A Cation‐Exchange Approach for the Fabrication of Efficient Methylammonium Tin Iodide Perovskite Solar Cells

Tin‐based halide perovskite materials have been successfully employed in lead‐free perovskite solar cells, but the overall power conversion efficiencies (PCEs) have been limited by the high carrier concentration from the facile oxidation of Sn²⁺ to Sn⁴⁺. Now a chemical route is developed for fabrication of high‐quality methylammonium tin iodide perovskite (MASnI₃) films: hydrazinium tin iodide (HASnI₃) perovskite film is first solution‐deposited using presursors hydrazinium iodide (HAI) and tin iodide (SnI₂), and then transformed into MASnI₃ via a cation displacement approach. With the two‐step process, a dense and uniform MASnI₃ film is obtained with large grain sizes and high crystallization. Detrimental oxidation is suppressed by the hydrazine released from the film during the transformation. With the MASnI₃ as light harvester, mesoporous perovskite solar cells were prepared, and a maximum power conversion efficiency (PCE) of 7.13 % is delivered with good reproducibility.     

Chitosan‐Assisted Crystallization and Film Forming of Perovskite Crystals through Biomineralization

Biomimetic mineralization is a powerful approach for the synthesis of advanced composite materials with hierarchical organization and controlled structure. Herein, chitosan was introduced into a perovskite precursor solution as a biopolymer additive to control the crystallization and to improve the morphology and film‐forming properties of a perovskite film by way of biomineralization. The biopolymer additive was able to control the size and morphology of the perovskite crystals and helped to form smooth films. The mechanism of chitosan‐mediated nucleation and growth of the perovskite crystals was explored. As a possible application, the chitosan–perovskite composite film was introduced into a planar heterojunction solar cell and increased power conversion efficiency relative to that observed for the pristine perovskite film was achieved. The biomimetic mineralization method proposed in this study provides an alternative way of preparing perovskite crystals with well‐controlled morphology and properties and extends the applications of perovskite crystals in photoelectronic fields, including planar‐heterojunction solar cells.     

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.     

Fast-growing procedure for perovskite films in planar heterojunction perovskite solar cells

A fast-growing procedure (FGP) to fabricate perovskite films with large grain sizes is described in this article. In the FGP method, the perovskite precursor solution is coated onto the substrates at a temperature of ~240 ℃. The solvent in the precursor solution evaporates quickly in about 2 s, resulting in the rapid formation of a perovskite film without further annealing process. Millimeter-scale perovskite grain clusters are obtained in the film. Based on such perovskite films, fabricated planar heterojunction perovskite solar cells give a power conversion efficiency (PCE) above 8%.     

An Efficient and Stable Perovskite Solar Cell with Suppressed Defects by Employing Dithizone as a Lead Indicator

The defects in perovskite films are one of the most non-negligible factors that can attenuate the performances of perovskite solar cell. This work fabricates defect-reduced perovskite film by using the lead indicator (dithizone) as an additive of perovskite functional layer. The dithizone can retard the crystallization rate of perovskite films, passivate the defects, and enhance the structure stability of perovskite by coordinating with lead atoms. As a result, the device doped with dithizone yields outstanding power conversion efficiency and stability.     

高效钙钛矿太阳能电池吸光层的设计与优化

本文设计了多元混合钙钛矿吸光层涂布液配方,并采用两步法组装了钙钛矿电池器件。由于两步法制备钙钛矿吸光层存在配方和工艺相对复杂的问题,导致电池器件性能难以提升,因此,本文采用正交实验的方法,筛选出影响电池器件性能的关键因素。针对关键因素设计了系列实验,通过观察钙钛矿层薄膜形貌,测试钙钛矿太阳能电池器件的光电性能,并采用多种表征手段研究了钙钛矿层薄膜性质,确定了关键因素的添加量,最后优选出钙钛矿电池吸光层的最佳配方,得到高质量的钙钛矿薄膜,电池的光电转换效率达到21.1%。     

