硅酸盐学报

过渡金属离子掺杂CsPbX₃（X=Cl, Br, I）型全无机钙钛矿纳米晶研究进展

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陈婷 ¹ , 武文魁 ¹ , 秦喆 ¹ , 郭春显 ¹ , 谢志翔 ¹ , 厉有鹏 ¹ , 徐彦乔 ²

硅酸盐学报 | 综合评述 2024,52(2): 694-705

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硅酸盐学报 |综合评述 2024 , 52 (2) : 694 -705

过渡金属离子掺杂CsPbX₃（X=Cl, Br, I）型全无机钙钛矿纳米晶研究进展

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陈婷¹, 武文魁¹, 秦喆¹, 郭春显¹, 谢志翔¹, 厉有鹏¹, 徐彦乔²

作者信息

^1．苏州科技大学材料与器件研究院，江苏苏州 215009

^2．景德镇陶瓷大学材料科学与工程学院，江西景德镇 333001

作者简介:

陈婷（1984—），女，博士，副教授。

Research Progress on Transition Metal Ion Doped CsPbX₃ (X=Cl, Br, I) Type All Inorganic Perovskite Nanocrystals

Ting CHEN¹, Wenkui WU¹, Zhe QIN¹, Chunxian GUO¹, Zhixiang XIE¹, Youpeng LI¹, Yanqiao XU²

Affiliations

^1.Institute of Materials Science & Devices, Suzhou University of Science and Technology, Suzhou 215009, Jiangsu, China

^2.School of Material Science and Engineering, Jingdezhen Ceramic Institute, Jingdezhen 333001, Jiangxi, China

CHEN Ting (1984-), female, Ph.D., Associate Professor. E-mail: chenting@mail.usts.edu.cn

出版时间: 2024-02-20 doi: 10.14062/j.issn.0454-5648.20230567

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CsPbX₃（X=Cl, Br, I）全无机钙钛矿纳米晶具有荧光量子产率高、半峰宽窄、发射波长易于调节等特性，在发光二极管、太阳能电池、光电探测器等领域具有广泛的应用前景。但由于其离子特性，纳米晶在光照、水分和加热等条件下的稳定性较差。金属离子掺杂可以影响纳米晶的电子能带结构，进而有效改善其光致发光性能。掺杂金属离子有主族金属离子、稀土金属离子和过渡金属离子。与前2种离子相比，过渡金属离子价格较低，同时掺杂后能有效的提高钙钛矿纳米晶的稳定性。本文综述了近几年来过渡金属离子（Mn²⁺、Ni²⁺、Cu²⁺、Zn²⁺等）掺杂对钙钛矿纳米晶性能的影响，分析了掺杂全无机钙钛矿纳米晶发展过程中面临的挑战，并对其今后的发展方向进行了展望。

关键词

全无机钙钛矿 / 纳米晶 / 离子掺杂 / 过渡金属 / 稳定性

Abstract

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All inorganic perovskite nanocrystals of CsPbX₃ (X=Cl, Br, I) have superior properties such as high fluorescence quantum yield, narrow half-peak width and easy adjustment of emission wavelength, etc., which have wide application prospects in light-emitting diodes, solar cells and photodetectors. However, CsPbX₃ nanocrystals have a poor stability under light, moisture and heating conditions due to their ionic properties, restricting their practical application. Metal ion doping can affect the electronic band structure of CsPbX₃ nanocrystals, thus effectively improving their photoluminescence properties. The doped metal ions can be divided into main group metal ion, rare-earth metal ion and transition metal ion. Transition metal ion has a lower price, and it can efficiently improve the stability of perovskite nanocrystals. This review represented recent work on the effect of transition metal ions (i.e., Mn²⁺, Ni²⁺, Cu²⁺, Zn²⁺, etc.) doping on the properties of perovskite nanocrystals. In addition, the challenges in the development of doped all-inorganic perovskite nanocrystals were analyzed, and the future development direction was also prospected.

