Antisolvent-Assisted Growth of Centimeter-Scale CsPbBr$_3$ Perovskite Single Crystals: A Theory-Guided Approach

TL;DR

This study develops a theory-guided, systematic antisolvent vapor-assisted crystallization method to produce large, high-quality CsPbBr$_3$ perovskite single crystals efficiently at room temperature.

Contribution

It introduces a rational, theory-based approach to optimize the growth conditions for large CsPbBr$_3$ single crystals using antisolvent vapor-assisted crystallization.

Findings

Crystals up to 1 cm in size were grown within one week.

The optimized process yields phase-pure, orthorhombic CsPbBr$_3$ crystals.

Crystals exhibit high crystallinity and thermal stability up to 550°C.

Abstract

The fabrication of large, high-quality single crystals (SCs) of all-inorganic cesium lead bromide (CsPbBr$_3$) via accessible methods remains a significant challenge. This work presents a systematic approach to optimize the antisolvent vapor-assisted crystallization (AVC) method, where the experimental design is guided by a theoretical methods at each step. A synergistic 9:1 (v/v) DMSO/DMF binary solvent was selected to balance solubility and kinetics, a choice rationalized by an analysis of Gutmann's donor numbers. Subsequently, ethanol was selected as a promising antisolvent by evaluating its properties against key criteria of miscibility and diffusion rate using Hansen Solubility Parameters (HSP) and Fick's law expressed in terms of saturated vapor pressure. Within this rationally-defined chemical system, the "growth window" was experimentally mapped, identifying an optimal precursor concentration of 0.35 M and a preliminary titration step to induce a controlled metastable state. The optimized protocol consistently yields phase-pure, orthorhombic CsPbBr$_3$ SCs up to 1 cm in size within one week at room temperature. The resulting crystals exhibit high crystallinity and thermal stability up to \SI{550}{\celsius}