锡基钙钛矿太阳能电池研究进展

自2009年以来,有机-无机卤化物钙钛矿因其独特的光学和电学性能,在光电材料领域受到了广泛的研究,尤其是Pb基的卤化物钙钛矿太阳能电池,目前光电转换效率高达创纪录的约25.2%,显示出强大的商业化潜力。然而,Pb元素的毒性及因而导致的环境隐患问题,一直是其产业化过程中的顾虑之一。因此,寻求能替代Pb的环境友好的元素,是一个十分重要的课题。Pb基钙钛矿材料优异的光电特性来源于Pb²⁺的最外层6s2孤对电子,与Pb元素同主族的Sn元素能够形成三维钙钛矿结构且同样具有惰性5s2外层电子结构,因而是替代Pb的首选。本文系统地介绍了Sn基钙钛矿的光学和电学性质,并从薄膜制备方法和不同的器件结构方面介绍Sn基钙钛矿太阳能电池的最新进展。     

Using steric hindrance to manipulate and stabilize metal halide perovskites for optoelectronics

The chemical instability of metal halide perovskite materials can be ascribed to their unique properties of softness, in which the chemical bonding between metal halide octahedral frameworks and cations is the weak ionic and hydrogen bonding as in most perovskite structures. Therefore, various strategies have been developed to stabilize the cations and metal halide frameworks, which include incorporating additives, developing two-dimensional perovskites and perovskite nanocrystals, etc. Recently, the important role of utilizing steric hindrance for stabilizing and passivating perovskites has been demonstrated. In this perspective, we summarize the applications of steric hindrance in manipulating and stabilizing perovskites. We will also discuss how steric hindrance influences the fundamental kinetics of perovskite crystallization and film formation processes. The similarities and differences of the steric hindrance between perovskite solar cells and perovskite light emission diodes are also discussed. In all, utilizing steric hindrance is a promising strategy to manipulate and stabilize metal halide perovskites for optoelectronics.

Manipulation on steric hindrance can influence the fundamental kinetics of perovskite crystallization and film formation, therefore stabilizing and passivating perovskite structures, and promoting the commercialization of stable perovskite devices.     

A Review on Cs-Based Pb-Free Double Halide Perovskites: From Theoretical and Experimental Studies to Doping and Applications

Despite the progressive enhancement in the flexibility of Pb-based perovskites for optoelectronic applications, regrettably, they are facing two main challenges; (1) instability, which originates from using organic components in the perovskite structure, and (2) toxicity due to Pb. Therefore, new, stable non-toxic perovskite materials are demanded to overcome these drawbacks. The research community has been working on a wide variety of Pb-free perovskites with different molecular formulas and dimensionality. A variety of Pb-free halide double perovskites have been widely explored by different research groups in search for stable, non-toxic double perovskite material. Especially, Cs-based Pb-free halide double perovskite has been in focus recently. Herein, we present a review of theoretical and experimental research on Cs-based Pb-free double halide perovskites of structural formulas Cs₂M⁺M³⁺X6 (M⁺ = Ag⁺, Na⁺, In⁺ etc.; M³⁺= Bi³⁺, In³⁺, Sb³⁺; X = Cl⁻, Br⁻, I¯) and Cs₂M⁴⁺X₆ (M⁴⁺ = Ti⁴⁺, Sn⁴⁺, Au⁴⁺ etc.). We also present the challenges faced by these perovskite compounds and their current applications especially in photovoltaics alongside the effect of metal dopants on their performance.     

Recent advances of lead-free metal halide perovskite single crystals and nanocrystals: synthesis,crystal structure,optical properties,and their diverse applications

Lead halide hybrid perovskites have received massive research attention because of their unique inherent photophysical properties that driven them for potential application in the fields of photovoltaics, light-emitting devices, lasing, X-ray detector, and so on. Perovskite single crystals and nanocrystals are generally synthesized via various low-cost solution-processed techniques. The emergence of simple growth approaches of perovskite structures enable to fabricate low-cost and highly efficient devices. However, toxicity of Pb atoms and instability of perovskite structures obstruct further commercialization of these technologies. Recent efforts have been shifted to discover novel, eco-friendly, and stable lead-free metal halide perovskite (LFHP) materials and exploring their different growth processes for various device applications. This review aims to provide an up-to-date analysis of recent progress report on LFHPs and will mainly focus on their growth processes in the single crystalline and nanocrystalline forms. This review also tries to understand how the perovskite crystal structure impacts on their fundamental properties. In addition, we discuss the current progress in various field of applications and their future aspects.     

