无机杂化钙钛矿团簇材料：介尺度钙钛矿材料发光性质研究

doi:10.11949/0438-1157.20220462

化工学报 ›› 2022, Vol. 73 ›› Issue (6): 2748-2756.DOI: 10.11949/0438-1157.20220462

• 材料化学工程与纳米技术 • 上一篇下一篇

无机杂化钙钛矿团簇材料：介尺度钙钛矿材料发光性质研究

徐珂(),史国强,薛冬峰()

中国科学院深圳先进技术研究院先进材料科学与工程研究所多尺度晶体材料研究中心，广东深圳 518055

收稿日期:2022-03-31 修回日期:2022-05-08 出版日期:2022-06-05 发布日期:2022-06-30
通讯作者: 薛冬峰
作者简介:徐珂（1990—），女，博士，助理研究员，ke.xu@siat.ac.cn
基金资助:
国家自然科学基金重大研究计划项目(91434118);国家自然科学基金重点项目(51832007);中国博士后科学基金第70批面上项目(2021M703364/2021M703363);广东省基础与应用基础研究基金委员会区域联合基金-青年基金项目(2021A1515110936);深圳市优秀科技创新人才培养项目(博士基础研究启动)(RCBS20210609104609043)

Inorganic hybrid perovskite cluster materials: luminescence properties of mesoscale perovskite materials

Ke XU(),Guoqiang SHI,Dongfeng XUE()

Multiscale Crystal Materials Research Center, Institute of Advanced Materials Science and Engineering, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, Guangdong, China

Received:2022-03-31 Revised:2022-05-08 Online:2022-06-05 Published:2022-06-30
Contact: Dongfeng XUE

摘要/Abstract

摘要：

近年来，介尺度钙钛矿材料体系中钙钛矿魔幻尺寸团簇（PMSCs）材料因具有优异的半导体特性而在新兴光电器件领域极具潜力。然而，介尺度PMSCs容易在合成过程中生成尺寸较大的介尺度钙钛矿量子点（PQDs），难以满足实际应用的需求。本研究采用配体辅助再沉淀（LAPR）方法，通过调节戊酸（VA）和油胺（OAm）配体比例制备了不同发光性质的无机杂化介尺度钙钛矿材料CsPbBr₃ PMSCs、CsPbBr₃ PMSCs/CsPbBr₃ PQDs混合物和CsPbBr₃ PQDs，研究并分析了PQDs和PMSCs的光学性质、形貌结构、稳定性和介尺度结构演变机理。研究发现，表面协同钝化配体VA和OAm的比例是反应能否生成介尺度纯相CsPbBr₃ PMSCs的关键。而且，当VA和OAm配体的表面钝化效果越佳越易生成发光性质优异的纯相CsPbBr₃ PMSCs。

关键词: 介尺度, 无机杂化钙钛矿, 团簇, 纳米结构, 合成, 稳定性, 发光性质

Abstract:

In the mesoscale perovskite material system, perovskite magic sized clusters (PMSCs) have great development prospects and application potential in the field of emerging optoelectronic devices due to their excellent semiconductor properties, such as narrow emission spectral band, high color purity, precise wavelength tunability, uniform particle size distribution, simple solution processing and synthesis process. However, the mesoscale PMSCs are easy to generate perovskite quantum dots (PQDs) with large size during the synthesis process, which is difficult to meet the needs of practical applications. To solve this problem, a simple and controllable ligand-assisted reprecipitation (LAPR) method was used to synthesize inorganic hybrid mesoscale perovskite materials of CsPbBr₃ PMSCs, CsPbBr₃ PMSCs/CsPbBr₃ PQDs mixtures and CsPbBr₃ PQDs with different luminescence properties by adjusting the ratio of valeric acid (VA) to oleylamine (OAm) surface ligands. The optical properties, morphological structure, stability and mesoscale structure evolution mechanism of the PQDs and PMSCs were studied and analyzed in detail. It is found that the ratio of surface synergistic passivation ligands VA to OAm is the key to whether the reaction can generate pure-phase CsPbBr₃ PMSCs. Moreover, when the surface passivation effect of VA and OAm ligands is optimal, it is easier to generate mesoscale pure-phase CsPbBr₃ PMSCs with excellent luminescence properties.

