钙钛矿太阳电池综述

基于有机-无机杂化钙钛矿材料(CH₃NH₃PbX₃)制备的太阳电池效率自2009年从3.8%增长到19.6%, 因其较高的光吸收系数, 较低的成本及易于制备等优势获得了广泛关注. 钙钛矿材料不仅可以作为光吸收层, 还可用作电子和空穴传输层, 以此制备出不同结构的钙钛矿太阳电池: 介孔结构、介观超结构、平面结构、无HTM层结构和有机结构. 除此之外, 钙钛矿材料制备方法的多样性使其更具吸引力, 目前已有一步溶液法、两步连续沉积法、双源共蒸发法和溶液-气相沉积法. 本文主要介绍了钙钛矿太阳电池的发展历程、工作原理及钙钛矿薄膜的制备方法等. 详细阐述了电池每一层的具体作用和针对现有的钙钛矿结构各层材料的优化, 最后介绍了钙钛矿太阳电池所面临的问题和发展前景, 以期对钙钛矿太阳电池有进一步的了解, 为制备新型高效的钙钛矿太阳电池打下坚实的基础.     

硒化锑薄膜太阳电池的模拟与结构优化研究

采用wx-AMPS模拟软件对硒化锑(Sb_2Se_3)薄膜太阳电池进行建模仿真,将CdS, ZnO和Sn02的模型应用到Sb_2Se_3太阳电池的电子传输层中.结果显示,应用CdS和ZnO都能实现较高的器件性能,并发现电子传输层电子亲和势(Xe-ETL)的变化能够调节Sb_2Se_3太阳电池内部的电场分布,是影响器件性能的关键参数之一.过高或者过低的Xe-ETL都会使电池的填充因子降低,导致电池性能劣化.当Xe-ETL为4.2eV时,厚度为0.6μm的Sb_2Se_3太阳电池取得了最优的7.87%的转换效率.应用优化好的器件模型,在不考虑Sb_2Se_3层缺陷态的理想情况下,厚度为3μm的Sb_2Se_3太阳电池的转换效率可以达到16.55%(短路电流密度J_(SC)=34.88 mA/cm~2、开路电压V_(OC)=0.59 V、填充因子FF=80.40%).以上模拟结果表明,Sb_2Se_3薄膜太阳电池在简单的器件结构下就能够获得优异的光电性能,具有较高的应用潜力.     

锂掺杂提高硫氰酸亚铜的电学特性及在钙钛矿太阳电池中的应用

高效钙钛矿太阳电池中通常采用有机p型半导体材料作为空穴传输层.有机材料在湿度、温度、紫外照射等环境因素下会出现严重的性能衰退,加速钙钛矿太阳电池的老化,成为实现其实际应用的主要障碍之一.本文提出采用无机硫氢酸亚铜(CuSCN)作为空穴传输材料,并通过锂掺杂提高其空穴传输特性;在此基础上采用聚[双(4苯基)(2,4,6-三甲基苯基)胺]修饰CuSCN表面,避免CuSCN和碘化铅(PbI₂)间的相互作用,实现了大晶粒、致密钙钛矿薄膜的制备,最终实现了钙钛矿太阳电池性能的有效提升.本工作为稳定、高效钙钛矿太阳电池的制备提供了可借鉴的策略.     

高效率钙钛矿太阳电池发展中的关键问题

钙钛矿太阳电池的迅速发展为解决未来能源问题带来一线曙光. 但是, 钙钛矿太阳电池在高效率电池器件的可重现性、稳定性以及性能评估等方面还面临着很多问题, 严重制约其今后的发展. 本文综述了钙钛矿太阳电池面世以来发生的重要进展, 以及存在的几个关键性问题. 从器件基本结构和基本工作原理出发, 本文重点讨论了光吸收层的光谱和形貌等性质对器件性能和可重现性的影响, 阐明了电子传输层和空穴阻隔层的重要作用, 论述了空穴传输层的相关进展以及其对器件稳定性的影响. 通过对以上关键问题的讨论和总结, 本文对钙钛矿太阳电池未来的研究发展进行了展望.     

