铅卤钙钛矿-聚合物复合材料的制备及应用

铅卤钙钛矿纳米晶具有优异的光电性能,在太阳能电池、光电探测和生物成像等领域展现出巨大的发展潜力。然而,铅卤钙钛矿纳米晶自身稳定性差的缺陷制约了其在实际生活中的应用。将铅卤钙钛矿纳米晶嵌入到聚合物中以制备钙钛矿-聚合物复合材料是近年来发展起来的一种有效增强钙钛矿稳定性的策略,特别是致密的聚合物基质赋予钙钛矿纳米晶优异的水稳定性。本文综述了近十年钙钛矿-聚合物复合材料的制备方法及在发光器件和生物医药等领域的应用,探讨了目前仍存在的一些问题和解决方法,并对未来这一领域的发展进行了展望。     

钙钛矿材料组分调控策略及其光电器件性能研究进展

近年来，钙钛矿太阳电池的光电转换效率取得了爆发式增长，这与电池中钙钛矿薄膜的制备工艺和材料组分密切相关.关于钙钛矿薄膜的制备方法，相关的研究报道及综述较多，然而钙钛矿材料组分调控方面的研究梳理工作相对缺乏.本综述总结了近年来不同组分体系钙钛矿材料的研究进展，包括有机无机铅卤钙钛矿、全无机铅卤钙钛矿、少铅钙钛矿以及无铅钙钛矿.重点介绍了不同体系中具有代表性的材料组分及其对器件性能的影响，旨在梳理通过组分调控提高钙钛矿电池的效率及稳定性的研究思路，最终实现商业化应用.     

金属离子掺杂全无机铅卤钙钛矿CsPbX_3纳米晶

无机铅卤钙钛矿CsPbX_3(X=Cl、Br、I或混合卤素)半导体纳米晶具有优异的光学和光电特性,是构筑照明、显示、光探测和光伏等多种光电器件颇有潜力的核心材料.这类材料在应用中存在的主要问题是如何协同调控或改善性能、提升稳定性并降低有毒铅的量. Pb~(2+)所在格位在决定其电子结构乃至光学和光电性能方面起着重要的作用.因此,最理想的方法是在Pb~(2+)的格位上有效且可控掺杂合适的金属离子.近年来,许多工作报道了CsPbX_3纳米晶的金属离子掺杂特性研究.为了更好地了解掺杂机制,未来开发出性能更优异的掺杂型钙钛矿材料,本文从掺杂离子、驱动力、掺杂策略及掺杂机理4个方面,分别总结了掺杂金属离子的种类及对光学和光电性能的影响,分析了掺杂剂中的阴离子和驱动力的作用,概述了主要的掺杂策略,系统阐述了后合成掺杂机理的核心思想,并指出了它们的不足之处,最后展望了今后在有效可控掺杂研究方面的一些挑战.     

表面包覆策略:提高全无机铯铅卤钙钛矿纳米晶的稳定性及其在照明显示领域的应用

全无机铯铅卤钙钛矿纳米晶具有荧光量子产率高、色纯度高、色域广等优异的光电性质,在发光二极管、太阳能电池和生物标记等领域具有广阔的应用前景。但由于其离子特性所导致该纳米晶的稳定性较差,严重阻碍了进一步推广应用。尽管已发展出许多提高稳定性的策略,如离子掺杂、表面钝化和表面包覆,但暴露于空气、水和极性溶剂等情况下如何保持钙钛矿纳米晶的稳定性仍然是目前亟待解决的重要问题。此外,钙钛矿纳米晶中的阴离子交换现象也限制了其在多色发光显示领域的应用。通过表面包覆可以有效提高钙钛矿纳米晶的稳定性,同时限制了纳米晶中的阴离子交换,因此近年来成为了科研工作者研究的热点。本文总结了造成钙钛矿纳米晶不稳定的原因,详细介绍了铅卤钙钛矿包覆工艺的研究进展及其在照明显示领域的应用,最后分析了全无机铯铅卤钙钛矿纳米晶发展过程中面临的挑战,并对未来的研究方向进行展望。     

无机铅卤钙钛矿纳米晶的合成、性能及应用

无机铅卤钙钛矿CsPbX₃(X=Cl,Br,I)纳米晶因具有较高荧光量子效率(~90%)、发光波长覆盖整个可见光谱(400~700 nm)、半高宽相对较窄(12~42 nm)等诸多优点而备受关注,这些性能使之成为当前最具有潜在应用价值的发光材料之一。 因此,近年来对该类无机铅卤钙钛矿材料的报道越来越多。 本文主要介绍了无机铅卤钙钛矿发光材料的发展历程、结构、制备方法、生长机理及当前的主要应用领域等,最后概括了无机铅卤钙钛矿发光材料在当前研究背景下所面临的问题并展望了下一阶段的发展方向,为进一步提高其光学性能及开发新型高效的无机铅卤钙钛矿发光材料奠定基础。     

