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削弱配体-溶剂亲和力以抑制表面钝化配体从钙钛矿纳米晶体上解吸。

Weakening Ligand-Liquid Affinity to Suppress the Desorption of Surface-Passivated Ligands from Perovskite Nanocrystals.

机构信息

Department of Medicinal Chemistry, Shantou University Medical College, Shantou, Guangdong Province 515041, P. R. China.

Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou, Guangdong Province 515063, P. R. China.

出版信息

Langmuir. 2022 Dec 20;38(50):15747-15755. doi: 10.1021/acs.langmuir.2c02630. Epub 2022 Dec 9.

DOI:10.1021/acs.langmuir.2c02630
PMID:36484684
Abstract

The interfacial migration of surface-bound ligands highly affects the colloidal stability and optical quality of semiconductor nanocrystals, of which the underlying mechanism is not fully understood. Herein, colloidal CsPbBr perovskite nanocrystals (PNCs) with fragile dynamic equilibrium of ligands are taken as the examples to reveal the important role of balancing ligand-solid/solvent affinity in suppressing the desorption of ligands. As a micellar surfactant, glycyrrhizic acid (GA) with bulky hydrophobic and hydrophilic groups exhibits a relatively smaller diffusion coefficient (∼440 μm/s in methanol) and weaker ligand-liquid affinity than that of conventional alkyl amine and carboxy ligands. Consequently, hydrophilic GA-passivated PNCs (PNCs-GA) show excellent colloidal stability in various polar solvents with dielectric constant ranging from 2.2 to 32.6 and efficient photoluminescence with a quantum yield of 85.3%. Due to the suppressed desorption of GA, the morphological and optical properties of PNCs-GA are well maintained after five rounds purification and two months long-term storage. At last, hydrophilic PNCs-GA are successfully patterned through inkjet- and screen-printing technology. These findings offer deep insights into the interfacial chemistry of colloidal NCs and provide a universal strategy for preparing high-quality hydrophilic PNCs.

摘要

表面结合配体的界面迁移极大地影响了半导体纳米晶体的胶体稳定性和光学质量,但其潜在机制尚不完全清楚。在此,我们以配体动态平衡脆弱的胶体 CsPbBr 钙钛矿纳米晶体(PNC)为例,揭示了平衡配体-固/溶剂亲合力在抑制配体解吸中的重要作用。作为一种胶束表面活性剂,具有较大疏水性和亲水性基团的甘草酸(GA)的扩散系数(在甲醇中约为 440μm/s)相对较小,与传统的烷基胺和羧基配体相比,配体-溶剂的亲合力较弱。因此,亲水 GA 钝化的 PNC(PNC-GA)在介电常数为 2.2 至 32.6 的各种极性溶剂中表现出优异的胶体稳定性和 85.3%的高效光致发光量子产率。由于 GA 的解吸受到抑制,PNC-GA 的形态和光学性能在经过五次提纯和两个月的长期储存后仍能得到很好的保持。最后,亲水 PNC-GA 可通过喷墨和丝网印刷技术进行图案化。这些发现为胶体 NC 界面化学提供了深入的见解,并为制备高质量的亲水 PNC 提供了一种通用策略。

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