平面异质结有机-无机杂化钙钛矿太阳电池研究进展

高效低成本太阳电池的研发是太阳能光伏技术大规模推广应用的关键. 近年来兴起的有机- 无机杂化钙钛矿(以下简称钙钛矿)太阳电池因具有光电能量转换效率高、制备工艺简单等优点, 引起了学术界和产业界的广泛关注, 具有广阔的发展前景. 其中平面异质结钙钛矿太阳电池因具有结构简单, 可低温制备等诸多优点, 成为目前研究的一个重要方向. 平面异质结钙钛矿太阳电池分为n-i-p型和p-i-n型两种结构. 其中钙钛矿分别与电子传输层和空穴传输层形成两个界面, 在这两个界面上实现电子和空穴的快速分离. 电子传输层和空穴传输层分别为电子和空穴提供了独立的输运通道. 平面异质结结构有利于钙钛矿太阳电池中电子和空穴的分离、传输和收集. 此外, 该结构不需要高温烧结的多孔结构氧化物骨架, 扩大了电子和空穴传输材料的选择范围. 可以根据钙钛矿材料的能带分布及载流子传输特性, 来选择能级和载流子传输速率更为匹配的传输材料. 本文对钙钛矿的材料特性, 平面异质结结构的由来及发展进行了简要的概述. 其中重点介绍了平面异质结钙钛矿太阳电池的结构特征、工作机理、钙钛矿/电荷传输层的界面特性, 以及电池性能的优化, 包括钙钛矿薄膜制备、空穴和电子传输层的优化等. 最后对钙钛矿电池的发展前景及存在问题进行了阐述, 为今后高效、稳定钙钛矿太阳电池的研究提供参考.     

FA1-xCsxPbI3-yBry钙钛矿材料优化及太阳电池性能计算

甲脒铅碘钙钛矿(FAPbI3)因其优异的光电性能而成为新兴太阳电池最具潜力的候选材料,但是稳定性较差成为制约其发展的主要瓶颈.通过离子掺杂可以有效地改善FAPbI3的稳定性,如通过共掺杂Cs^+和Br^-形成FA1-xCsxbI3-yBry钙钛矿材料,其耐热及耐水稳定性得到显著改善.本文利用第一性原理计算了FA1-xCsxPbI3-yBry(x=0.125,y=0-0.6)体系的几何结构、电子结构和光学性质.通过分析发现Cs^+和Br^-的掺入使得体系能量降低,FA0.875Cs0.125PbI2.96 Br0.04最稳定.利用等效光学导纳法模拟计算了平面结构钙钛矿太阳电池的吸收率、载流子收集效率、外量子效率、短路电流密度、开路电压和伏安特性.对于FA1-xCsxPb I3-yBry钙钛矿太阳电池,当x=0.125,y=0.04,厚度为0.5—1.0μm时,电池的短路电流密度均为24.7mA·cm^-2,开路电压为1.06 V.结果表明Cs^+和Br^-的共掺杂在没有降低电池短路电流的同时提高了体系的稳定性,可为实验上制备高效稳定的钙钛矿太阳电池提供理论参考.     

基于聚合物非富勒烯体系PM6:Y6的钙钛矿/有机集成太阳电池光伏性能优化

通过工艺创新和薄膜优化技术成功制备基于CH₃NH₃PbI₃/PM6:Y6(BTP-4F)的钙钛矿/有机集成太阳电池(IPOSCs).通过添加剂1-8二碘辛烷DIO的调控和热退火处理,极大优化CH3NH3PbI3/PM6:Y6混合薄膜质量和获得层间欧姆接触.与此同时,近红外区有机层的空穴和电子迁移率为8.3×10^–3 cm²/(V·s)和8.8×10^–3 cm²/(V·s),可以和可见区钙钛矿层的空穴和电子迁移率相匹配,实现在微观通路上达到载流子运输平衡,导致器件具有高短路电流密度Jsc和高填充因子FF.另外,通过优化聚合物非富勒烯体系PM6:Y6质量比例混合成膜,使得薄膜中的非辐射复合位点密度和载流子复合明显减少,使得电子和空穴的提取和传输更加高效,能够提供更大的驱动力来改善载流子传输,同时形成更宽的耗尽区来抑制载流子复合以提高器件的开路电压Voc.优化的集成太阳能电池的短路电流密度提升到25.88 A/cm2,开路电压Voc增加到1...     

