Intermarriage of Halide Perovskites and Metal-Organic Framework Crystals

This Review examines how the intermarriage of perovskite and metal-organic framework crystals brings new paradigms for material design and functionality. The strategic combination of halide perovskites and metal–organic frameworks (MOFs) has generated a new family of porous composite materials that will enable new applications, including optoelectronic, catalysis, sensing, and data encryption. This Review surveys the current progress of this exciting new area. Fundamental aspects, including perovskite nucleation and growth, heterojunction electron–hole transfer, electronic structure, and luminescence within confined spaces, are highlighted, with suggestions of approaches by which guest confinement within MOFs can be synthetically designed. We further address the underlying principles and discuss the new insights and tools for the manipulation of these composite materials for the development of synthetic microporous semiconducting composites, as well as new strategies for host–guest interfacial engineering.     

Solubility of Hybrid Halide Perovskites in DMF and DMSO

Solution methods remain the most popular means for the fabrication of hybrid halide perovskites. However, the solubility of hybrid perovskites has not yet been quantitively investigated. In this study, we present accurate solubility data for MAPbI₃, FAPbI₃, MAPbBr₃ and FAPbBr₃ in the two most widely used solvents, DMF and DMSO, and demonstrate huge differences in the solubility behavior depending on the solution compositions. By analyzing the donor numbers of the solvents and halide anions, we rationalize the differences in the solubility behavior of hybrid perovskites with various compositions, in order to take a step forward in the search for better processing conditions of hybrid perovskites for solar cells and optoelectronics.     

铅卤钙钛矿敏化型太阳能电池的研究进展

铅卤钙钛矿太阳能电池由于其低廉的成本, 简易的制备工艺和具有商业化潜力的效率等优点, 在最近两年里成为太阳能领域广受关注的新星. 铅卤钙钛矿太阳能电池的结构, 材料合成和制作工业在短时期内发生多项革命性的变化. 铅卤钙钛矿敏化型太阳能电池从最初使用液体电解液的敏化电池, 演变为固态敏化电池. 铅卤钙钛矿也从最初沉积在介孔膜的空隙的传统敏化结构, 演变为介孔空隙填充和致密覆盖层结合的混合型敏化结构. 通过这些结构的演化和材料制备的进步, 敏化型铅卤钙钛矿太阳能电池具备了较高的稳定性和高效率的两大优点. 对铅卤钙钛矿敏化型太阳能电池的研究进展进行简要综述.     

Lights and Shadows of DMSO as Solvent for Tin Halide Perovskites

In 2020 dimethyl sulfoxide (DMSO), the ever-present solvent for tin halide perovskites, was identified as an oxidant for Sn^II. Nonetheless, alternatives are lacking and few efforts have been devoted to replacing it. To understand this trend it is indispensable to learn the importance of DMSO on the development of tin halide perovskites. Its unique properties have allowed processing compact thin-films to be integrated into tin perovskite solar cells. Creative approaches for controlling the perovskite crystallization or increasing its stability to oxidation have been developed relying on DMSO-based inks. However, increasingly sophisticated strategies appear to lead the field to a plateau of power conversion efficiency in the range of 10–15 %. And, while DMSO-based formulations have performed in encouraging means so far, we should also start considering their potential limitations. In this concept article, we discuss the benefits and limitations of DMSO-based tin perovskite processing.     

超卤素掺杂立方相卤化物钙钛矿太阳能电池材料第一性原理研究

卤化物钙钛矿（ABC₃）太阳能电池由于其优异的光电性质引起了人们的广泛关注,对结构中的A位及B位离子进行等价离子取代是调控钙钛矿材料禁带宽度的有效方法之一.本文研究拟用超卤素离子团簇（BeX₃^-,MgX₃^-,BX₄^-,AlX₄^-,SiX₅^-,PX₆^-,X＝F,Cl）对立方相CsPbI₃钙钛矿中的I^-离子进行部分掺杂或完全取代,设计了一系列基于超卤素团簇掺杂的新型卤化物钙钛矿太阳能电池材料,并运用第一性原理的方法对材料的结构和性质进行了模拟研究.结果表明,采用上述超卤素离子团簇对CsPbI₃钙钛矿中的I^-离子进行部分掺杂比全部取代后得到的结构体系禁带宽度小;采用PCl₆^-团簇取代I^-离子得到的CsPb （PCl₆）₃体系的禁带宽度是1.58 eV,其导带底部主要由Cl原子的3p轨道、P原子的3s轨道以及Pb原子的6p轨道杂化组成,该材料是一种潜在的钙钛矿太阳能电池材料.     