锡钙钛矿太阳能电池的进展与展望

金属卤素钙钛矿是目前最有前景的高效低成本新型太阳能电池材料,但是目前还存在环境友好性和理论效率极限较低的问题。锡钙钛矿环境友好,而且其带隙更窄理论转换效率更高,吸引了广泛的关注。锡钙钛矿太阳能电池(TPSC)近年来发展迅速,是目前效率最高的无铅钙钛矿太阳能电池。本文先介绍了锡钙钛矿的晶体结构、能带结构和光电性质,然后总结了最近在锡钙钛矿领域有代表性的工作和提高光电转化效率的策略,最后讨论了锡钙钛矿发展面临的挑战和未来的发展方向。     

Alkyl-Chain-Regulated Charge Transfer in Fluorescent Inorganic CsPbBr3 Perovskite Solar Cells

Improved charge extraction and wide spectral absorption promote power conversion efficiency of perovskite solar cells (PSCs). The state-of-the-art carbon-based CsPbBr₃ PSCs have an inferior power output capacity because of the large optical band gap of the perovskite film and the high energy barrier at perovskite/carbon interface. Herein, we use alkyl-chain regulated quantum dots as hole-conductors to reduce charge recombination. By precisely controlling alkyl-chain length of ligands, a balance between the surface dipole induced charge coulomb repulsive force and quantum tunneling distance is achieved to maximize charge extraction. A fluorescent carbon electrode is used as a cathode to harvest the unabsorbed incident light and to emit fluorescent light at 516 nm for re-absorption by the perovskite film. The optimized PSC free of encapsulation achieves a maximum power conversion efficiency up to 10.85 % with nearly unchanged photovoltaic performances under 80 %RH, 80 °C, or light irradiation in air.     

平板结构高效钙钛矿太阳能电池的旋涂溶液溶剂工程

自2009年首次应用于太阳能电池中以来,有机铅卤化物钙钛矿材料得到了极大关注.据文献报道,有机铅卤化物钙钛矿材料在不同结构的太阳能电池中都得到了应用,其中与有机太阳能电池类似的平板结构钙钛矿具有结构简单、制备容易等优点,非常适合用于柔性电池和多节电池等各种应用.在平板结构的太阳能电池中,制备高质量的钙钛矿薄膜至关重要.真空热蒸镀法虽然可以制备厚度均匀的钙钛矿薄膜,获得高的器件性能,但是设备成本较高,不利于大规模生产.而在溶液法中,早期的一步旋涂法和两步法由于没有多孔金属氧化物的支撑,很难制备均匀的钙钛矿平板薄膜;而气相辅助的两步法虽然制备的薄膜比较均匀,但反应时间却比较长.程一兵研究组采用在旋涂N,N-二甲基甲酰胺(DMF)溶液时滴加氯苯使钙钛矿快速析出结晶的方法,制备了高质量的均匀的CH3NH3PbI3薄膜. Seok研究组采用1,4-丁内酯(GBL)和二甲基亚砜(DMSO)的混和溶剂,在旋涂时滴加甲苯的方法,在多孔二氧化钛上也制得了均匀的CH3NH3PbI3薄膜,取得了很高转化效率(16.7%),但缺少对不同溶剂比例的细致研究,另外,也没有对平板结构电池性能进行研究.
　　本文采用DMF-DMSO和GBL-DMSO作为混合溶剂在二氧化钛致密层上旋涂制备了平板结构的钙钛矿薄膜,并且对混合溶剂的比例对器件性能的影响进行了详细的考察和优化.当纯DMF或纯GBL作为旋涂溶剂时,得到的CH3NH3PbI3钙钛矿薄膜含有大量不连续的晶粒,表面的覆盖度很差,对入射光的吸收远弱于连续均匀的薄膜.而且XRD结果表明,纯DMF或纯GBL作为旋涂溶剂的薄膜残留有前驱体的杂质,对器件性能非常不利.而采用DMSO作为旋涂溶剂时,制得的薄膜表面则比较均匀,几乎达到100%的覆盖.这主要是由于在旋涂溶液中形成了PbI2-CH3NH3I-DMSO的中间相,这样可以避免纯DMF或纯GBL溶剂蒸发时PbI2和CH3NH3I的剧烈反应,因此退火后制得的CH3NH3PbI3薄膜非常均匀.然而由于纯DMSO的高粘度和低挥发速度,并不是非常适合作为旋涂溶剂,因此我们将DMF和GBL加入到DMSO中形成混合溶剂来考察对制备的钙钛矿薄膜质量和器件性能的影响.扫描电镜结果表明,加入20%~40%体积分数的DMF时,形成的薄膜表面非常均匀而且晶粒尺寸很大,达到微米级别,这样有利于减少晶界处的复合,提高电池性能.继续增加DMF比例会导致晶粒减小,晶界和孔隙增多,薄膜表面也更加粗糙.而加入GBL时得到的晶粒要远小于加入DMF时的尺寸,并且随着GBL比例的增加,薄膜的表面变得更加粗糙,孔隙明显增多,严重影响电池性能. XRD结果表明,纯DMSO和混合溶剂制得的薄膜都没有前驱体的残留.紫外可见吸收光谱表明,随着DMF比例的增加,吸收逐渐增强;而随着GBL比例的增加,吸收逐渐减弱.这主要由于不同比例溶剂制得的薄膜厚度有所差异造成的.
　　由相关的薄膜制备的平板结构太阳能电池I-V测试表明：当使用DMF-DMSO混合溶剂时,随着DMF比例由0%增至40%,短路电流和开路电压逐渐增加,填充因子略微减小,总体上导致光电转化效率逐渐增大.随着DMF继续增多,开路电压和填充因子的减小导致转化效率逐渐降低.而当使用GBL-DMSO混合溶剂时,主要受到短路电流的影响,电池的效率明显低于含DMF的混合溶剂的情况,而且随着GBL增多,电池效率逐渐降低.电池的最高转化效率达到了16.5%,最高功率点下固定电压扫描得到的稳态效率也达到了14.4%,高于报道中采用类似结构的电池的性能.由于在整个电池制备过程中,整个实验过程都低于100°C,该方法非常适合未来推广到柔性太阳能电池和多节太阳能电池上.     

