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.     

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.     

固态照明用稀土荧光粉和无机量子点:机遇与挑战

白光发光二极管(w-LED)固态照明器件具有使用寿命长、环保节能、体积小及安全性高等优点,经过10多年的发展已基本取代传统白炽灯、荧光灯而成为新一代照明光源。 荧光转换材料作为w-LED中的核心材料,直接影响着器件的性能指标。 因此,开发高性能荧光转换材料对进一步提升w-LED器件性能至关重要。 本文围绕稀土荧光粉和无机量子点这两类固态照明用无机发光材料进行介绍,综述了w-LED用稀土荧光粉的结构设计、组成及发光性能调控等方面的进展,代表性地介绍了以ZnS为代表的硫族化合物、铅卤钙钛矿和碳点3类典型的光致发光量子点及其w-LED的设计与光谱调控研究工作,最后提出了稀土荧光粉和无机量子点作为固态照明用荧光转换材料所存在的机遇和挑战。     

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。     

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。     

如何提升铅卤钙钛矿量子点的稳定性?

钙钛矿量子点因其优越的光电性能(如可调节的发光、窄的发光谱线、高的量子效率以及方便制备等)成为半导体发光领域的研究热点之一.虽然钙钛矿量子点在发光二极管方面具有良好的应用前景,但要想实现其商业化,仍然面临着很多问题.首先是稳定性较差,钙钛矿量子点在光、热、空气中会发生不可逆转的降解,进而导致严重的荧光猝灭,这一缺点严重地阻碍了其在实际中的应用.铅卤钙钛矿较差的稳定性也受到了研究者的广泛关注,近年来,许多工作报道了提升钙钛矿量子点稳定性的有效方法.本文详细分析了铅卤钙钛矿量子点不稳定性的来源,包括钙钛矿结构的不稳定性以及环境应力诱导下的降解,总结了近年来关于提升钙钛矿量子点稳定性的基本方法,并提出了改善铅卤钙钛矿量子点稳定性的一些建议.     

Ce/Tb/Mn共激活单基质白光发射稀土无铅双钙钛矿与白光LED器件

金属铅卤钙钛矿由于其优异的光电性能已经广泛应用于各种光电器件当中,包括太阳能电池、发光二极管器件(LED)、光电检测器等,然而铅基钙钛矿的毒性和差的稳定性仍是当前相关研究的巨大挑战。通过水热法成功合成了一种低毒性和高效的无铅稀土双钙钛矿,通过三基色发光中心Ce/Tb/Mn的能量传递调控,获得了一种稀土双钙钛矿单基质白光发射材料Cs_2NaCe_xTb_(1-x)Cl_6:xMn~(2+),系统研究了其晶体结构、激发、发射光谱和能量传递机制与效率。研究结果表明:Cs_2NaCe_(0.2)Tb_(0.8)Cl_6:1%Mn~(2+)在紫外区域表现出强而较宽的吸收,呈现较强的暖白光发射,其量子效率为67.25%。此外,该材料在UV-LED (365 nm, 150 mW·cm~(-2))照射60 min后,样品的发光强度降低仅仅为5%;在100和200℃下热处理30 min后,样品的发光强度降低仅仅为5%和14%;结合商用365 nm LED芯片,得到了理想的暖白光LED,其色坐标为(x=0.41,y=0.46),色温为3849 K。上述结果提出了一种高效单基质镧系全无机双钙钛矿用于白色发光二极管(WLEDs)的潜在方法。     

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.     

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。     

激光作用铅卤钙钛矿的机理与应用

近年来,铅卤钙钛矿纳米晶因其易制备,低成本,高性能等特性引起了人们极大的关注。钙钛矿纳米晶的光电性能优越应用潜力巨大,然而稳定性问题制约着它进一步发展,使其无法与已经商业化的应用相匹敌。针对钙钛矿材料的稳定性问题,人们展开了很多研究,其中一个方面就是光照稳定性。该方面的研究可以为制备高稳定性钙钛矿材料和器件奠定基础,还可以利用光照(特别是激光)来调控钙钛矿的结构和性能,拓展其在光电领域的全方位应用。本文专注于激光照射下钙钛矿的变化及其相关应用,首先综述了激光辐照铅卤钙钛矿时出现的变化现象以及微观机理;其次,基于这些变化机理,介绍了最近研究人员如何使用激光技术对钙钛矿薄膜和器件进行性能调控,以及激光直写钙钛矿技术的相关应用。     

Photoredox Organic Synthesis Employing Heterogeneous Photocatalysts with Emphasis on Halide Perovskite

Lately, heterogeneous semiconductor materials have been explored as an emerging type of efficient photocatalyst for photoredox organic synthesis. Among these semiconductors, lead halide perovskite materials demonstrate unique properties towards excellent charge separation and charge transfer, extremely long charge carrier migration, high efficiency in visible light absorption, and long excited states lifetimes, etc., as proved in ground-breaking solar cell applications, garnering necessary merits for an efficient catalytic system for photoredox organic reactions. Here, the latest progress in heterogeneous semiconductor materials towards this endeavor is examined, with particular emphasis on lead halide perovskite nanocrystals (NCs) in photocatalytic organic synthesis.     