Rapid Growth of Halide Perovskite Single Crystals: From Methods to Optimization Control

Metal halide perovskites are emerging as new generation optoelectronic materials due to their high carrier mobility, long carrier diffusion length and large light absorption coefficient, which have broad applications in solar cell, light‐emitting diode, laser, photodetector and transistors. Perovskite single crystal is an ideal platform for discerning the intrinsic properties of these materials. In some cases, perovskite single crystals are better candidates to gain high performance optoelectronics. However, the growth of perovskite single crystals is time and cost consuming, which has an obvious disadvantage for device exploration. Therefore, fast growth technique is highly desirable in not only promoting the use of perovskites in commercial applications but also facilitating deep physical investigation of the materials. In this review, we summarize thoroughly the development of fast growth of the halide perovskites single crystal. Specifically, we highlight the progress of rapid growth techniques with emphasis on the optimization control.     

Band‐Edge Luminescence from Oxide and Halide Perovskite Semiconductors

Because perovskite crystals exhibit unique magnetic, conductive, and optical properties, they have been the subject of many fundamental investigations in various research fields. However, investigations related to their use as optoelectronic device materials are still in their early days. Regarding oxide perovskites, which have been investigated for a long time, the efficiency of photoluminescence (PL) induced by band‐to‐band transitions is extremely low because of the localized nature of the carriers in these materials. On the other hand, halide perovskites exhibit a highly efficient band‐edge PL attributable to the recombination of delocalized photocarriers. Therefore, it is expected that this class of high‐quality materials will be advantageous for optoelectronic devices such as solar cells and light‐emitting diodes. In this Minireview, we discuss various aspects of the PL properties and carrier dynamics of SrTiO₃ and CH₃NH₃PbX₃ (X=I, Br), which are representative oxide and halide perovskites.     

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。     

手性钙钛矿的结构维度与光电特性

近十年,有机无机杂化钙钛矿凭借其新颖优异的光电特性而引起广泛关注。最近,手性钙钛矿由于结合了钙钛矿材料和手性材料各自独特性能,在三维显示、光学信息处理、量子光学、生物探测、自旋电子等方面具有重要应用价值。根据有机、无机组分的空间分布,可以对手性钙钛矿的结构维度进行分类。本文以手性钙钛矿的不同结构维度为出发点,分别阐述了一维、二维和三维手性钙钛矿的晶体结构、光学和光电特性,包括圆二色性、圆偏振光致发光和光电探测等特性。考虑到二维手性钙钛矿具有独特的范德华层状晶体结构,重点介绍了其与其它二维材料组合成二维异质结构方面的工作。最后,分别从材料制备和器件应用的角度,总结了手性钙钛矿的重点挑战问题和未来发展方向。     

A review on two-dimensional (2D) and 2D-3D multidimensional perovskite solar cells: Perovskites structures,stability, and photovoltaic performances

Perovskite solar cells (PSCs) fabricated with two-dimensional (2D) halide and 2D-3D mixed-halide materials are remarkable for their optoelectronic properties. The 2D perovskite structures are extremely stable but show limited charge transport and large bandgap for solar cell applications. To overcome these challenges, multidimensional 2D-3D perovskite materials are used to maintain simultaneously, a long-term stability, and high performance. In this review, we discuss the recent progress and the advantages of 2D and 2D-3D perovskite materials as absorber for solar cell applications. First, we discuss the structure and the unique properties of 2D and multidimensional 2D-3D perovskites materials. Second, the stability of 2D and 2D-3D mixed perovskites and the perspects of PSCs are hashed out.     

Materials design for perovskite SOFC cathodes

Abstract  

This article focuses on perovskite materials for application as cathode material in solid oxide fuel cells. In order to develop new promising materials it is helpful to classify already known perovskite materials according to their properties and to identify certain tendencies. Thereby, composition-dependent structural data and materials properties are considered. Structural data under consideration are the Goldschmidt tolerance factor, which describes the stability of perovskites with respect to other structures, and the critical radius and lattice free volume, which are used as geometrical measures of ionic conductivity. These calculations are based on the ionic radii of the constituent ions and their applicability is discussed. A potential map of perovskites as a tool to classify simple ABO₃ perovskite materials according to their electrical conduction behavior is critically reviewed as a structured approach to the search for new cathode materials based on more complex perovskites with A and/or B-site substitutions. This article also covers the approaches used to influence electronic and the ionic conductivity. The advantage of mixed ionic electronic conductors in terms of the oxygen exchange reaction is addressed and their important properties, namely the oxygen-exchange coefficient and the oxygen diffusion coefficient, and their effect on the oxygen reduction reaction are presented.     