Improved Photovoltaic Performance from High Quality Perovskite Thin Film Grown with the Assistance of PC71BM

The strategy of sequentially spin-coating a perovskite film from the perovskite precursor and an electron transporting layer of [6,6]-phenyl-C_(71)-butyric acid methyl ester(PC_(71)BM) is developed to simplify the fabrication procedure of perovskite solar cells. X-ray diffraction and scanning electron microscopy indicate that PC_(71)BM film on perovskite layer can retard the evaporation of dimethyl sulfoxide(DMSO) efficiently, thus prolonging the transformation of intermediate phase to perovskite crystals, leading to a high quality perovskite thin film. The solar cells with the structure of indium tin oxides(ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS)/CH_3NH_3PbI_3/PC_(71)BM/bathocuproine(BCP)/Ag made from this simplified method exhibit a higher efficiency(12.68%) than those from the conventional one-step method(9.49%).     

压强对钙钛矿薄膜形貌和结晶性影响的研究

采用新型简便的方法控制钙钛矿层薄膜的结晶过程,对优化制备工艺、获得高性能器件至关重要。本文采用调节真空度的方法有效控制钙钛矿层结晶,系统地研究了压强的作用及其对晶体生长、薄膜形成及器件性能的影响。采用扫描电子显微镜(SEM)、紫外-可见吸收光谱、X射线衍射光谱(XRD)谱图等手段对钙钛矿层的形貌及结晶程度进行了分析表征。在此基础上,制备出器件结构为Glass/ITO/PEDOT:PSS/CH3NH3PbI3/PCBM/Al的钙钛矿太阳能电池,考察了不同压强下的器件性能。结果表明:随压强降低,钙钛矿层结晶程度明显提高,孔洞减少,表面覆盖率提高。同时,器件的短路电流、填充因子以及光电转化效率均随压强降低而提高,器件效率由原来的10.38%提高到12.36%,提高了19%。     

Alkyl‐Chain‐Regulated Charge Transfer in Fluorescent Inorganic CsPbBr3 Perovskite Solar Cells

Improved charge extraction and wide spectral absorption promote power conversion efficiency of perovskite solar cells (PSCs). The state‐of‐the‐art carbon‐based CsPbBr₃ PSCs have an inferior power output capacity because of the large optical band gap of the perovskite film and the high energy barrier at perovskite/carbon interface. Herein, we use alkyl‐chain regulated quantum dots as hole‐conductors to reduce charge recombination. By precisely controlling alkyl‐chain length of ligands, a balance between the surface dipole induced charge coulomb repulsive force and quantum tunneling distance is achieved to maximize charge extraction. A fluorescent carbon electrode is used as a cathode to harvest the unabsorbed incident light and to emit fluorescent light at 516 nm for re‐absorption by the perovskite film. The optimized PSC free of encapsulation achieves a maximum power conversion efficiency up to 10.85 % with nearly unchanged photovoltaic performances under 80 %RH, 80 °C, or light irradiation in air.     

