogenide solar modules,but it has not been studied in perovskite solar modules(PSMs).In this work,we use complementary microscopy and spectroscopy techniques to show that Na diffusion occurs in the fabrication process of PSMs.Na diffuses vertically inside P1 lines and then laterally from P1 lines into the active area for up to 360 pm.We propose that this process is driven by the high temperatures the devices are exposed to during CTL and perovskite annealing.The diffused Na preferentially binds with Br,forming Br-poor,l-rich perovskite and a species rich in Na and Br(Na-Br)close to P1 lines.Na-Br passivates defect sites,reducing non-radiative recombination in the perovskite and boosting its luminescence by up to 5×.Na-Br is observed to be stable after 12 weeks of device storage,suggesting long-lasting effects of Na diffusion.Our results not only point to a potential avenue to increase PSM performance but also highlight the possibility of unabated Na diffusion throughout a module's lifetime,especially if accelerated by the electric field and elevated temperatures achievable during device operation.

Carbon-based perovskite solar cells: From single-junction to modules

Perovskite solar cells(PSCs)have attracted more and more attention in the scientific community due to their high performance and simple fabrication process.In the past few years,emerging technologies have made manufacturing large-scale PSC modules possible.However,stability and fabrication issues still limit the modularization and commercialization of PSCs.Carbon materials have been widely used in PSCs to overcome these challenges due to their excellent optical,electrical,and mechanical properties.In addition,the hydrophobic properties of certain carbon materials are highly effective at protecting the perovskite film from moisture and improving the stability of PSCs.All these superior properties have made carbon one of the most promising materials to fabricate future highperformance PSC modules with long service lifetimes.In this review,recent developments of carbon-based materials in different layers of single-junction PSCs will first be discussed,with an emphasis on functionalities related to PSCs’stability and modularization.Then,current improvements and future discussions in the manufacturing of monolithic PSC modules will be reviewed in detail.

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.

Surface modulation of halide perovskite films for efficient and stable solar cells

As the main distribution place of deep-level defects and the entrance of water, the interface is critical to determining both the power conversion efficiency(PCE) and the stability of perovskite solar cells(PSCs). Suitable interface design can dramatically passivate interface defects and optimize energy level alignment for suppressing the nonradiative recombination and effectively extracting the photogenerated carriers towards higher PCE. Meanwhile, a proper interface design can also block the interface diffusion of ions for high operational stability. Therefore, interface modification is of great significance to make the PSCs more efficient and stable. Upon optimized material choices, the three-dimensional halide perovskite graded junction layer, low-dimensional halide perovskite interface layer and organic salt passivation layer have been constructed on perovskite films for superior PSCs, yet a systematic review of them is missing. Thus, a guide and summary of recent advances in modulating the perovskite films interface is necessary for the further development of more efficient interface modification.

Playdough-like carbon electrode: A promising strategy for high efficiency perovskite solar cells and modules

Carbon-based perovskite solar cells(C-PSCs)are promising candidates for large-scale photovoltaic applications due to their theoretical low cost and high stability.However,the fabrication of high-performance C-PSCs with large-area electrodes remains challenging.In this work,we propose a novel playdough-like graphite putty as top electrode in the perovskite devices.This electrode with soft nature can form good contact with the holetransporting layer and the conductive substrate at room temperature by a simple pressing technique,which facilitates the fabrication of both small-area devices and perovskite solar modules.In this preliminary research,the corresponding small devices and modules can achieve efficiencies of 20.29%(~0.15 cm^(2))and 16.01%(~10 cm^(2)),respectively.Moreover,we analyze the limitations of the optical and electrical properties of this playdough-like graphite electrode on the device performance,suggesting a direction for further improvement of C-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.

Additives in metal halide perovskite films and their applications in solar cells

The booming growth of organic-inorganic hybrid lead halide perovskite solar cells have made this promising photovoltaic technology to leap towards commercialization.One of the most important issues for the evolution from research to practical application of this technology is to achieve high-throughput manufacturing of large-scale perovskite solar modules.In particular,realization of scalable fabrication of large-area perovskite films is one of the essential steps.During the past ten years,a great number of approaches have been developed to deposit high quality perovskite films,to which additives are introduced during the fabrication process of perovskite layers in terms of the perovskite grain growth control,defect reduction,stability enhancement,etc.Herein,we first review the recent progress on additives during the fabrication of large area perovskite films for large scale perovskite solar cells and modules.We then focus on a comprehensive and in-depth understanding of the roles of additives for perovskite grain growth control,defects reduction,and stability enhancement.Further advancement of the scalable fabrication of high-quality perovskite films and solar cells using additives to further develop large area,stable perovskite solar cells are discussed.

Solution-processed perovskite solar cells

Perovskite solar cells(PSCs) have emerged as one of the most promising candidates for photovoltaic applications. Low-cost, low-temperature solution processes including coating and printing techniques makes PSCs promising for the greatly potential commercialization due to the scalability and compatibility with large-scale, roll-to-roll manufacturing processes. In this review, we focus on the solution deposition of charge transport layers and perovskite absorption layer in both mesoporous and planar structural PSC devices. Furthermore, the most recent design strategies via solution deposition are presented as well, which have been explored to enlarge the active area, enhance the crystallization and passivate the defects, leading to the performance improvement of PSC devices.

