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通过中间异质结构将聚(马来酸酐-1-十八烯)修饰的胶体CsPbBr纳米晶体转化为稳定的CsPbBr钙钛矿发光体。

Transforming colloidal CsPbBr nanocrystals with poly(maleic anhydride--1-octadecene) into stable CsPbBr perovskite emitters through intermediate heterostructures.

作者信息

Baranov Dmitry, Caputo Gianvito, Goldoni Luca, Dang Zhiya, Scarfiello Riccardo, De Trizio Luca, Portone Alberto, Fabbri Filippo, Camposeo Andrea, Pisignano Dario, Manna Liberato

机构信息

Nanochemistry Department, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy.

Analytical Chemistry Lab, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy.

出版信息

Chem Sci. 2020 Apr 21;11(15):3986-3995. doi: 10.1039/D0SC00738B. Epub 2020 Mar 20.

Abstract

The preparation of strongly emissive CsPbBr perovskite nanocrystals with robust surface passivation is a challenge in the field of lead halide perovskite nanomaterials. We report an approach to prepare polymer-capped CsPbBr perovskite nanocrystals by reacting oleylammonium/oleate-capped CsPbBr nanocrystals with poly(maleic anhydride--1-octadecene) (PMAO). PMAO contains succinic anhydride units that are reactive towards the oleylamine species present on the CsPbBr nanocrystals' surface and produces polysuccinamic acid, which, in turn, triggers the CsPbBr to CsPbBr conversion. The transformation occurs through the formation of CsPbBr-CsPbBr heterostructures as intermediates, which are captured because of the mild reactivity of PMAO and are investigated by high-resolution electron microscopy. The CsPbBr-CsPbBr heterostructures demonstrate a dual emission at cryogenic temperature with an indication of the energy transfer from CsPbBr to CsPbBr. The fully-transformed CsPbBr NCs have high photoluminescence quantum yield and enhanced colloidal stability, which we attribute to the adhesion of polysuccinamic acid to the NC surface through its multiple functional groups in place of oleate and alkylammonium ligands. The PMAO-induced transformation of CsPbBr NCs opens up a strategy for the chemical modification of metal halide NCs initially passivated with nucleophilic amines.

摘要

制备具有强表面钝化作用的强发射性CsPbBr钙钛矿纳米晶体是卤化铅钙钛矿纳米材料领域的一项挑战。我们报道了一种通过使油胺/油酸封端的CsPbBr纳米晶体与聚(马来酸酐-1-十八烯)(PMAO)反应来制备聚合物封端的CsPbBr钙钛矿纳米晶体的方法。PMAO含有琥珀酸酐单元,其对CsPbBr纳米晶体表面存在的油胺物种具有反应性,并产生聚琥珀酰胺酸,进而引发CsPbBr向CsPbBr的转变。这种转变通过形成CsPbBr-CsPbBr异质结构作为中间体而发生,由于PMAO的温和反应性,这些中间体被捕获,并通过高分辨率电子显微镜进行研究。CsPbBr-CsPbBr异质结构在低温下表现出双重发射,表明存在从CsPbBr到CsPbBr的能量转移。完全转变后的CsPbBr纳米晶体具有高光致发光量子产率和增强的胶体稳定性,我们将其归因于聚琥珀酰胺酸通过其多个官能团取代油酸和烷基铵配体而附着在纳米晶体表面。PMAO诱导的CsPbBr纳米晶体转变为最初用亲核胺钝化的金属卤化物纳米晶体的化学修饰开辟了一种策略。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c517/8045465/e2d3e100c143/d0sc00738b-f1.jpg

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