Supersaturation controlled growth of MAFAPbI<Subscript>3</Subscript> perovskite film for high efficiency solar cells

Controlling the nucleation and growth of organic-inorganic hybrids perovskite is of key importance to improve the morphology and crystallinity of perovskite films. However, the growth mechanism of perovskite films based on classical crystallization theory is not fully understood. Here, we develop a supersaturation controlled strategy (SCS) to balance the nucleation and crystal growth speeds. By this strategy, we are able to find an ideal supersaturation region to realize a balance of nucleation and crystal growth, which yields highly crystallized perovskite films with micrometer-scale grains. Besides, we provide a thoughtful analysis of nucleation and growth based on the fabrication of the perovskite films. As a result, the highest photovoltaic power conversion efficiencies (PCE) of 19.70% and 20.31% are obtained for the planar and the meso-superstructured devices, respectively. This strategy sheds some light for understanding the film growth mechanism of high quality perovskite film, and it provides a facile strategy to fabricate high efficiency perovskite solar cells.     

Supersaturation controlled growth of MAFAPbI_3 perovskite film for high efficiency solar cells

Controlling the nucleation and growth of organic-inorganic hybrids perovskite is of key importance to improve the morphology and crystallinity of perovskite films. However, the growth mechanism of perovskite films based on classical crystallization theory is not fully understood. Here, we develop a supersaturation controlled strategy(SCS) to balance the nucleation and crystal growth speeds. By this strategy, we are able to find an ideal supersaturation region to realize a balance of nucleation and crystal growth, which yields highly crystallized perovskite films with micrometer-scale grains. Besides, we provide a thoughtful analysis of nucleation and growth based on the fabrication of the perovskite films. As a result, the highest photovoltaic power conversion efficiencies(PCE) of 19.70% and 20.31% are obtained for the planar and the meso-superstructured devices, respectively. This strategy sheds some light for understanding the film growth mechanism of high quality perovskite film, and it provides a facile strategy to fabricate high efficiency perovskite solar cells.     

钙钛矿太阳能电池中吸收层的研究进展

钙钛矿太阳能电池因具有成本低、制备容易和光电性能优异等突出特点受到了广泛关注.钙钛矿太阳能电池能量转化效率已从2009年的3.8%提升到2019年的25.2%.我们在文中重点总结了钙钛矿电池吸收层的制备工艺,掺杂和晶体组成、结构调控方面取得的重要进展,以及这些突破对电池效率提高的贡献,同时也提出了钙钛矿太阳能电池发展仍需要解决的问题.     

Porous copper zinc tin sulfide thin film as photocathode for double junction photoelectrochemical solar cells

Porous copper zinc tin sulfide (CZTS) thin film was prepared via a solvothermal approach. Compared with conventional dye-sensitized solar cells (DSSCs), double junction photoelectrochemical cells using dye-sensitized n-type TiO(2) (DS-TiO(2)) as the photoanode and porous p-type CZTS film as the photocathode shows an increased short circuit current, external quantum efficiency and power conversion efficiency.     

Bulk heterojunction perovskite solar cells incorporated with solution-processed TiOx nanoparticles as the electron acceptors