Key words: mesoscale, inorganic hybrid perovskite, cluster, nanostructure, synthesis, stability, luminescence properties

中图分类号:

O 649.4

徐珂, 史国强, 薛冬峰. 无机杂化钙钛矿团簇材料：介尺度钙钛矿材料发光性质研究[J]. 化工学报, 2022, 73(6): 2748-2756.

Ke XU, Guoqiang SHI, Dongfeng XUE. Inorganic hybrid perovskite cluster materials: luminescence properties of mesoscale perovskite materials[J]. CIESC Journal, 2022, 73(6): 2748-2756.

图/表 5

图1 PbBr2 MSCs、CsPbBr3 PMSCs、CsPbBr3 PMSCs/CsPbBr3 PQDs混合物和CsPbBr3 PQDs样品的紫外吸收光谱和荧光发射光谱

Fig.1 Ultraviolet-Visible (UV-Vis) absorption and photoluminescence (PL) spectra for PbBr2 MSCs, CsPbBr3 PMSCs, CsPbBr3 PMSCs /CsPbBr3 PQDs mixture and CsPbBr3 PQDs samples

表1 PbBr2 MSCs、CsPbBr3 PMSCs、CsPbBr3 PMSCs/CsPbBr3 PQDs混合物和CsPbBr3 PQDs样品的PLQYs、发射峰值和发射峰半峰宽（FHWM）值

Table 1 Summary of PLQYs， emission peaks， and FWHM of PbBr2 MSCs， CsPbBr3 PMSCs， CsPbBr3 PMSCs /CsPbBr3 PQDs mixture and CsPbBr3 PQDs samples

Sample	PLQY/%	Emission pesk/nm	FWHM/nm
PbBr₂ MSCs	4	397	10.20
CsPbBr₃PMSCs	82	405	11.13
CsPbBr₃ PMSCs/CsPbBr₃ PQDs	76	421/503	11.13/22.41
CsPbBr₃PQDs	57	524	18.45

图2 CsPbBr3 PMSCs、CsPbBr3 PMSCs/CsPbBr3 PQDs和CsPbBr3 PQDs的TEM图和粒径分布直方图

Fig.2 TEM image and particle size distribution histogram of CsPbBr3 PMSCs, CsPbBr3 PMSCs/CsPbBr3 PQDs and CsPbBr3 PQDs, respectively

图3 CsPbBr3 PMSCs、CsPbBr3 PMSCs/CsPbBr3 PQDs和CsPbBr3 PQDs样品的稳定性(a) 在空气和黑暗环境下:相对荧光强度与测试时间的函数曲线;(b) 在黑暗环境下异丙醇溶剂测试:相对荧光强度随时间连续衰减曲线

Fig.3 Stability of CsPbBr3 PMSCs, CsPbBr3 PMSCs/CsPbBr3 PQDs and CsPbBr3 PQDs samples(a) under air and in the dark: the normalized fluorescence intensity as a function of exposure time; (b) determined by means of an isopropanol test in the dark: the relative fluorescence intensity as a function of isopropanol exposure time

图4 PbBr2 MSCs、CsPbBr3 PMSCs、CsPbBr3 PMSCs/CsPbBr3 PQDs和CsPbBr3 PQDs结构演变示意图(紫色、灰色和绿色小球分别代表Cs原子、Pb原子和Br原子)

Fig.4 Schematic illustration of the structural evolution of PbBr2 MSCs, CsPbBr3 PMSCs, CsPbBr3 PMSCs/CsPbBr3 PQDs mixture and CsPbBr3 PQDs (the purple, gray and green spheres in the schematic diagram represent Cs atoms, Pb atoms and Br atoms, respectively)

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无机杂化钙钛矿团簇材料：介尺度钙钛矿材料发光性质研究

Inorganic hybrid perovskite cluster materials: luminescence properties of mesoscale perovskite materials

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