Synthesis of Lead‐free CsGeI3 Perovskite Colloidal Nanocrystals and Electron Beam‐induced Transformations

Colloidal nanocrystals (NCs) of metal halide perovskite have recently aroused great research interest, due to their remarkable optical and electronic properties. We report a solution synthesis of a new member in this category, that is, all‐inorganic lead‐free cesium germanium iodine (CsGeI₃) perovskite NCs. These CsGeI₃ colloidal NCs are confirmed to adopt a rhombohedral structure. Moreover, the electron beam‐induced transformations of these lead‐free perovskite NCs have been investigated for the first time. The fracture of single‐crystalline CsGeI₃ nanocubes occurs first, followed by the emergence and growth of cesium iodine (CsI) single crystals and the final fragmentation into small debris with random orientations. Notably, the electron‐reduced Ge species in CsGeI₃ nanocubes exhibit a distinctive transformation path, compared to heavier Pb atoms in lead halide perovskite NCs.     

Facile low-temperature solid-state synthesis of efficient blue-emitting Cs3Cu2I5 powder phosphors for solid-state lighting

The discovery of new environmentally friendly luminescent materials with high photoluminescence quantum yield and long-term stability is critical for future solid-state lighting and displays applications. Although lead halide perovskite materials with excellent optical properties have been extensively investigated in recent years because they hold tremendous promise in optoelectronic devices, the toxicity of lead and poor air-stability still hinder their commercial applications. Moreover, while substantial work has been done on three-dimensional (3D) perovskite halides, the zero-dimensional (0D) halide emitters with bright luminescence remain elusive. Herein we report a facile solid-state reaction method to prepare an efficient lead-free all-inorganic halide material with 0D structure, Cs₃Cu₂I₅, with photoluminescence quantum yield up to 80%. Under ultraviolet excitation at 313 nm, the Cs₃Cu₂I₅ powder phosphors show a strong blue photoluminescence emission with peak at 445 nm and CIE color coordinates of (0.1486, 0.0873). Notably, Cs₃Cu₂I₅ exhibits good color stability at high temperatures and outstanding stability towards air exposure exceeding one month (30 days). These findings not only open up a door for the development of promising highly emissive low-dimensional halide materials for lighting and displays, but also offer a new scalable approach for the potential mass production of halide emitters.     

Completely Amine-Free Open-Atmospheric Synthesis of High-Quality Cesium Lead Bromide (CsPbBr3) Perovskite Nanocrystals

Cesium lead halide perovskite nanocrystals (NCs) CsPbX₃ (X=Cl, Br, and I) have been prominent materials in the last few years due to their high photoluminescence quantum yield (PLQY) for light-emitting diodes and other significant applications in photovoltaics and optoelectronics. In colloidal CsPbX₃ synthesis, the most commonly used ligands are oleic acid and oleylamine. The latter plays an important role in surface passivation but may also be responsible for poor colloidal stability as a result of facile proton exchange leading to the formation of labile oleylammonium halide, which pulls halide ions out of the NC surface. Herein, a facile, efficient, completely amine-free synthesis of cesium lead bromide perovskite nanocrystals using hydrobromic acid as halide source and tri-n-octylphosphane as ligand under open-atmospheric conditions is demonstrated. Hydrobromic acid serves as labile source of bromide ion, and thus this three-precursor approach (separate precursors for Cs, Pb, Br) gives more control than a conventional single-source precursor for Pb and Br (PbBr₂). The use of HBr paved the way to eliminate oleylamine, and thus the formation of labile oleylammonium halide can be completely excluded. Various Cs:Pb:Br molar ratios were studied and optimum conditions for making very stable CsPbBr₃ NCs with high PLQY were found. These completely amine-free CsPbBr₃ perovskite NCs synthesized under bromine-rich conditions exhibit good stability and durability for more than three months in the form of colloidal solutions and films, respectively. Furthermore, stable tunable emission across a wide spectral range through anion exchange was demonstrated. More importantly, this work reports open-atmosphere-stable CsPbBr₃ NCs films exhibiting strong PL, which can be further used for optoelectronic device applications.     