卤化钙钛矿型纳米晶的光学性能及应用研究进展

本文重点论述了全无机卤化钙钛矿型(ABX_3)纳米晶的光学性能及应用.介绍了这类纳米晶的制备方法:常压溶剂热法和离子交换法,并进一步阐述其光学性能(主要包括光吸收性能和发光性能)及相关应用(主要包括发光二极管和太阳能电池及其在激光材料、光电探测器和光催化剂领域的应用).这类材料优异的光电性能使其在其它领域也具有潜在的应用价值.     

无铅卤系钙钛矿纳米晶:新一代光催化材料

由于TiO₂光催化材料具有反应速度快、稳定性好、不产生二次污染等优点,常被应用于污染物降解、CO₂还原、制氢等领域,然而TiO₂可见光利用率低,限制了其进一步广泛应用。近年来,无铅卤系钙钛矿纳米晶由于其带隙可调、可见光吸收能力强等优势在光催化领域显示出巨大的潜力。相关研究表明:无铅卤系钙钛矿纳米晶可成功应用于CO₂还原、有机污染物降解等领域,效果显著。基于此,本文首先阐述了无铅卤系钙钛矿纳米晶的制备方法,并系统地总结了其在CO₂还原、制氢、污染物降解、NO去除等领域的应用研究进展,最后就现阶段无铅卤系钙钛矿纳米晶光催化材料研究中存在的问题及今后的研究方向进行了分析和展望。     

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.     

金属卤化物钙钛矿光电材料和器件

2009年ABX₃钙钛矿晶型的甲胺铅卤CH₃NH₃PbX₃(X=I、Br、Cl)钙钛矿材料首次应用于太阳能电池,但初始报道效率低、稳定性差。2012年后,可溶液法制备的钙钛矿太阳能电池凭借其吸光系数高、激子结合能低等优点,迅速表现出低成本和高效率的突出优势,并在光电器件等交叉领域具有很强的应用潜力。因此,钙钛矿太阳能电池被Science杂志评为2013年度国际十大科技进展,是化学和材料领域特别是光伏领域新兴的变革性技术之一。钙钛矿太阳能电池材料与器件的发展一直面临大面积、高效率、稳定性和环境友好性等挑战,对应的是钙钛矿晶体可控生长、缺陷钝化、器件优化材料稳定性和铅毒性等科学问题。     

手性钙钛矿纳米材料的构筑及光电性能

金属卤化物钙钛矿纳米材料因其丰富的化学结构和优异的光电性能,已成为一种极具应用前景的半导体材料。在钙钛矿无机框架中引入有机手性分子后,能够比较容易地得到手性钙钛矿纳米材料,从而可以极大地推动智能光电材料和自旋电子器件的快速发展。本文将综述手性钙钛矿纳米材料的构筑与手性产生机理的最新研究进展,包括一维手性钙钛矿纳米线、二维及准二维手性有机-无机杂化钙钛矿纳米片、三维手性钙钛矿纳米晶、超分子组装体系中诱导的手性钙钛矿纳米晶等。值得注意的是,不同种类的手性钙钛矿纳米材料在圆二色性、圆偏振发光、铁电性、自旋电子学等方面展现出优异的光电性能及巨大的应用前景。但是,有关手性钙钛矿纳米材料的研究目前还处于初级阶段,其中很多机理还存在争议,许多基础性和应用型的工作也有待开展。     

Chemical regulation of metal halide perovskite nanomaterials for efficient light-emitting diodes

Metal halide perovskite nanomaterials emerged as attractive emitting materials for light-emitting diodes (LEDs) devices due to their high photoluminescence quantum yield (PLQY), narrow bandwidth, high charge-carrier mobility, bandgap tunability, and facile synthesis. In the past few years, it has been witnessed an unprecedented advance in the field of metal halide perovskite nanomaterials based LEDs (PeLEDs) with a rapid external quantum efficiency (EQE) increase from 0.1% to 14.36%. From the viewpoint of material chemistry, the chemical regulation of metal halide perovskite nanomaterials made a great contribution to the efficiency improvement of PeLEDs. In this review, we categorize the strategies of chemical regulation as A-site cation engineering, B-site ion doping, X-site ion exchange, dimensional confinement, ligand exchange, surface passivation and interface optimization of transport layers for improving the EQEs of PeLEDs. We also show the potentials of chemical regulation strategies to enhance the stability of PeLEDs. Finally, we present insight toward future research directions and an outlook to further improve EQEs and stabilities of PeLEDs aiming to practical applications.     