Two-Dimensional Halide Perovskites: Approaches to Improve Optoelectronic Properties

Three-dimensional (3D) halide perovskites (HPs) are in the spotlight of materials science research due to their excellent photonic and electronic properties suitable for functional device applications. However, the intrinsic instability of these materials stands as a hurdle in the way to their commercialization. Recently, two-dimensional (2D) HPs have emerged as an alternative to 3D perovskites, thanks to their excellent stability and tunable optoelectronic properties. Unlike 3D HPs, a library of 2D perovskites could be prepared by utilizing the unlimited number of organic cations since their formation is not within the boundary of the Goldschmidt tolerance factor. These materials have already proved their potential for applications such as solar cells, light-emitting diodes, transistors, photodetectors, photocatalysis, etc. However, poor charge carrier separation and transport efficiencies of 2D HPs are the bottlenecks resulting in inferior device performances compared to their 3D analogs. This minireview focuses on how to address these issues through the adoption of different strategies and improve the optoelectronic properties of 2D perovskites.     

钙钛矿材料制备中的溶剂配位效应

钙钛矿材料具有吸收系数大、载流子迁移率高、可溶液加工等特点,在太阳能电池、发光二极管、光电探测等领域具有潜在的应用价值。钙钛矿的光电性质与其维度、尺寸、形貌密切相关,因此研究材料的生长是实现高性能器件应用的基础。钙钛矿前驱体与溶剂之间的配位作用对钙钛矿的生长过程具有重要影响。本综述总结了钙钛矿前驱体与溶剂之间的配位作用对钙钛矿单晶、多晶薄膜、量子点三类体系制备的影响,讨论了在上述材料制备中的溶剂配位效应,特别是溶剂配位效应所形成的溶剂化物对材料生长过程,以及所制备的材料(形貌、晶相、缺陷、稳定性)的影响。最后,我们对这一研究方向存在的问题和挑战进行了分析和展望。     

新型有机-无机杂化钙钛矿发光材料的研究进展

作为近几年来光伏领域最具竞争力的材料之一,有机-无机杂化钙钛矿受到了广泛的重视。除了在光伏领域的潜在应用,钙钛矿材料也显示出了独特的光致发光与电致发光特性。本综述回顾了近期有机-无机杂化钙钛矿材料的快速发展历程,详细介绍了其在发光领域的研究进展与应用前景;概括了钙钛矿发光材料的特性及影响因素、发光原理、光谱可调节性,重点介绍了形貌对钙钛矿发光性能的影响;进而探讨了钙钛矿材料在发光二极管、激光器件以及发光场效应晶体管领域最新的应用进展。最后,展望了钙钛矿材料的关键性热点问题以及所面临的挑战,并尝试给未来钙钛矿材料的商业化途径指出方向。     

All-in-one: a new approach toward robust and solution-processable copper halide hybrid semiconductors by integrating covalent,coordinate and ionic bonds in their structures

Conventional inorganic semiconductors are best known for their superior physical properties and chemical robustness, and their widespread use in optoelectronic devices. However, implementation of these materials in many other applications has been hindered by their poor solubility and/or solution-processability, a longstanding drawback that is largely responsible for issues such as high cost. While recent progress on hybrid perovskites, an important class of inorganic–organic hybrid materials, has shed light on the development of high-performance solution processable semiconductors, they rely heavily on toxic metals and generally suffer from framework instability. To address these issues, a new group of hybrid semiconductors based on anionic copper(i) halide and cationic organic ligands has been developed. These compounds are noted as All-In-One (AIO) structures as they consist of covalently bonded anionic CuX inorganic modules that form both coordinate and ionic bonds with cationic organic ligands. Studies demonstrate that framework stability and solution processibility of these materials are greatly enhanced as a result of such bonds. In the perspective, we highlight the development of this newly emerged type of materials including their crystal structures, chemical and physical properties and possible applications. The untapped potential that the AIO approach can offer for other hybrid families is also discussed.

This Perspective features the newly emerged AIO-type Cu(i)X-based hybrid semiconductors and showcases their structural diversity, solution-processability, framework stability, important photophysical properties and related potential applications.     