All‐Inorganic CsPbX3 Perovskite Solar Cells: Progress and Prospects

Recently, lead halide‐based perovskites have become one of the hottest topics in photovoltaic research because of their excellent optoelectronic properties. Among them, organic‐inorganic hybrid perovskite solar cells (PSCs) have made very rapid progress with their power conversion efficiency (PCE) now at 23.7 %. However, the intrinsically unstable nature of these materials, particularly to moisture and heat, may be a problem for their long‐term stability. Replacing the fragile organic group with more robust inorganic Cs⁺ cations forms the cesium lead halide system (CsPbX₃, X is halide) as all‐inorganic perovskites which are much more thermally stable and often more stable to other factors. From the first report in 2015 to now, the PCE of CsPbX₃‐based PSCs has abruptly increased from 2.9 % to 17.1 % with much enhanced stability. In this Review, we summarize the field up to now, propose solutions in terms of development bottlenecks, and attempt to boost further research in CsPbX₃ PSCs.     

锡基钙钛矿太阳电池光吸收材料

钙钛矿太阳电池以其优异的光吸收特性、载流子传输能力以及简单的制备工艺,成为太阳电池领域研究的热点。高效、无污染、低成本一直是太阳电池领域追求的目标。然而,传统钙钛矿太阳电池由于其光吸收材料中含重金属元素铅,对环境有较大影响,从而限制了此类钙钛矿太阳电池的进一步商业化应用。基于此,科学家们都在致力于寻找新的无铅钙钛矿材料。在众多无铅钙钛矿材料中,锡基钙钛矿材料由于其相对较小的毒性、合适的带隙以及相应器件具有较高的能量转换效率等优点,成为最有希望应用于钙钛矿太阳电池的替代材料。然而,锡基钙钛矿太阳电池也存在一些弱点,其能量转换效率和器件稳定性相较于铅基钙钛矿太阳电池仍然存在很大差距,器件制备过程中对空气十分敏感。为了更好地解决这些问题,对锡基钙钛矿材料及器件性能的各种影响因素进行系统地研究势在必行。文章分类介绍了各类锡基钙钛矿材料及其在太阳电池中的应用,包括有机-无机杂化锡基钙钛矿材料,锡铅混合钙钛矿材料和全无机锡基钙钛矿材料,综述了锡基钙钛矿材料及其相应器件性能的最新研究进展,并且讨论了影响器件性能的各项因素,最后对锡基钙钛矿太阳电池未来的发展做出了展望。     

Lead‐Free Solar Cells based on Tin Halide Perovskite Films with High Coverage and Improved Aggregation

Two simple methods to improve tin halide perovskite film structure are introduced, aimed at increasing the power conversion efficiency of lead free perovskite solar cells. First, a hot antisolvent treatment (HAT) was found to increase the film coverage and prevent electrical shunting in the photovoltaic device. Second, it was discovered that annealing under a low partial pressure of dimethyl sulfoxide vapor increased the average crystallite size. The topographical and electrical qualities of the perovskite films are substantively improved as a result of the combined treatments, facilitating the fabrication of tin‐based perovskite solar cell devices with power conversion efficiencies of over 7 %.     

卤化钙钛矿太阳能电池材料理论研究进展

卤化钙钛矿由于具有低成本、高效率等特点,最近作为非常有前景的太阳能电池吸收层材料被广泛研究。卤化钙钛矿型太阳能电池效率在短短的几年间由3.8%(2009年)迅速增加到22.1%(2016年)。卤化钙钛矿型太阳能电池的出现彻底改变了太阳能电池领域,不仅因为它们快速增长的效率,而且因为它们在材料生长和结构方面的可控性。卤化钙钛矿型太阳能电池的优越性能说明卤化钙钛矿材料具有独特的物理性质。在本综述中,我们总结了卤化钙钛矿材料最近几年在结构、电学、光学方面的理论研究成果,这些都与它们在太阳能电池方面的应用密切相关。我们也将探讨一些卤化钙钛矿型太阳能电池目前遇到的挑战以及可能的理论解决途径。     

阴极界面修饰层改善平面p-i-n型钙钛矿太阳能电池的光伏性能

有机/无机杂化金属卤化物钙钛矿半导体材料结合了有机材料良好的溶液可加工性以及无机材料优越的光电特性,近几年受到了热捧,成为太阳能电池领域一颗耀眼的明星. 伴随着钙钛矿薄膜结晶过程和形貌的优化、器件结构的改进以及电极界面材料的开发,这类有机/无机杂化金属卤化物钙钛矿太阳能电池的光电转换效率从最初的3.8%迅速提高到目前最高的22.1%. 其中界面工程在提升器件性能上发挥着极其重要的作用. 本文总结了平面p-i-n型钙钛矿太阳能电池中阴极界面修饰层（CBL）的研究进展. CBL从材料上讲可分为无机金属氧化物、金属或金属盐以及有机材料,从构成上讲可分为单层CBL、双层CBLs以及共混型CBL. 本文对这些类型的CBL分别给予详细的介绍. 最后,我们归纳出CBL在改善器件效率和稳定性上所起的作用以及理想CBL所应满足的要求,希望能为以后阴极界面修饰材料的设计提供一定的借鉴.     