优化反式平面钙钛矿太阳电池性能的简便方法——利用PEDOT:PSS与DMSO共混空穴传输层

优化界面接触、增强界面处载流子传输对于提高钙钛矿电池性能具有重要意义。本研究将适量二甲基亚砜（DMSO）添加到聚（3,4-乙烯二氧噻吩）-聚（苯乙烯磺酸盐）(PEDOT∶PSS)空穴传输层中,改善了空穴传输层的导电性和空穴传输特性,有效提高了反式平面钙钛矿太阳能电池光伏性能。短路电流(J_sc)从21.29 mA/cm²提高到22.15 mA/cm²,填充因子（FF）从76.35%提高到80.09%,转换效率（PCE）从16.02%提高到17.01%。薄膜与器件性能综合测试结果表明,DMSO的掺入使PEDOT∶PSS发生适度相分离,形成更好的PEDOT导电通道,增强了PEDOT∶PSS的导电特性。稳态光致发光光谱呈现出显著的荧光猝灭效应,也表明掺杂DMSO后PEDOT∶PSS的空穴提取能力得到提高,钙钛矿活性层与阳极之间的空穴传输更加顺畅,有助于实现高达80%以上的填充因子。本研究为改善反式平面钙钛矿太阳电池或有机太阳电池光伏性能提供了一种高效、简便的方法,具有很好的现实意义。     

宽带隙钙钛矿材料及太阳电池的研究进展

金属卤化物钙钛矿太阳电池在近几年获得了巨大进展.目前单结钙钛矿太阳电池转化效率已经达到25.2%.经过带隙调整得到的1.63 e V及以上的宽带隙钙钛矿太阳电池是制备多结叠层太阳电池中顶部吸收层的最佳材料.除高效叠层太阳电池外,宽带隙钙钛矿在光伏建筑一体化以及光解水制氢等领域中也有着广阔的应用前景.然而这种钙钛矿薄膜本身缺陷较多,在光照下还容易发生卤素分离,这也是限制宽带隙钙钛矿太阳电池发展的关键因素.本文综述了目前宽带隙钙钛矿及太阳电池的发展现状,最后对其未来发展前景进行了展望.     

钙钛矿太阳电池中各功能层的光辐照稳定性研究进展

钙钛矿太阳电池简单的制备工艺、低廉的成本和优异的性能使其有望替代已产业化的硅太阳电池,革新现有能源供给结构,然而,钙钛矿太阳电池的稳定性差制约了其产业化进程,本文分别介绍了光辐照下,钙钛矿薄膜内部本征的离子迁移行为和由此产生的磁滞、荧光淬灭/增强和电池失效问题;以及典型的TiO2/钙钛矿界面的紫外光不稳定、空穴传输层和...     

锡基钙钛矿太阳能电池载流子传输层的探讨

锡基钙钛矿太阳能电池可避免铅元素对环境带来的污染,近年来已成为光伏领域的研究热点.本文以SCAPS-1D太阳能电池数值模拟软件为平台,对不同电子传输层和不同空穴传输层的锡基钙钛矿太阳能电池器件的性能进行数值仿真对比,从理论上分析不同载流子传输层的锡基钙钛矿太阳能电池的性能差异.结果显示,载流子传输层与钙钛矿层的能带对齐...     

准二维钙钛矿太阳能电池的研究进展

目前,钙钛矿太阳能电池的光电转换效率已超过25％,飞速提升的效率使得人们越来越期待商业化的应用,但钙钛矿材料的稳定性问题却是其商业化所面临的最大挑战,准二维钙钛矿有望解决这一问题.利用大的有机间隔阳离子的疏水性和热稳定性,以及更高的晶体形成能和更加稳固的结构,准二维钙钛矿能够有效提高钙钛矿的稳定性.此外,准二维钙钛矿对...     

Theoretical design of azaacene-based non-fullerene electron transport material used in inverted perovskite solar cells

ABSTRACT

Inverted perovskite solar cells (PSCs) have attracted much attention due to their low-temperature and solution-based process. Electron transport layers are important components in inverted PSCs. Non-fullerene n-type organic small molecules seem to be more attractive as electron transport layers, because their structures are easy to be synthesised and modified. In this paper, density functional theory and semi-classical Marcus electron transfer theory were used to explore the electron transport properties in three azaacene derivatives, including one experimentally reported molecule, 1,4,9,16-tetrakis((triisopropylsilyl)ethynyl)quinoxalino[2^?,3^?:4^″,5^″]cyclopenta[1^″,2^″,3^″:5^′,6^′]acenaphtho[1^′,2^′:5,6]pyrazino[2,3-b]phenazine (1), and two theoretically designed molecules (2 and 3). Compound 2 is formed by substituting i-Pr groups in compound 1 with H atoms, which is designed to evaluate the effect of i-Pr groups on the electron transport properties. Compound 3 is designed by adding one more benzopyrazine group to the conjugation structure of compound 1. It shows that i-Pr group can increase HOMO and LUMO energy levels and improve solubility in organic solvent and hydrophobicity. Enlarging conjugation can not only decrease LUMO energy level and electron reorganisation energy, but also can increase solubility and electron mobility. So our designed compound 3 is expected to be a potential electron transport material in inverted PSCs.     