蓝光钙钛矿发光二极管:机遇与挑战

金属卤化钙钛矿由于具有优异的光电性能(如:高电子/空穴迁移率,高荧光量子产率,高色纯度,以及光色可调性等),成为应用于发光二极管(LED)的理想材料。近年来,钙钛矿LED的发展十分迅速,红光和绿光钙钛矿LED的外量子效率(EQE)均已超过20%。然而,蓝光(尤其是深蓝光)钙钛矿LED的EQE以及稳定性依然相对落后,这严重制约了钙钛矿LED在高性能、广色域显示领域和高显色指数白光照明领域的应用。因此,总结现阶段蓝光钙钛矿LED的发展,并剖析其机遇与挑战,对未来蓝光甚至整个钙钛矿LED领域的发展至关重要。本文将蓝光钙钛矿LED根据光色细分为天蓝光、纯蓝光、深蓝光三大部分进行总结,回顾了三种LED器件的发展历程,并详细阐述了现阶段实现他们的主要手段以及相关的基础原理,最后分析了它们各自的问题并提出了相应的解决思路。     

反溶剂法快速合成高效发光二维锡卤钙钛矿材料

铅卤钙钛矿材料由于其优异的光电性质而受到了广泛关注. 但是, 材料中铅的毒性问题极大地阻碍了其大规模应用. 因此, 寻找与铅卤钙钛矿具有相似光电性质的非铅卤化物钙钛矿材料十分重要. 其中, 锡基卤化物钙钛矿被认为是铅基钙钛矿材料最佳的替代材料之一. 本文通过简便的反溶剂方法, 合成了一系列新型二维(RNH₃)₂SnX₄(R为烷基链, X=Br^-, I^-)钙钛矿材料. 研究结果表明, 所合成的材料具有优异的荧光发射性质, 发光量子效率高达98.5%, 比三维ASnX₃[A=Cs⁺, 甲胺(MA⁺), 甲脒(FA⁺)等]型钙钛矿表现出更好的稳定性. 本文所采用的合成方法简单易行, 有利于实现金属卤化物钙钛矿材料的大规模合成及在固态照明器件和显示器件领域的工业应用.     

Synthesis of BaZrS3 and BaHfS3 Chalcogenide Perovskite Films Using Single-Phase Molecular Precursors at Moderate Temperatures

Chalcogenide perovskites have garnered interest for applications in semiconductor devices due to their excellent predicted optoelectronic properties and stability. However, high synthesis temperatures have historically made these materials incompatible with the creation of photovoltaic devices. Here, we demonstrate the solution processed synthesis of luminescent BaZrS₃ and BaHfS₃ chalcogenide perovskite films using single-phase molecular precursors at sulfurization temperatures of 575 °C and sulfurization times as short as one hour. These molecular precursor inks were synthesized using known carbon disulfide insertion chemistry to create Group 4 metal dithiocarbamates, and this chemistry was extended to create species, such as barium dithiocarboxylates, that have never been reported before. These findings, with added future research, have the potential to yield fully solution processed thin films of chalcogenide perovskites for various optoelectronic applications.     

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。     

金属卤化物钙钛矿纳米晶高效发光二极管的制备与器件性能优化

金属卤化物钙钛矿作为一类新型的离子型直接带隙半导体材料在电致发光二极管(LED)中有着重要应用前景. 但实现其应用的前提在于金属卤化物钙钛矿材料需要保持高的发光效率和好的稳定性. 为了提高金属卤化物钙钛矿作为LED发光层的激子结合效率, 从而提升其发光效率, 设计和合成金属卤化物钙钛矿纳米晶材料是一个有效途径. 目前, 基于纳米晶材料设计的金属卤化物钙钛矿LED在绿光和红光(包括近红外光)范围已经展现了高的发光亮度和外量子效率(EQE), 其中最高EQE已经超过了20%, 但其稳定性仍无法满足器件应用的要求. 此外, 更值得关注且更重要的是, 蓝光钙钛矿LED的发光亮度和EQE目前仍然不高. 如何制备高效、 稳定的金属卤化物钙钛矿纳米晶LED, 特别是蓝光LED, 是一个具有重大应用前景且具有挑战性的课题. 本文重点介绍了金属卤化物钙钛矿纳米发光层的结构设计和合成方法及金属卤化物钙钛矿LED的研究进展, 分析了金属卤化物钙钛矿LED不稳定的原因, 并对金属卤化物钙钛矿LED研究面临的挑战和未来发展方向进行了总结与展望.