徐天成， 李金凯， 刘宗明

济南大学 材料科学与工程学院，山东 济南250022

引用格式：

徐天成，李金凯，刘宗明.表面修饰提升CsPbBr₃钙钛矿纳米晶的稳定性［J］.中国粉体技术，2024，30（5）：1-8.

XU Tiancheng，LI Jinkai，LIU Zongming. Surface modification strategy improves stability of CsPbBr₃ perovskite nanocrystals［J］.China Powder Science and Technology，2024，30（5）：1-8.

DOI：10.13732/j.issn.1008-5548.2024.05.001

收稿日期： 2024-05-13， 修回日期： 2024-05-26， 上线日期： 2024-07-23。

基金项目： 国家自然科学基金项目，编号：51402125；山东省自然科学基金项目，编号 ：ZR2020ME045、ZR2020ME046；济南市“新高校20条”项目，编号：2021GXRCO99、T202204。

第一作者简介： 徐天成（1997—，男，硕士生，研究方向为半导体发光材料。E-mail：mse_xutc@163. com。

通信作者简介： 李金凯（1985—），男，副教授，博士，硕士生导师，研究方向为稀土及半导体发光材料。E-mail：mse_lijk@ujn. edu. cn。

摘要：【目的】分析不同配体添加量对CsPbBr₃钙钛矿纳米晶表面修饰后的光学性能影响，实现纳米晶稳定性和光学性能提升。【方法】通过水相合成方法合成CsPbBr₃钙钛矿纳米晶， 制备过程原位引入短碳链的L-天冬氨酸（L-aspartate，L-Asp）和油胺（oleylamine，OAm）配体对纳米晶的表面进行修饰， 并研究Cs₄PbBr₆向CsPbBr₃的晶相转变机制。【结果】L-Asp和OAm配体均匀吸附于纳米晶表面，使纳米晶在水中具有优异的分散性，且结晶性良好； CsPbBr₃钙钛矿纳米晶的最大发射波长为517 nm处，半峰宽为17 nm，分散在水中11 h后依旧能够具有绿色发射且发射峰位没有明显移动。【结论】经L-Asp和OAm配体修饰的CsPbBr₃钙钛矿纳米晶在保持优异光学性能的同时还具有良好的溶液稳定性。

关键词： 钙钛矿；纳米晶；表面修饰；光学性能；L-天冬氨酸；油胺

Abstract

Objective In recent years，all-inorganic lead halide perovskite （CsPbX₃，X=Cl，Br，I）nanocrystals，a type of nanoscale composite material， have attracted significant attention from materials scientists. With a high photoluminescent quantum yield， an extremely narrow full width at half maximum （FWHM）， tunable emission across the visible spectrum， and high carrier mobility， CsPbX₃ is rapidly becoming one of the most promising materials for optoelectronic devices. However， due to their unique properties， perovskite materials exhibit low stability in aqueous solutions and typically need to be synthesized in non-polar organic solvents to prevent decomposition. To enhance stability， it is necessary to modify their surface with hydrophobic groups，which greatly restricts their application in aqueous environments. To overcome these challenges， researchers are exploring green，simple，aqueous-phase synthesis methods to directly synthesize perovskite nanocrystals with specific functions. Traditional synthesis methods typically avoid water to prevent adverse effects on the structure and properties of the highly water-sensitive perovskite nanocrystals. Nonetheless， recent research has shown that the presence of water is not always a disadvantage. In this study，the stability and optical properties of CsPbBr₃ perovskite nanocrystals were improved by introducing L-aspartate ligands instead of OA ligands.

Methods The entire synthesis process was conducted in air without inert gas protection， as shown in Fig. 1. CsBr （0.4 mmol） and PbBr₂ （0.4 mmol） were dissolved in 10 mL of N， N-dimethylacetamide （DMA） solution， heated to 50 ^oC， and magnetically stirred for 45 min until completely dissolved. Subsequently， 800 μL of OAm was added， during which the solution gradually changed from colorless to white turbid. The precursor was recorded as Cs₄PbBr₆ NCs. After 15 min of continued stirring， 1 mL of the white precursor solution was added into deionized water containing L-aspartate. After 10 s of reaction， the resulting mixture was centrifuged for subsequent characterization. The produced sample was recorded as CsPbBr₃-L-Asp.

Results and Discussion With the gradual addition of aspartic acid from 0.05 mmol to 0.3 mmol in 10 mL of deionized water， the PL intensity of the prepared samples first increased and then decreased， while the emission peak remained stable at 517 nm without significant shifts. The full width at half maximum of 17 nm had a high color purity. The CsPbBr₃ NCs synthesized with an optimal addition of 0.15 mmol of aspartic acid exhibited the best PL intensity. Digital photos of CsPbBr₃ NCs prepared with different L-aspartate amounts under a 365 nm portable UV lamp were shown in Fig. 3（c）. Perovskite nanocrystals are prone to degradation in polar environments due to their ionic properties. Fig. 6（a） showed the PL spectra of nanocrystals soaked in aqueous solution for 11 h with changes over time， illustrating that the emission peak maintained its original shape without significantly shifts during the whole test process. Fig. 6（b） showed the fluorescence intensity changes over time， indicating a slow decrease within 1 h， retaining about 95% of the initial value. After 11 h of continuous soaking， the nanocrystals still showed weak green fluorescence under ultraviolet light.

Conclusion CsPbBr₃-L-Asp perovskite nanocrystals were successfully prepared using water phase synthesis method. CsPbBr₃-L-Asp exhibits good crystallization with a maximum emission peak at 517 nm， FHWM of 17 nm， and fluorescence lifetime of 49.45 ns. Surface modification with L-aspartic acid and OAm allows the nanocrystals to emit green light after 11 h soaking in water without significant changes to the emission peak.

Keywords： perovskite；nanocrystal； surface modification； optical property； L-aspartate； oleylamine

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