Enhanced Performance of Camphorsulfonic Acid-Doped Perovskite Solar Cells

High-quality perovskite film with large grains and therefore reduced grain boundaries plays a significant role in improving the power conversion efficiency (PCE) and ensuring good long-term stability of the perovskite solar cells. In this work, we found that adding camphorsulfonic acid (CSA), a Lewis base, to the perovskite solution results in the crystallization of larger perovskite grains. By varying the concentration of CSA, we found that the optimal concentration of the additive is 1 mg/mL, which leads to an 20% increase in PCE of the cells compared to the reference CSA-free cell. Interestingly, we observed that the PCE of cells with an excess of CSA was initially poor, but may increase significantly over time, possibly due to CSA migration to the hole-transporting layer, leading to an improvement in its conductivity.     

环境友好型无铅卤化物钙钛矿太阳能电池研究进展

ABX₃(A为甲胺、甲脒等有机离子或铯离子,B为铅或锡等金属离子,X为溴、碘等卤化物离子)卤化物钙钛矿材料具有优异的光电特性,是当前太阳能电池研究的前沿和热点之一。然而,这类太阳能电池普遍面临含毒性元素铅和稳定性差等问题,极大地阻碍了钙钛矿太阳能电池商业化应用进程。因此,发展新型高效无铅钙钛矿太阳能电池势在必行。本文评述了环境友好型无铅卤化物钙钛矿太阳能电池的最新研究动态和进展,探讨了该类太阳能电池的制备、性能及其稳定性等问题,展望了其未来发展趋势。     

Retardation of Trap-Assisted Recombination in Lead Halide Perovskite Solar Cells by a Dimethylbiguanide Anchor Layer

Reaching the full potential of solar cells based on photo-absorbers of organic-inorganic hybrid perovskites requires highly efficient charge extraction at the interface between perovskite and charge transporting layer. This demand is generally challenged by the presence of under-coordinated metal or halogen ions, causing surface charge trapping and resultant recombination losses. These problems can be tackled by introducing a small molecule interfacial anchor layer based on dimethylbiguanide (DMBG). Benefitting from interactions between the nitrogen-containing functional groups in DMBG and unsaturated ions in CH₃NH₃PbI₃ perovskites, the electron extraction of TiO₂ is dramatically improved in association with reduced Schottky–Read–Hall recombination, as revealed by photoluminescence spectroscopy. As a consequence, the power conversion efficiency of CH₃NH₃PbI₃ solar cells is boosted from 17.14 to 19.1 %, showing appreciably reduced hysteresis. The demonstrated molecular strategy based on DMBG enables one to achieve meliorations on key figures of merit in halide perovskite solar cells with improved stability.     

钙钛矿型太阳电池研究进展

自从2009年钙钛矿材料被应用到太阳电池领域,到现在仅6年的时间里,钙钛矿型太阳电池的光伏转换效率从约3%提高到20.1%,受到全球瞩目。 本文对近年来钙钛矿型太阳电池的发展进行了综述,介绍了钙钛矿吸光材料的性能及其制备,总结了钙钛矿型太阳电池器件结构及其内在机理,探讨了该类型电池待突破的方向和可能的解决途径,阐述了钙钛矿型太阳电池的进展历程,展望了未来发展方向。     

Reducing Detrimental Defects for High‐Performance Metal Halide Perovskite Solar Cells

In several photovoltaic (PV) technologies, the presence of electronic defects within the semiconductor band gap limit the efficiency, reproducibility, as well as lifetime. Metal halide perovskites (MHPs) have drawn great attention because of their excellent photovoltaic properties that can be achieved even without a very strict film‐growth control processing. Much has been done theoretically in describing the different point defects in MHPs. Herein, we discuss the experimental challenges in thoroughly characterizing the defects in MHPs such as, experimental assignment of the type of defects, defects densities, and the energy positions within the band gap induced by these defects. The second topic of this Review is passivation strategies. Based on a literature survey, the different types of defects that are important to consider and need to be minimized are examined. A complete fundamental understanding of defect nature in MHPs is needed to further improve their optoelectronic functionalities.     