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。     

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.     

Stability of Perovskite Solar Cells: A Prospective on the Substitution of the A Cation and X Anion

In recent years, organometal trihalide perovskites have emerged as promising materials for low‐cost, flexible, and highly efficient solar cells. Despite their processing advantages, before the technology can be commercialized the poor stability of the organic–inorganic hybrid perovskite materials with regard to humidity, heat, light, and oxygen has be to overcome. Herein, we distill the current state‐of‐the‐art and highlight recent advances in improving the chemical stability of perovskite materials by substitution of the A‐cation and X‐anion. Our hope is to pave the way for the rational design of perovskite materials to realize perovskite solar cells with unprecedented improvement in stability.     

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.     

A hybrid organic-inorganic perovskite with robust SHG switching

Owing to the diversity of structure and potential applications in the field of electrics,sensors,and light-emitting diodes,lead halide perovskites have attracted great attention in recent years.Especially those lead halide perovskites with non-centrosymmetric crystal structures usually exhibit nonlinear optical（NLO） characteristics,which may endow them photoelectricity switching functionality.In this work,a lead-based hybrid organic-inorganic perovskite（HOIP） material,trimethyliodomethylammonium...     

Phase Transition Engineering of Host Perovskite toward Optimal Exsolution-facilitated Catalysts for Carbon Dioxide Electrolysis

The in situ exsolution technique of nanoparticles has brought new opportunities for the utilization of perovskite-based catalysts in solid oxide cells. However, the lack of control over the structural evolution of host perovskites during the promotion of exsolution has restricted the architectural exploitation of exsolution-facilitated perovskites. In this study, we strategically broke the long-standing trade-off phenomenon between promoted exsolution and suppressed phase transition via B-site supplement, thus broadening the scope of exsolution-facilitated perovskite materials. Using carbon dioxide electrolysis as an illustrative case study, we demonstrate that the catalytic activity and stability of perovskites with exsolved nanoparticles (P-eNs) can be selectively enhanced by regulating the explicit phase of host perovskites, accentuating the critical role of the architectures of perovskite scaffold in catalytic reactions occurring on P-eNs. The concept demonstrated could potentially pave the way for designing the advanced exsolution-facilitated P-eNs materials and unveiling a wide range of catalytic chemistry taking place on P-eNs.     

X-site doping in ABX3 triggers phase transition and higher Tc of the dielectric switch in perovskite

Material stability is always the key factor for applied materials especially the working environment that requires higher temperature sensitivity or temperature fluctuation range. In which, the stimulus-response perovskite materials are just sensitive to stability to ensure the accuracy and stability of the signals, in the applied devices of batteries and memory storage devices and so on. However, it is still a tremendous challenge to improve the stability of perovskite materials, and maintain reliability in the devices. Here, a novel ABX₂X'₁ (X-site doping in an ABX₃) compound [CEMP]-[CdBr₂(SCN)] (1, CEMP = 1-(2-chloro-ethyl)-1-methyl-piperidine) with remarkable high-temperature reversible dielectric switching behavior was proposed. The strategy of [SCN]⁻doping in perovskite for improving the stability was successfully achieved. Meanwhile, the steric hindrance is increased while the energy barrier is also increased by replacing hydrogen with flexible groups, which leads to a high-temperature reversible phase transition. The new finding provides a new direction to enrich new applications and design ideas of perovskite materials. Especially the X-site strategy of doping or substitution in the ABX₃, it will promote ingenious and perfect experimental results in material synthesis and performance improvement by chemistry disciplines.     

高效医学传感钙钛矿材料研究进展

卤化物钙钛矿材料作为一种新型半导体材料，具有优异的光电转换特性、能级结构可调、易于加工、结构和尺寸以及形貌可调、改性后优异的生物相容性等优点，在医学检测传感器中具有广阔的应用前景。本综述讨论了钙钛矿材料在生物医学传感领域的研究进展，钙钛矿医学传感器能通过光电转换、全光转换、电催化等多种物理或化学机制实现传感，具有可灵活选择的器件结构、性能指标和信号传递方式，用于人体代谢物质、神经递质、癌症相关物质和药物等医学物质的检测。钙钛矿医学传感器将为未来的医工多学科融合提供新希望，加快医工融合发展。     

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. Graphical abstract