Synthesis of double perovskite and quadruple perovskite nanocrystals through post-synthetic transformation reactions

Lead-free halide perovskite nanocrystals (NCs) represent a group of emerging materials which hold promise for various optical and optoelectronic applications. Exploring facile synthetic methods for such materials has been of great interest to not only fundamental research but also technological implementations. Herein, we report a fundamentally new method to access lead-free Bi-based double perovskite (DP) and quadruple perovskite (or layered double perovskite, LDP) NCs based on a post-synthetic transformation reaction of Cs₃BiX₆ (X = Cl, Br) zero-dimensional (0D) perovskite NCs under mild conditions. The produced NCs show good particle uniformity, high crystallinity, and comparable optical properties to the directly synthesized NCs. The relatively slow kinetics and stop-on-demand feature of the transformation reaction allow real-time composition–structure–property investigations of the reaction, thus elucidating a cation-alloyed intermediate-assisted transformation mechanism. Our study presented here demonstrates for the first time that post-synthetic transformation of 0D perovskite NCs can serve as a new route towards the synthesis of high-quality lead-free perovskite NCs, and provides valuable insights into the crystal structures, excitonic properties and their relationships of perovskite NCs.

Lead-free perovskite nanocrystals are synthesized by post-synthetic transformation reactions. The post-synthetic transformations show the structural flexibility of zero-dimensional perovskite nanocrystal materials.     

Inorganically functionalized PbS-CdS colloidal nanocrystals: integration into amorphous chalcogenide glass and luminescent properties

Inorganic semiconductor nanocrystals (NCs) with bright, stable, and wavelength-tunable luminescence are very promising emitters for various photonic and optoelectronic applications. Recently developed strategies for inorganic surface capping of colloidal NCs using metal chalcogenide complexes have opened new perspectives for their applications. Here we report an all-inorganic surface functionalization of highly luminescent IR-emitting PbS-CdS NCs and studies of their luminescence properties. We show that inorganic capping allows simple low-temperature encapsulation of inorganic NCs into a solution-cast IR-transparent amorphous As(2)S(3) matrix. The resulting all-inorganic thin films feature stable IR luminescence in the telecommunication wavelength region. The high optical dielectric constant of As(2)S(3) also helps reduce the dielectric screening of the radiating field inside the quantum dot, enabling fast radiative recombination in PbS-CdS NCs.     

Lead‐Free Halide Perovskite Nanocrystals: Crystal Structures,Synthesis, Stabilities,and Optical Properties

In recent years, there have been rapid advances in the synthesis of lead halide perovskite nanocrystals (NCs) for use in solar cells, light emitting diodes, lasers, and photodetectors. These compounds have a set of intriguing optical, excitonic, and charge transport properties, including outstanding photoluminescence quantum yield (PLQY) and tunable optical band gap. However, the necessary inclusion of lead, a toxic element, raises a critical concern for future commercial development. To address the toxicity issue, intense recent research effort has been devoted to developing lead‐free halide perovskite (LFHP) NCs. In this Review, we present a comprehensive overview of currently explored LFHP NCs with an emphasis on their crystal structures, synthesis, optical properties, and environmental stabilities (e.g., UV, heat, and moisture resistance). In addition, strategies for enhancing optical properties and stabilities of LFHP NCs as well as the state‐of‐the‐art applications are discussed. With the perspective of their properties and current challenges, we provide an outlook for future directions in this rapidly evolving field to achieve high‐quality LFHP NCs for a broader range of fundamental research and practical applications.     

醋酸铅作为铅源合成CH3NH3PbBr3-xClx纳米晶体颗粒

Lead acetate, which is highly soluble in dimethylformamide, was used to synthesize mixed halide perovskite CH₃NH₃PbBr_3-xCl_x (MA = CH₃NH₃, 0 ≤ x ≤ 3) nanocrystals (NCs). This method provides an approach to address the low solubility of lead halides, especially lead chloride. Different Br/Cl ratios in MAPbBr_3-xCl_x lead to various optical properties. The photoluminescence emission peak can be tuned from 399 to 527 nm. Their full-widths at half-maxima (FWHM) are about 20 nm. MAPbBr_3-xCl_x NCs have an average diameter of ~(11 ± 3) nm and have uniform dispersion in toluene. The MAPbBr₃ NCs have a long average recombination lifetime (τ_ave = 97.4 ns) and a photoluminescence quantum yield (PLQY) of up to 73%.