When Aggregation-Induced Emission Meets Perovskites: Efficient Defect-Passivation and Charge-Transfer for Ambient Fabrication of Perovskite Solar Cells

The intrinsic defects in perovskite film can serve as non-radiative recombination center to limit the performance and stability of metal halide perovskite solar cells (PSCs). The additive engineering in perovskite film is always applied to produce high-efficiency PSCs in recent years. Here, a typical donor-acceptor (D−A) structured aggregation-induced emission (AIE) molecule tetraphenylethene-2-dicyano-methylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TPE-TCF) was introduced into perovskite film. The D−A structure of TPE-TCF molecule provided additional charge transfer channels, contributing to transporting electron of TPE-TCF-based device. The cyano (C≡N) of TPE-TCF can interact with the uncoordinated Pb to from a relatively stable intermediate, PbI₂⋅TPE-TCF, resulting in the slower crystal growth, reduced the defects at the grain boundaries and suppressed carrier recombination. As a consequence, the power conversion efficiency (PCE) of TPE-TCF-modified PSCs achieved a remarkably enhanced from 15.63 to 19.66 % with negligible hysteresis, which was prominent in methylammonium lead iodide-based devices fabricated under ambient condition. Furthermore, the PSCs modified by AIE molecule possessed an outstanding stability and maintain about 86 % of the initial PCE after 300 h storage in air at 25–35 °C with a high relative humidity (RH) of ≈85 %. This work suggests that incorporating AIE molecule into perovskite is a promising strategy for facilitating high-performance PSCs commercialization in ambient environment without glovebox.     

In Quest of Environmentally Stable Perovskite Solar Cells: A Perspective

Inorganic-organic halide perovskites pose a once-in-a-generation opportunity to revolutionize photovoltaic technology as they are excellent semiconductor candidates with a combination of many desirable attributes. Specifically, halide perovskite solar cells with extremely high device efficiency are easily fabricated and present great promise for commercialization in the near future. However, their non-ideal environmental stability under real operating conditions can limit their further development. Both the academic and industrial research communities have been devoting considerable effort to overcome this critical deficiency through material and device engineering. Significant progress has been reported in this direction, and in this perspective, we review the recent strategies that promise to improve solar cell stability focusing on two interwoven topics. The first one is the development of environmentally stable semiconductor materials, while the second one is dedicated to the reported progress in improving solar cell device stability. Although, the currently adopted methods have not resolved the above problems, yet they build a foundation of principles for future advances to overcome them. In this regard, we believe commercial perovskite-related photovoltaics might indeed be on the horizon, not only replacing the currently commercially available ones, but also improving them.     

全无机钙钛矿太阳电池的制备及稳定性

全无机钙钛矿太阳电池因其热稳定性好、载流子迁移率高,可用于制备叠层电池等优点备受关注.随着人们对全无机钙钛矿太阳电池的深入研究和制备工艺的持续优化,全无机钙钛矿太阳电池的光电转换效率已经突破19％.然而,全无机钙钛矿材料相稳定性较差,这使得实现全无机钙钛矿太阳电池在空气环境下制备和长期使用面临巨大挑战.众多科研工作者通...     

A Comprehensive Review on Perovskite Solar Cells Integrated Photo-supercapacitors and Perovskites-Based Electrochemical Supercapacitors

Perovskite solar cells (PSCs) have rapidly become a prevalent photovoltaic technology owing to their simple structure, low processing cost, and remarkable increase in solar-to-electric power conversion efficiency (PCE). However, the intermittent nature of solar radiation induces some technical and financial challenges for its practical applications as a reliable power source. To address this issue, the integration of PSCs with supercapacitors (SCs) in the form of integrated photo-supercapacitors (IPSs) has gathered significant attention. This integration can balance energy availability and demand, reduce energy wastage, and stabilize power output for portable and wearable electronics. Meanwhile, the excellent optoelectronic properties with mixed electronic and ionic conductivity of metal halide perovskites (MHPs) have expanded their application as electrode and electrolyte materials for SCs and photo-supercapacitors (PSs) applications. This review provides an all-inclusive summary of the current state-of-the-art research progress of PSCs-IPSs and MHPs-based SCs and PSs by highlighting their basics and integration approaches. It also discusses the challenges and prospects of these materials and technologies.     

界面修饰策略在钙钛矿太阳能电池中的应用

目前钙钛矿太阳能电池的认证效率已达25.2%,被认为是下一代最有希望的薄膜太阳能电池候选者。但通过溶液加工方法制备的钙钛矿薄膜不可控的形貌与较差的结晶性是制约器件稳定性提升和大面积生产的主要原因。为了有效解决这一难题,研究者们通常在电荷传输层与钙钛矿层之间进行界面修饰。本文从界面修饰的角度出发,总结了不同界面修饰策略在钙钛矿太阳能电池中的应用,并展望了界面修饰在低成本和大面积钙钛矿太阳能电池的应用前景。