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-OMeTAD, 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.     

蒸汽辅助溶液过程制备钙钛矿材料及钙钛矿太阳能电池

有机无机杂化钙钛矿材料被广泛应用于光电器件领域,特别是其作为太阳能电池的吸光材料,受到学术界和工业界越来越多的关注。钙钛矿太阳能电池的产业化进程正在进行中,而在进一步降低制备成本、提高电池转换效率的同时,研究出一种操作简单且可重复性高的制备钙钛矿薄膜的技术具有十分重要的意义。与其他传统的溶液处理方法不同,蒸汽辅助溶液过程(VASP)处理法避免了薄膜在生长过程中溶解以及溶剂化作用,抑制了晶核的形成,使薄膜快速重组,获得致密的高质量钙钛矿薄膜。目前报道,基于此薄膜制备的平面结构钙钛矿太阳能电池转换效率高达16.8%。本文综述了低温(150℃)VASP法制备的钙钛矿薄膜及光伏器件的相关研究进展,并对该技术的产业化前景做了展望。VASP制备过程简单、薄膜性能优异且可重复性高,为进一步制备大面积、高质量薄膜提供了可能。     

Advances in stable and flexible perovskite solar cells

Roll-to-roll (R2R) production is an innovative approach and is fast becoming a very popular industrial method for high throughput and mass production of solar cells. Replacement of costly indium tin oxide (ITO), which conventionally has served as the transparent electrode would be a great approach for roll to roll production of flexible cost effective solar cells. Indium tin oxide (ITO) and fluorine-doped tin oxide (FTO) are brittle and ultimately limit the device flexibility. Perovskite solar cells (PSCs) have been the centre of photovoltaic research community during the recent years owing to its exceptional performance and economical prices. The best reported PSCs fabricated by employing mesoporous TiO₂ layers require elevated temperatures in the range of 400–500 °C which limits its applications to solely glass substrates. In such a scenario developing flexible PSCs technology can be considered a suitable and exciting arena from the application point of view, them being flexible, lightweight, portable, and easy to integrate over both small, large and curved surfaces.     

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.     

Modulation of light absorption by optical spacer in perovskite solar cells

Lead halide perovskite solar cells with planar heterojunction configuration have recently attracted tremendous attention because of their excellent power conversion efficiencies. The modulation of optical absorption by using an optical spacer layer is a unique method to enhance the device efficiency. Here, we demonstrate the application of thin ZnO layer that act as an optical spacer that enhance the power conversion efficiency perovskite devices from 8.92% to 10.7%, which is mainly due to increment in short‐circuit current density by 16% compared to the reference solar cell. The simulation data revealed that ZnO acts as an optical spacer layer that shifts length (average) of electric field |E|² distribution from 500 nm to 750 nm wavelength is 25 nm in the perovskite layer. Which represents that exciton generation region is moved to near the hole transport layer that enhances the exciton dissociation efficiency and device efficiency.     

Pentacene as a hole transport material for high performance planar perovskite solar cells

A cost-effective and efficient organic semiconductor pentacene was developed as a hole transport layer (HTL) material to replace classical PEDOT:PSS for planar perovskite solar cells (PSCs). As expected, the pentacene based device exhibits power conversion efficiency (PCE) of 15.90% (J_sc of 19.44 mA/cm², V_oc of 1.07 V, and FF of 77%), comparable to the PEDOT:PSS based device (PCE of 15.65%, J_sc of 18.78 mA/cm², V_oc of 1.07 V, and FF of 77%) under the same experimental conditions. The excellent performance of vacuum deposited pentacene is mainly attributed to the high efficient charge extraction and transfer in device due to the high-quality perovskite film grown on the top of pentacene substrate and a favorable energy-level alignment together with a desired downward band bending formed at the perovskite/pentacene interface. Our research has confirmed that pentacene could be served as a promising HTL material to achieve effective and potentially economical planar type PSCs.