Yang Hanjun, Cai Tong, Dube Lacie, Chen Ou
Department of Chemistry, Brown University 324 Brook St. Providence Rhode Island 02912 USA
Chem Sci. 2022 Mar 30;13(17):4874-4883. doi: 10.1039/d2sc00574c. eCollection 2022 May 4.
Lead-free halide perovskite nanocrystals (NCs) represent a group of emerging materials which hold promise for various optical and optoelectronic applications. Exploring facile synthetic methods for such materials has been of great interest to not only fundamental research but also technological implementations. Herein, we report a fundamentally new method to access lead-free Bi-based double perovskite (DP) and quadruple perovskite (or layered double perovskite, LDP) NCs based on a post-synthetic transformation reaction of CsBiX (X = Cl, Br) zero-dimensional (0D) perovskite NCs under mild conditions. The produced NCs show good particle uniformity, high crystallinity, and comparable optical properties to the directly synthesized NCs. The relatively slow kinetics and stop-on-demand feature of the transformation reaction allow real-time composition-structure-property investigations of the reaction, thus elucidating a cation-alloyed intermediate-assisted transformation mechanism. Our study presented here demonstrates for the first time that post-synthetic transformation of 0D perovskite NCs can serve as a new route towards the synthesis of high-quality lead-free perovskite NCs, and provides valuable insights into the crystal structures, excitonic properties and their relationships of perovskite NCs.
无铅卤化物钙钛矿纳米晶体(NCs)是一类新兴材料,在各种光学和光电子应用中具有广阔前景。探索此类材料的简便合成方法不仅对基础研究具有重要意义,对技术应用也至关重要。在此,我们报道了一种全新的方法,即在温和条件下,基于CsBiX(X = Cl,Br)零维(0D)钙钛矿纳米晶体的合成后转化反应,制备无铅铋基双钙钛矿(DP)和四重钙钛矿(或层状双钙钛矿,LDP)纳米晶体。所制备的纳米晶体表现出良好的颗粒均匀性、高结晶度,以及与直接合成的纳米晶体相当的光学性质。转化反应相对较慢的动力学和按需停止的特性使得能够对反应进行实时的组成-结构-性质研究,从而阐明了阳离子合金化中间体辅助的转化机制。我们在此展示的研究首次表明,0D钙钛矿纳米晶体的合成后转化可作为合成高质量无铅钙钛矿纳米晶体的新途径,并为钙钛矿纳米晶体的晶体结构、激子性质及其关系提供了有价值的见解。