Recent Progress in Large-Area Perovskite Photovoltaic Modules

Perovskite solar cells(PSCs)have undergone a dramatic increase in laboratory-scale effi ciency to more than 25%,which is comparable to Si-based single-junction solar cell effi ciency.However,the effi ciency of PSCs drops from laboratory-scale to large-scale perovskite solar modules(PSMs)because of the poor quality of perovskite fi lms,and the increased resistance of large-area PSMs obstructs practical PSC applications.An in-depth understanding of the fabricating processes is vital for precisely controlling the quality of large-area perovskite fi lms,and a suitable structural design for PSMs plays an impor-tant role in minimizing energy loss.In this review,we discuss several solution-based deposition techniques for large-area perovskite fi lms and the eff ects of operating conditions on the fi lms.Furthermore,diff erent structural designs for PSMs are presented,including the processing technologies and device architectures.

Efficient fully laser-patterned flexible perovskite modules and solar cells based on low-temperature solution-processed SnO2/mesoporous-TiO2 electron transport layers

Efficient flexible perovskite solar cells and modules were developed using a combination of SnO2 and mesoporous-TiO2 as a fully solution-processed electron transport layer （ETL）. Cells using such ETLs delivered a maximum power conversion efficiency （PCE） of 14.8%, which was 30% higher than the PCE of cells with only SnO2 as the ETL. The presence of a mesoporous TiO2 scaffold layer over SnO2 led to higher rectification ratios, lower series resistances, and higher shunt resistances. The cells were also evaluated under 200 and 400 lx artificial indoor illumination and found to deliver maximum power densities of 9.77 μW/cm^2 （estimated PCE of 12.8%） and 19.2 μW/cm^2 （estimated PCE of 13.3%）, respectively, representing the highest values among flexible photovoltaic technologies reported so far. Furthermore, for the first time, a fully laser-patterned flexible perovskite module was fabricated using a complete three-step laser scribing procedure （P1, P2, P3） with a PCE of 8.8% over an active area of 12 cm^2 under an illumination of 1 sun.

Understanding the role of interconnecting layer on determining monolithic perovskite/organic tandem device carrier recombination properties

As one of the core parts of two-terminal(2 T) monolithic tandem photovoltaics, the interconnecting layers(ICLs) play a critical role in modulating the carrier transport and recombination between the sub-cells,and thus influencing the tandem device performance. Here, for the first time, the relationship between ICLs architecture and 2 T monolithic perovskite/organic tandem device performance has been studied by investigating the change of ICLs composition layer thickness on the ICLs optical and electrical properties, sub-cells EQE properties, and tandem device J-V properties. It is revealed that the ability of ICLs on modulating the sub-cells carrier balance properties is strongly associated with its composited layers thickness, and the tandem device carrier balance properties can be reflected by the relative EQE intensity between the sub-cells. Finally, with a deep understanding of the mechanisms, rational design of ICLs can be made to benefit the tandem device development. Based on the optimized ICL a high PCE of 20.03% is achieved.

Bilayer metal halide perovskite for efficient and stable solar cells and modules

To reach the target of carbon neutral,a transition from fossil energy to renewable energy is unavoidable.Photovoltaic technology is considered one of the most prominent sources of renewable energy.Recently,metal halide perovskite materials have attracted tremendous interest in the areas of optoelectronic devices due to their ease of processing and outstanding performance.To date,perovskite solar cells(PSCs)have shown high power conversion efficiency up to 25.7%and 31.3%for the perovskite-silicon tandem solar cells,which promises to revolutionize the PV landscape.However,the stability of PSCs under operating conditions has yet to match state-of-the-art silicon-based solar cell technology,in which the stability of the absorbing layer and relevant interfaces is the primary challenge.These issues become more serious in the larger area solar modules due to the additional interfaces and more defects within the perovskite.Bilayer perovskite film composed of a thin low dimensional perovskite layer and a three-dimensional perovskite layer shows great potential in fabricating solar cells with high efficiency and stability simultaneously.In this review,recent advancements,including composition design and processing methods for constructing bilayer perovskite films are discussed.We then analyze the challenges and resolutions in deposition bilayer perovskite films with scalable techniques.After summarizing the beneficial effect of the bilayer structure,we propose our thinking of feasible strategies to fabricate high efficiency perovskite solar modules with a long lifetime.Finally,we outline the directions for future work that will push the perovskite PV technology toward commercialization.

Improving intrinsic stability for perovskite/silicon tandem solar cells

Monolithic hybrid halide perovskite/crystalline silicon(c-Si)tandem solar cells have demonstrated their great potential to surpass the theoretical efficiency limit of single-junction devices.However,the stability of perovskite sub-cells is inferior to that of the c-Si solar cells that have been commercialized,casting serious doubt about the lifetime of the entire device.During device operation,light and heat are inevitable,which requires special attention.Herein,we review the current understandings of the intrinsic stability of perovskite/c-Si tandems upon light and/or heat aging.First,we summarize the recent understandings regarding light facilitated ion migration,materials decomposition,and phase segregation.In addition,the reverse bias effect on the stability of tandem modules caused by uneven illumination is discussed.Second,this review also summarizes the thermalinduced degradation and mismatch issue,which underlines the system design of perovskite/c-Si tandems.Third,recent strategies to improve the intrinsic stability of perovskite/c-Si tandems under light and/or heat are reviewed,such as composition engineering,crystallinity enhancement,interface modification,material optimization,and device structure modification.At last,we present several potential research directions that have been overlooked,and hope those are helpful for future research on perovskite based tandem solar cells.