【Adv.Mater.】苏州大学廖良生、王亚坤等|突破30%效率与万小时寿命！AM最新综述全面解锁钙钛矿量子点LED的商业化密码
文章标题： Bridging Synthesis and Device Performance in Perovskite Quantum Dot Light-Emitting Diodes
通讯作者： Wan-Shan Shen, Ya-Kun Wang, Liang-Sheng Liao
文章概要
引言
钙钛矿量子点因其极高的色彩纯度、宽广的可调带隙以及接近理想状态的光致发光量子产率，已经成为开发下一代高性能发光二极管最具潜力的发光材料之一。相比于传统的有机发光二极管和传统二六族半导体量子点，钙钛矿量子点在显示技术所需的色域覆盖率上展现出压倒性的优势，其溶液法制备工艺也大幅降低了生产成本。然而，在通往实际商业化应用的道路上，钙钛矿量子点高表面积比带来的大量缺陷态、电场作用下的离子迁移以及器件层面的载流子注入不平衡等关键瓶颈，严重制约了器件的稳定性和发光效率。为了攻克这些难题，本篇发表于《Advanced Materials》的重磅综述系统性地阐述了一个高度整合的“合成—表面—器件”全栈优化框架，旨在打通材料底层物理机制与宏观器件构筑之间的壁垒，为实现高商业可行性的钙钛矿量子点发光二极管提供清晰详实的工艺路线图。
Schematic overview of the integrated “synthesis–surface–device” optimization framework for high-performance PQD-LEDs.
主要实验及结论
在材料合成的源头阶段，研究人员通过深入挖掘钙钛矿晶体结构中的结构容忍因子与动态无序效应，系统调控了量子点的核心光电特性。不仅经典的热注射法和配体辅助再沉淀法得到了工艺参数上的极限优化，诸如微流体平台与机器学习相结合的自驱动流体实验室等先进合成范式也被引入，极大地提升了量子点的尺寸均匀性与批量制备的重现性。在此基础上，组分工程通过在A位引入大尺寸的甲脒或胍离子来松弛晶格应变，或者在B位进行异价和同价的多阳离子共掺杂，从晶格结构内部显著提高了不稳定相的形成能，成功抑制了非辐射复合中心的产生，为后续构筑兼具高发光效率与强抗环境干扰能力的发射层奠定了坚实的晶体学基础。
(a) Scheme of crystal structure and composition of ABX3 perovskites. (b) Correlations between tolerance factor and crystal structure of perovskite materials. Reproduced from ref. [41]. Copyright 2016, American Chemical Society. (c) Band structure of lead halide perovskites. (d) PL emission spectra of colloidal perovskite CsPbX3 QDs (X = Cl, Br, I) with different anion composition. Reproduced from ref. [32]. Copyright 2015, American Chemical Society. (e) UV–vis absorption and PL emission spectra with different particle sizes. Reproduced from ref. [61]. Copyright 2017, American Chemical Society. (f) Illustration of how the band structure of materials changes as quantum confinement increases due to reductions in PQD size below the Bohr diameter. Reproduced from ref. [22]. Copyright 2024, Royal Society of Chemistry.
针对量子点表面极其活跃且易脱落的动态配体壳层，表面工程开展了全方位的配体化学结构改性与核壳结构构筑。根据软硬酸碱理论，研究引入了结合力更强的软路易斯碱配体、多齿螯合配体以及整体电中性的两性离子配体，牢固锚定表面的未配位铅离子并填补卤素空位。这些创新的短链或分支状配体设计不仅在不破坏胶体稳定性的前提下大幅降低了空间位阻，将固体薄膜的光致发光量子产率从传统配体大幅流失造成的骤降中挽救出来，还成功消除了阻碍电荷隧穿的绝缘屏障。此外，通过 epitaxial 生长构筑诸如双钙钛矿、宽带隙半导体或者将量子点原位镶嵌于刚性沸石及金属有机框架中，实现了物理隔绝与电荷局域化的完美双赢。
(a) Illustration of the effect of size on the exciton binding energy. (b) Recombination process for bulk and weakly-confined free-carrier-dominated systems. (c) Recombination process for strongly-confined exciton-dominated systems. Figure made with inspiration from ref. [22].
