全无机钙钛矿量子点的研究进展

doi:10.11896/cldb.201905008

材料导报

2019, Vol. 33

Issue (5): 777-783 https://doi.org/10.11896/cldb.201905008

无机非金属及其复合材料

全无机钙钛矿量子点的研究进展

王恩胜, 余丽萍, 廉世勋, 周文理

湖南师范大学化学化工学院,长沙 410081

An Overview on Advances in All-inorganic Perovskite Quantum Dots

WANG Ensheng, YU Liping, LIAN Shixun, ZHOU Wenli

College of Chemistry Engineering, Hunan Normal University, Changsha 410081

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摘要近年来,在各类光电材料中,钙钛矿量子点以优异的性能脱颖而出。相对于有机-无机杂化钙钛矿量子点,全无机钙钛矿量子点(IPQDs)的稳定性更高。 IPQDs因具有光吸收系数高、发射光谱窄、光致发光量子产率(PLQY)高、组成与尺寸可调、发射光谱可调以及光致发光和电致发光等特性而备受关注,是当前最具潜力的光电材料之一,广泛应用于发光二极管(LEDs)、太阳能电池、光电探测器、激光等领域。
IPQDs材料尚存在许多问题,主要体现在以下几方面:(1)发光机理不够明确。仍需要大量全面而系统的研究来揭示其优异光电性能背后的内在机制。(2)CsPbCl₃的PLQY较低,需要进一步提高。(3) 成分铅具有毒性。铅在IPQDs中的角色需要进一步剖析,为进一步发展无铅或少铅的钙钛矿材料奠定理论基础。(4)稳定性差。IPQDs在极性溶剂中极易分解或团聚;对光、氧气、湿度和温度的稳定性差;易发生阴离子交换。(5)量子点表面的长链绝缘配体不利于晶粒间电荷迁移。在充分钝化量子点表面的前提下,尽可能地减少配体对电荷迁移的阻碍是发展高效LEDs的有效途径。(6)为适应规模化生产,需要进一步优化制备工艺。
近年来,研究者主要从亟待解决的毒性和稳定性问题展开研究,并取得了重大进展。通过使用无毒或低毒的金属(如Mn、Sn等)来全部或部分取代Pb,以及用聚合物材料来包覆IPQDs,均为解决该材料的毒性问题提供了有效方案。而通过掺杂Mn²⁺可提高钙钛矿晶格的形成能,从根源上改善了IPQDs的热稳定性。此外,利用有机、无机或高分子等材料包覆IPQDs,可以有效避免其与外界环境接触,进而提高该材料的稳定性。
本文全面综述了近年来有关IPQDs的研究进展,包括合成方法、形貌、光学性质和表面性质。着重分析了该材料存在的稳定性和铅的毒性问题以及目前的解决方案。探讨了该材料在发光二极管、太阳能电池、光电探测器以及激光领域的应用前景。最后,总结了该材料有待解决的问题并展望了未来的发展方向。

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关键词: 全无机钙钛矿量子点表面性质稳定性光致发光

Abstract: In recent years, perovskite quantum dots stand out for their excellent photoelectric properties among all kinds of optoelectronic materials. Compared with organic-inorganic hybrid perovskite quantum dots, all-inorganic perovskite quantum dots (IPQDs) show higher chemical stability. IPQDs have aroused tremendous interest owing to their high absorption coefficient, narrow full-width at half maximum, high photoluminescence quantum yield (PLQY), controllable composition and size, tunable emission spectrum, photoluminescence and electroluminescence dual characteristics. These excellent properties have made IPQDs become one of the most promising optoelectronic materials, and widely used in light emitting diodes (LEDs), solar cell, photodetector, laser and other fields.
Unfortunately, there still exist many problems in IPQDs. Ⅰ.The luminescence mechanism of IPQDs is not clear enough. A large number of comprehensive and systematic studies are still needed to reveal the mechanism for their excellent photoelectric performance. Ⅱ. The PLQY of CsPbCl₃ is low and needs further improvement. Ⅲ. Pb in IPQDs is toxic. Further analysis of the impact of Pb in IPQDs should be carry out so as to lay a theoretical foundation for development of lead-free or lead-less QDs materials. Ⅳ.IPQDs are unstable, and they are easy to decompose or agglomerate in polar solvents. The IPQDs, especially CsPbI₃, exhibit poor stability under light, oxygen, high humidity and temperature. Anion exchange can occur easily when different IPQDs are mixed. Ⅴ. Long chain insulation ligands on the surface of QDs hinder the charge-transfer between crystal grains. On the premise of sufficient passivation of quantum dots surface, an effective way to develop highly efficient LEDs is to minimize the hindrance of ligands to charge transfer. Ⅵ. Further optimization of preparation process is required for the sake of adapting to large-scale production.
Researchers have devoted themselves to reduce the toxicity and improve the stability, and significant progress has been made in recent years. Effective ways have been developed to solve the toxicity of IPQDs by completely or partially replacing Pb with non-toxic or low toxic metals (like Mn and Sn), and coating IPQDs with polymers or metal oxides. Moreover, doping Mn²⁺ into IPQDs can increase formation energy of perovskite lattice, and thereby enhance the thermal stability of IPQDs. Besides, using organic, inorganic or polymer materials to coat IPQDs can avoid the contact of IPQDs with external environment, thus the stability of IPQDs can be also improved.
This article provides an overall review on the recent advances in all-inorganic perovskite quantum dots, including synthesis methods, morphology, optical and surface properties of IPQDs. The stability of IPQDs, the toxicity of Pb and the current solutions are analyzed. The application prospects of IPQDs in light-emitting diodes, solar cells, photodetectors and lasers are discussed. Finally, some problems and outlook of future deve-lopment directions of IPQDs are pointed out.

Key words: all-inorganic perovskite quantum dots surface properties stability photoluminescence

出版日期: 2019-03-10 发布日期: 2019-03-12

ZTFLH:	O613.4
	O649.4

基金资助: 国家自然科学基金青年基金(21501058);湖南师范大学化学生物学及中药分析教育部重点实验室开放基金资助课题(KLCBTCMR18-14)

作者简介: 周文理,生于1982年。2012年于中山大学无机化学专业取得博士学位。2012—2015年分别在湖南师范大学和中国台湾大学进行了两年和一年的博士后研究工作。2015年受聘于湖南师范大学化学化工学院副教授。目前,主要从事无机发光材料与器件的研究工作。chemwlzhou@hunnu.edu.cn。王恩胜,2016年6月毕业于安阳师范学院,获得理学学士学位。现为湖南师范大学化学化工学院硕士研究生,在周文理副教授的指导下进行研究。目前主要研究领域为无机纳米发光材料。

引用本文:

王恩胜, 余丽萍, 廉世勋, 周文理. 全无机钙钛矿量子点的研究进展[J]. 材料导报, 2019, 33(5): 777-783.
WANG Ensheng, YU Liping, LIAN Shixun, ZHOU Wenli. An Overview on Advances in All-inorganic Perovskite Quantum Dots. Materials Reports, 2019, 33(5): 777-783.

链接本文:

http://www.mater-rep.com/CN/10.11896/cldb.201905008 或 http://www.mater-rep.com/CN/Y2019/V33/I5/777

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