Chemical Availability of Bromide Dictates CsPbBr3 Nanocrystal Growth

Abstract

Lack of detailed understanding of the growth mechanism of CsPbBr3 nanocrystals has hindered sophisticated morphological and chemical control of this important emerging optoelectronic material. Here, we have elucidated the growth mechanism by slowing the reaction kinetics. When 1-bromohexane is used as an alternative halide source, bromide is slowly released into the reaction mixture, extending the reaction time from ~3 seconds to greater than 20 minutes. This enables us to monitor the phase evolution of products over the course of reaction, revealing that CsBr is the initial species formed, followed by Cs4PbBr6, and finally CsPbBr3. Further, formation of monodisperse CsBr nanocrystals is demonstrated in a bromide-deficient and lead-abundant solution. The CsBr can only be transformed into CsPbBr3 nanocubes if additional bromide is added. Our results indicate a fundamentally different growth mechanism for CsPbBr3 in comparison with more established semiconductor nanocrystal systems and reveal the critical role of the chemical availability of bromide for the growth reactions.<br>

Highly Stable Amine-Free CsPbBr3 Perovskite Nanocrystals for Perovskite-Based Display Applications

“…48 Bromine ions (Br − ) are sufficiently accessible as HBr during the reaction, which is believed to be generated by the nucleophilic substitution [SN 2 ] reaction between bromooctane and acetate/oleate. 61,62 The complete experimental details can be seen in the Supporting Information (SI). As-synthesized BrOct_amine-free CsPbBr 3 PNCs were cleaned with the nonpolar solvent hexane, and other impurities and excess surfactants were removed from the reaction mixture.…”