Realizing Reduced Imperfections via Quantum Dots Interdiffusion in High Efficiency Perovskite Solar Cells

Realization of reduced ionic (cationic and anionic) defects at the surface and grain boundaries (GBs) of perovskite films is vital to boost the power conversion efficiency of organic–inorganic halide perovskite (OIHP) solar cells. Although numerous strategies have been developed, effective passivation still remains a great challenge due to the complexity and diversity of these defects. Herein, a solid-state interdiffusion process using multi-cation hybrid halide perovskite quantum dots (QDs) is introduced as a strategy to heal the ionic defects at the surface and GBs. It is found that the solid-state interdiffusion process leads to a reduction in OIHP shallow defects. In addition, Cs⁺ distribution in QDs greatly influences the effectiveness of ionic defect passivation with significant enhancement to all photovoltaic performance characteristics observed on treating the solar cells with Cs_0.05(MA_0.17FA_0.83)_0.95PbBr₃ (abbreviated as QDs-Cs5). This enables power conversion efficiency (PCE) exceeding 21% to be achieved with more than 90% of its initial PCE retained on exposure to continuous illumination of more than 550 h.     

An Efficient Approach to Fabricate Air-Stable Perovskite Solar Cells via Addition of a Self-Polymerizing Ionic Liquid

Despite the excellent photovoltaic properties achieved by perovskite solar cells at the laboratory scale, hybrid perovskites decompose in the presence of air, especially at high temperatures and in humid environments. Consequently, high-efficiency perovskites are usually prepared in dry/inert environments, which are expensive and less convenient for scale-up purposes. Here, a new approach based on the inclusion of an in situ polymerizable ionic liquid, 1,3-bis(4-vinylbenzyl)imidazolium chloride ([bvbim]Cl), is presented, which allows perovskite films to be manufactured under humid environments, additionally leading to a material with improved quality and long-term stability. The approach, which is transferrable to several perovskite formulations, allows efficiencies as high as 17% for MAPbI₃ processed in air % relative humidity (RH) ≥30 (from an initial 15%), and 19.92% for FAMAPbI₃ fabricated in %RH ≥50 (from an initial 17%), providing one of the best performances to date under similar conditions.     

钙钛矿太阳能电池:从高效率到稳定性

钙钛矿太阳能电池(Perovskite solar cells,PSCs)由于制备工艺简单、价格便宜、转换效率高、可制备柔性器件等优点引起广泛关注。近年来,钙钛矿太阳能电池的转换效率不断被刷新,迅速实现了对多晶硅太阳能电池的超越,使其具有巨大的商业潜力。然而,稳定性成为阻碍钙钛矿太阳能电池商业化的一大问题。介绍了钙钛矿太阳能电池的结构,综述了钙钛矿太阳能电池所取得的研究进展,总结了获得高效率钙钛矿太阳能电池的方法,重点分析了提高钙钛矿太阳能电池稳定性的策略,并指出钙钛矿太阳能电池的发展方向。     

Improved Efficiency and Stability of Perovskite Solar Cells Induced by CO Functionalized Hydrophobic Ammonium‐Based Additives

Because of the rapid rise of the efficiency, perovskite solar cells are currently considered as the most promising next‐generation photovoltaic technology. Much effort has been made to improve the efficiency and stability of perovskite solar cells. Here, it is demonstrated that the addition of a novel organic cation of 2‐(6‐bromo‐1,3‐dioxo‐1H‐benzo[de]isoquinolin‐2(3H)‐yl)ethan‐1‐ammonium iodide (2‐NAM), which has strong Lewis acid and base interaction (between C?O and Pb) with perovskite, can effectively increase crystalline grain size and reduce charge carrier recombination of the double cation FA_0.83MA_0.17PbI_2.51Br_0.49 perovskite film, thus boosting the efficiency from 17.1 ± 0.8% to 18.6 ± 0.9% for the 0.1 cm² cell and from 15.5 ± 0.5% to 16.5 ± 0.6% for the 1.0 cm² cell. The champion cell shows efficiencies of 20.0% and 17.6% with active areas of 0.1 and 1.0 cm², respectively. Moreover, the hysteresis behavior is suppressed and the stability is improved. The result provides a promising route to further elevate efficiency and stability of perovskite solar cells by the fine tuning of triple organic cations.     