In the past ten years, perovskite solar cells were rapidly developed, but the intrinsic unbalanced charge carrier diffusion lengths within perovskite materials were not fully addressed by either a planar heterojunction or meso-superstructured perovskite solar cells. In this study, we report bulk heterojunction perovskite solar cells, where perovskite materials CH₃NH₃PbI₃ is blended with solution-processed n-type TiO_x nanoparticles as the photoactive layer. Studies indicate that one-step solution-processed CH₃NH₃PbI₃:TiO_x bulk-heterojunction thin film possesses enhanced and balanced charge carrier mobilities, superior film morphology with enlarged crystal sizes, and suppressed trap-induced charge recombination. Thus, bulk heterojunction perovskite solar cells by CH₃NH₃PbI₃ mixed with 5 wt% of TiO_x, which is processed by one-step method rather than typical two-step method, show a short-circuit current density of 20.93 mA/cm², an open-circuit voltage of 0.90 V, a fill factor of 80% and with a corresponding power conversion efficiency of 14.91%, which is more than 30% enhancement as compared with that of perovskite solar cells with a planar heterojunction device structure. Moreover, bulk heterojunction perovskite solar cells possess enhanced device stability. All these results demonstrate that perovskite solar cells with a bulk heterojunction device structure are one of apparent approaches to boost device performance.     

界面钝化策略:提高钙钛矿太阳能电池的稳定性

近年来,新兴起的有机无机杂化钙钛矿太阳能电池突飞猛进,在短短十年里其光电转化效率从3.8%迅速发展到目前25.2%的认证效率,被视为最具有应用潜力的新型高效率太阳能电池之一。虽然钙钛矿太阳能电池具有很高的光电转换效率已与多晶硅薄膜电池相媲美,但是电池的长期稳定性仍是阻碍其商业化的一大挑战。钙钛矿表面和晶界存在大量的缺陷,界面钝化来提高钙钛矿太阳能电池的稳定性是非常重要且有效的策略。二维钙钛矿材料是有机胺层与无机层交替的层状钙钛矿,具有体积较大的有机铵阳离子,与传统的三维钙钛矿材料相比对于环境的稳定性较好,并且结构灵活可调,在三维钙钛矿表面修饰二维钙钛矿层钝化缺陷,在提高钙钛矿太阳能电池效率的同时又保证了稳定性,另外,合适的钝化剂分子也能够非常有效地钝化缺陷。本文总结了钙钛矿太阳能电池的不稳定因素,归纳了钙钛矿太阳能电池界面钝化方面的研究进展,指出了二维钙钛矿材料发展的巨大潜力以及寻找合适钝化剂分子的原则,期望能够为获得高性能的钙钛矿太阳能电池进而实现商业化提供有益的指导。     

离子液体对钙钛矿太阳能电池性能的影响

利用1-乙基-3-甲基咪唑溴盐(EMIMBr)、1-己基-3-甲基咪唑溴盐(HMIMBr)、双三氟甲烷磺酰亚胺锂(LiTFSI)以及1-乙基-3-甲基咪唑氯盐(EMICl)和双氟磺酰亚胺钾(KFSI)制备了1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐(EMITFSI)、1-己基-3-甲基咪唑双三氟甲磺酰亚胺盐(HMITFSI)和1-乙基-3-甲基咪唑鎓二(氟甲磺酰基)亚胺盐(EMIFSI)3种离子液体。 用氯苯稀释的离子液体对钙钛矿活性层进行浸泡处理,探究了离子液体对钙钛矿形貌以及钙钛矿太阳能电池性能的影响。 结果表明,HMITFSI处理后太阳能电池的填充因子从0.71提高到了0.74,光电转换效率也有了一定提高,钙钛矿薄膜的表面形貌得到了改善,而EMITFSI和EMIFSI的处理反而降低了钙钛矿太阳能电池的性能,证实离子液体可以影响钙钛矿的结晶形貌。     

Inkjet-Printed TiO2/Fullerene Composite Films for Planar Perovskite Solar Cells

Perovskite solar cells have garnered and held international research interest, due to ever-climbing power conversion efficiency values, now >25 %. Some high efficiency configurations utilize a compact TiO₂ layer underneath a mesoporous TiO₂ layer, both of which require high temperature annealing steps that could hinder perovskite commercialization. To address the high thermal budget, we chose to use inkjet-printing to combine the two layers into a single TiO₂ film, which incorporates both nanoparticle and molecular precursor as well as organic fullerene additives. We printed the ink on fluorine-doped tin oxide, and after annealing at various temperatures, we found that 400 °C was the optimum annealing temperature for the inkjet-printed electron transport layers, which is significantly lower than the 500 °C required to anneal typical mesoporous TiO₂ films.