Schematic representation of the electronic band structure of (a) typical defect-intolerant semiconductors and (b) lead halide perovskites. (c) Typical point defects in PQDs, including vacancies, interstitial and antisite atoms, in order of increasing formation energy (or decreasing probability of occurrence), and their depths in the bandgap. Figure made with inspiration from ref. [55]. (d) Proportions of monomolecular, bimolecular, and Auger recombination for 3D perovskites as a function of carrier density, derived from theoretical calculations using the recombination constants of 3D perovskites. (e) Proportions of the same recombination mechanisms for PQDs, calculated using the recombination constants of quasi-2D perovskites. Figure 5d,e are reproduced from ref. [21]. Copyright 2025, Wiley-VCH GmbH. (f) Schematic illustration of dynamic disorder in halide perovskites and its effect on wavefunction overlap. Reproduced from ref. [76]. Copyright 2021, American Chemical Society.
在器件工程的落地实施层面，协同优化电荷注入效率、辐射复合效率与光提取效率成为了推动整个体系接近理论极限的核心动力。通过引入共轭导电配体进行界面偶极工程调控，或者对空穴传输层实施掺杂改性，成功消除了深能级电荷注入势垒，使器件内部的电子和空穴通量趋于完美的化学计量比，从而在低驱动电压下有效遏制了因电荷积聚引发的俄歇复合与焦耳热效应。为了解决长期以来高达百分之八十的光子被束缚在器件内部无法逸出的尴尬局面，器件设计通过对量子点薄膜进行超薄化控制来调低折射率以减少波导损耗，并利用功能配体诱导过渡偶极矩进行水平取向排列，再辅以纳米级微结构表面粗糙化与局域表面等离激元共振效应。这一系列精密的器件架构改良成功斩断了由离子迁移和热损耗相互放大的恶性退化级联反应，将绿光和红光器件的外量子效率推向了百分之三十以上的顶峰，并使工作寿命跨越了万小时的实用化门槛，同时也为最为棘手的深蓝光器件相分离难题提供了基于空间局域限域的全新解题思路。
(a) Schematic illustration for preparation of CsPbBr3–zeolite composites with blue fluorescence of CsPbBr3 QDs. (b) SEM images and (c) the particle size distribution of microsized silicalite-1. (d) SEM images and (e) the particle size distribution of nanosized silicalite-1 zeolites. (f) Effect of different zeolite sizes on the diffusion path of CsPbBr3 QDs. Figure 15 is reproduced from ref. [180]. Copyright 2024, American Chemical Society.
(a) A typical architecture of a perovskite LED. The contributions of each active layer to various processes are listed on the right. (b) Schematic diagram of the working mechanism of PQD-LEDs. (c) Energy levels of some commonly used electrodes, HTLs, PQDs, and ETLs, with data obtained from ref. [60].
总结及展望
这篇综述不仅仅是对过去几年钙钛矿量子点发光二极管突破性进展的复盘，更是面向未来微型显示技术、柔性穿戴设备以及量子信息科学等前沿领域的关键宣言。未来的研究重心将彻底走出单纯依赖试错的传统工艺范式，转向利用先进的算力进行可编程配体的理性设计，并依托连续流微流体平台将实验室成果真正转化为工业级的大面积薄膜制造流线。尽管在纯溴化物的深蓝光效率与抗相分离稳定性上仍需要开展兼具理论深度与工程韧性的攻坚战，但通过化学、物理学与器件微电子学的深度跨学科融合，钙钛矿量子点发光二极管正以前所未有的姿态，加速从高校和科研院所的实验台上走向千家万户的商用显示屏幕。