Dual Defect-Passivation Using Phthalocyanine for Enhanced Efficiency and Stability of Perovskite Solar Cells

Semiconducting molecules have been employed to passivate traps extant in the perovskite film for enhancement of perovskite solar cells (PSCs) efficiency and stability. A molecular design strategy to passivate the defects both on the surface and interior of the CH₃NH₃PbI₃ perovskite layer, using two phthalocyanine (Pc) molecules (NP-SC₆-ZnPc and NP-SC₆-TiOPc) is demonstrated. The presence of lone electron pairs on S, N, and O atoms of the Pc molecular structures provides the opportunity for Lewis acid–base interactions with under-coordinated Pb²⁺ sites, leading to efficient defect passivation of the perovskite layer. The tendency of both NP-SC₆-ZnPc and NP-SC₆-TiOPc to relax on the PbI₂ terminated surface of the perovskite layer is also studied using density functional theory (DFT) calculations. The morphology of the perovskite layer is improved due to employing the Pc passivation strategy, resulting in high-quality thin films with a dense and compact structure and lower surface roughness. Using NP-SC₆-ZnPc and NP-SC₆-TiOPc as passivating agents, it is observed considerably enhanced power conversion efficiencies (PCEs), from 17.67% for the PSCs based on the pristine perovskite film to 19.39% for NP-SC₆-TiOPc passivated devices. Moreover, PSCs fabricated based on the Pc passivation method present a remarkable stability under conditions of high moisture and temperature levels.     

Versatility of Carbon Enables All Carbon Based Perovskite Solar Cells to Achieve High Efficiency and High Stability

Carbon‐based perovskite solar cells (PVSCs) without hole transport materials are promising for their high stability and low cost, but the electron transporting layer (ETL) of TiO₂ is notorious for inflicting hysteresis and instability. In view of its electron accepting ability, C₆₀ is used to replace TiO₂ for the ETL, forming a so‐called all carbon based PVSC. With a device structure of fluorine‐doped tin oxide (FTO)/C₆₀/methylammonium lead iodide (MAPbI₃)/carbon, a power conversion efficiency (PCE) is attained up to 15.38% without hysteresis, much higher than that of the TiO₂ ones (12.06% with obvious hysteresis). The C₆₀ ETL is found to effectively improve electron extraction, suppress charge recombination, and reduce the sub‐bandgap states at the interface with MAPbI₃. Moreover, the all carbon based PVSCs are shown to resist moisture and ion migration, leading to a much higher operational stability under ambient, humid, and light‐soaking conditions. To make it an even more genuine all carbon based PVSC, it is further attempted to use graphene as the transparent conductive electrode, reaping a PCE of 13.93%. The high performance of all carbon based PVSCs stems from the bonding flexibility and electronic versatility of carbon, promising commercial developments on account of their favorable balance of cost, efficiency, and stability.     

The Role of Bulk and Interface Recombination in High‐Efficiency Low‐Dimensional Perovskite Solar Cells

2D Ruddlesden–Popper perovskite (RPP) solar cells have excellent environmental stability. However, the power conversion efficiency (PCE) of RPP cells remains inferior to 3D perovskite‐based cells. Herein, 2D (CH₃(CH₂)₃NH₃)₂(CH₃NH₃)_n?1Pb_nI_3n+1 perovskite cells with different numbers of [PbI₆]^4? sheets (n = 2–4) are analyzed. Photoluminescence quantum yield (PLQY) measurements show that nonradiative open‐circuit voltage (V_OC) losses outweigh radiative losses in materials with n > 2. The n = 3 and n = 4 films exhibit a higher PLQY than the standard 3D methylammonium lead iodide perovskite although this is accompanied by increased interfacial recombination at the top perovskite/C₆₀ interface. This tradeoff results in a similar PLQY in all devices, including the n = 2 system where the perovskite bulk dominates the recombination properties of the cell. In most cases the quasi‐Fermi level splitting matches the device V_OC within 20 meV, which indicates minimal recombination losses at the metal contacts. The results show that poor charge transport rather than exciton dissociation is the primary reason for the reduction in fill factor of the RPP devices. Optimized n = 4 RPP solar cells had PCEs of 13% with significant potential for further improvements.     