Transition metal ion doping CsPbX₃ nanocrystals (NCs) are explored extensively. Mn²⁺ doping can improve the formation energy of CsPbX₃ NCs with a high stability. Mn²⁺ doping exists in wide-band-gap perovskite hosts where the excitation energy is transferred to Mn d-state, resulting in short-range tunable yellow-orange d-d emissions. Low concentration Mn²⁺ doping is beneficial to enhancing the exciton emission, and the Mn²⁺-doping sample has a long PL lifetime. Ni²⁺ doping can eliminate the structural defects of CsPbX₃ NCs, resulting in the improvement of the lattice order. Compared with the undoped sample, doping Ni²⁺ also induces the formation energy of CsPbX₃ NCs and triggers the phase transition of CsPbBr₃ from orthorhombic to cubic, which is attributed to the lattice strain due to the size mismatch of Ni²⁺ and Pb²⁺. Ni²⁺ doping reduces the non-radiative recombination efficiency and increases the fluorescence intensity of the CsPbX₃ NCs. Cu²⁺ doping sample maintains a cubic crystal structure of the initial phase. When Cu²⁺ with the smaller radius (i.e., 0.72 Å) replaces Pb²⁺ ion with the larger radius (i.e., 1.19 Å), the shrinkage of lattice contraction regulates the tolerance factor of the [PbBr₆]^4- octahedron, and increases the lattice formation energy, resulting in high stability and fluorescence intensity of NCs. Compared with Pb²⁺ (i.e., 1.19 Å), Zn²⁺ has smaller ion radius (i.e., 0.74 Å) and a lower toxicity. The introduction of Zn²⁺ can effectively passivate the surface and internal defects of CsPbX₃ NCs. Doping Co²⁺ can increase the formation energy, improve the short-range order of the lattice, and enhance the different monochromatic band edge emission without introducing new composite channels. Doping Cr³⁺ can regulate the structure and the optical properties of NCs. Doping Fe²⁺/Fe³⁺ has some advantages like low cost, high electrical conductivity and magnetic properties. Moreover, an appropriate amount of Fe²⁺ doping improves the size uniformity of CsPbX₃ NCs, as well as increases the PLQY and the average PL lifetime due to the decrease of the defect state and nonradiation recombination of NCs. Furthermore, the application of transition metal ion doped CsPbX₃ NCs in white light-emitting diode (WLED), solar cells and laser devices was outlined. The employment of doping transition metal ions into perovskites can improve the optical properties and stability, which energetically facilitate their applications. Finally, the main future research directions of transition metal ion doped CsPbX₃ NCs were concluded.

Summary and prospects

Transition metal doping can promote the radiative recombination of excitons, and the defect formation energies of V_Cs, V_Br and V_Pb are effectively improved, resulting in an improvement of the luminescence performance of CsPbX₃ NCs. However, some problems need to be solved in the future. The PL linewidth of nanocrystals for the application of bioluminescence imaging and LED fields needs to be reduced. The external quantum efficiency (EQE) and luminous efficacy (LE) of transition metal doped CsPbX₃ NCs still need to be improved, compared to that of Cd-based QDs. Finally, there are still potential risks associated with the reaction, and the PLQY still needs to be further improved. The investigation of transition metal ion doping all-inorganic CsPbX₃ NCs has a profound impact on the scientific research and commercial applications of fluorescent materials.

Key words

all-inorganic perovskite / nanocrystals / ion doping / transition metals / stability

引用本文

陈婷, 武文魁, 秦喆, 郭春显, 谢志翔, 厉有鹏, 徐彦乔. 过渡金属离子掺杂CsPbX₃（X=Cl, Br, I）型全无机钙钛矿纳米晶研究进展. 硅酸盐学报, 2024 , 52 (2) : 694 -705 . DOI: 10.14062/j.issn.0454-5648.20230567

Ting CHEN, Wenkui WU, Zhe QIN, Chunxian GUO, Zhixiang XIE, Youpeng LI, Yanqiao XU. Research Progress on Transition Metal Ion Doped CsPbX₃ (X=Cl, Br, I) Type All Inorganic Perovskite Nanocrystals[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (2) : 694 -705 . DOI: 10.14062/j.issn.0454-5648.20230567

基金

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国家自然科学基金(52062019)
江苏省高校青蓝工程

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2024年第52卷第2期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230567

接收时间：2023-08-01
首发时间：2026-10-22
出版时间：2024-02-20

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收稿日期：2023-08-01
修回日期：2023-08-24

基金

国家自然科学基金(52062019)

江苏省高校青蓝工程

作者信息

^1．苏州科技大学材料与器件研究院，江苏苏州 215009

^2．景德镇陶瓷大学材料科学与工程学院，江西景德镇 333001

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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