Isomer‐Pure Bis‐PCBM‐Assisted Crystal Engineering of Perovskite Solar Cells Showing Excellent Efficiency and Stability

A fullerene derivative (α‐bis‐PCBM) is purified from an as‐produced bis‐phenyl‐C₆₁‐butyric acid methyl ester (bis‐[60]PCBM) isomer mixture by preparative peak‐recycling, high‐performance liquid chromatography, and is employed as a templating agent for solution processing of metal halide perovskite films via an antisolvent method. The resulting α‐bis‐PCBM‐containing perovskite solar cells achieve better stability, efficiency, and reproducibility when compared with analogous cells containing PCBM. α‐bis‐PCBM fills the vacancies and grain boundaries of the perovskite film, enhancing the crystallization of perovskites and addressing the issue of slow electron extraction. In addition, α‐bis‐PCBM resists the ingression of moisture and passivates voids or pinholes generated in the hole‐transporting layer. As a result, a power conversion efficiency (PCE) of 20.8% is obtained, compared with 19.9% by PCBM, and is accompanied by excellent stability under heat and simulated sunlight. The PCE of unsealed devices dropped by less than 10% in ambient air (40% RH) after 44 d at 65 °C, and by 4% after 600 h under continuous full‐sun illumination and maximum power point tracking, respectively.     

Planar‐Structure Perovskite Solar Cells with Efficiency beyond 21%

Low temperature solution processed planar‐structure perovskite solar cells gain great attention recently, while their power conversions are still lower than that of high temperature mesoporous counterpart. Previous reports are mainly focused on perovskite morphology control and interface engineering to improve performance. Here, this study systematically investigates the effect of precise stoichiometry, especially the PbI₂ contents on device performance including efficiency, hysteresis and stability. This study finds that a moderate residual of PbI₂ can deliver stable and high efficiency of solar cells without hysteresis, while too much residual PbI₂ will lead to serious hysteresis and poor transit stability. Solar cells with the efficiencies of 21.6% in small size (0.0737 cm²) and 20.1% in large size (1 cm²) with moderate residual PbI₂ in perovskite layer are obtained. The certificated efficiency for small size shows the efficiency of 20.9%, which is the highest efficiency ever recorded in planar‐structure perovskite solar cells, showing the planar‐structure perovskite solar cells are very promising.     

Defect‐Engineering‐Enabled High‐Efficiency All‐Inorganic Perovskite Solar Cells

The emergence of cesium lead iodide (CsPbI₃) perovskite solar cells (PSCs) has generated enormous interest in the photovoltaic research community. However, in general they exhibit low power conversion efficiencies (PCEs) because of the existence of defects. A new all‐inorganic perovskite material, CsPbI₃:Br:InI₃, is prepared by defect engineering of CsPbI₃. This new perovskite retains the same bandgap as CsPbI₃, while the intrinsic defect concentration is largely suppressed. Moreover, it can be prepared in an extremely high humidity atmosphere and thus a glovebox is not required. By completely eliminating the labile and expensive components in traditional PSCs, the all‐inorganic PSCs based on CsPbI₃:Br:InI₃ and carbon electrode exhibit PCE and open‐circuit voltage as high as 12.04% and 1.20 V, respectively. More importantly, they demonstrate excellent stability in air for more than two months, while those based on CsPbI₃ can survive only a few days in air. The progress reported represents a major leap for all‐inorganic PSCs and paves the way for their further exploration in order to achieve higher performance.     

Argon Plasma Treatment to Tune Perovskite Surface Composition for High Efficiency Solar Cells and Fast Photodetectors

The surface composition of perovskite films is very sensitive to film processing and can deviate from the optimal, which generates unfavorable defects and results in efficiency loss in solar cells and slow response speed in photodetectors. An argon plasma treatment is introduced to modify the surface composition by tuning the ratio of organic and inorganic components as well as defect type before deposition of the passivating layer. It can efficiently enhance the charge collection across the perovskite–electrode interface by suppressing charge recombination. Therefore, perovskite solar cells with argon plasma treatment yield enhanced efficiency to 20.4% and perovskite photodetectors can reach their fastest respond speed, which is solely limited by the carrier mobility.     

Quasi‐Heteroface Perovskite Solar Cells

Perovskite solar cells (PSCs) have attracted unprecedented attention due to their rapidly rising photoelectric conversion efficiency (PCE). In order to further improve the PCE of PSCs, new possible optimization path needs to be found. Here, quasi‐heteroface PSCs (QHF‐PSCs) is designed by a double‐layer perovskite film. Such brand new PSCs have good carrier separation capabilities, effectively suppress the nonradiative recombination of the PSCs, and thus greatly improve the open‐circuit voltage and PCE. The root cause of the performance improvement is the benefit from the additional built‐in electric field, which is confirmed by measuring the external quantum efficiency under applied electric field and Kelvin probe force microscope. Meanwhile, an intermediate band gap perovskite layer can be obtained simply by combining a wide band gap perovskite layer with a narrow band gap perovskite layer. Tunability of the band gap is obtained by varying the film thicknesses of the narrow and wide band gap layers. This phenomenon is quite different from traditional inorganic solar cells, whose band gap is determined only by the narrowest band gap layer. It is believed that these QHF‐PSCs will be an effective strategy to further enhance PCE in PSCs and provide basis to further understand and develop the perovskite materials platform.     

Novel Meso‐Superstructured Solar Cells with a High Efficiency Exceeding 12%

The dye‐sensitized solar cell (DSSC) is representative of next generation photovoltaic devices. State‐of‐the‐art DSSCs have been established for two decades. However, the recent application of organic‐inorganic hybrid perovskites on nanoparticle Al₂O₃ film has totally changed the DSSC structure, leading to a new type of solar cell — meso‐superstructured solar cells (MSSCs) with a high power conversion efficiency exceeding 12%. This article summarizes this impressive progress and discusses the challenges of MSSCs.     

Fluorinated Low‐Dimensional Ruddlesden–Popper Perovskite Solar Cells with over 17% Power Conversion Efficiency and Improved Stability

Low‐dimensional Ruddlesden–Popper perovskites (RPPs) exhibit excellent stability in comparison with 3D perovskites; however, the relatively low power conversion efficiency (PCE) limits their future application. In this work, a new fluorine‐substituted phenylethlammonium (PEA) cation is developed as a spacer to fabricate quasi‐2D (4FPEA)₂(MA)₄Pb₅I₁₆ (n = 5) perovskite solar cells. The champion device exhibits a remarkable PCE of 17.3% with a J_sc of 19.00 mA cm^?2, a V_oc of 1.16 V, and a fill factor (FF) of 79%, which are among the best results for low‐dimensional RPP solar cells (n ≤ 5). The enhanced device performance can be attributed as follows: first, the strong dipole field induced by the 4‐fluoro‐phenethylammonium (4FPEA) organic spacer facilitates charge dissociation. Second, fluorinated RPP crystals preferentially grow along the vertical direction, and form a phase distribution with the increasing n number from bottom to the top surface, resulting in efficient charge transport. Third, 4FPEA‐based RPP films exhibit higher film crystallinity, enlarged grain size, and reduced trap‐state density. Lastly, the unsealed fluorinated RPP devices demonstrate superior humidity and thermal stability. Therefore, the fluorination of the long‐chain organic cations provides a feasible approach for simultaneously improving the efficiency and stability of low‐dimensional RPP solar cells.