Insertion of metal cations into hybrid organometallic halide perovskite nanocrystals for enhanced stability: eco-friendly synthesis, lattice strain engineering, and defect chemistry studies.

Abstract

In this work, we developed a facile and environmentally friendly synthesis strategy for large-scale preparation of Cr-doped hybrid organometallic halide perovskite nanocrystals. In the experiment, methylammonium lead bromide, CH3NH3PbBr3, was efficiently doped with Cr3+ cations by eco-friendly method at low temperatures to grow crystals via antisolvent-crystallization. The as-synthesized Cr3+ cation–doped perovskite nanocrystals displayed ∼45.45% decrease in the (100) phase intensity with an enhanced Bragg angle (2θ) of ∼15.01° compared to ∼14.92° of pristine perovskites while retaining their cubic (221/Pm-cm, ICSD no. 00-069-1350) crystalline phase of pristine perovskites. During synthesis, an eco-friendly solvent, ethanol, was utilized as an antisolvent to grow nanometer-sized rod-like crystals. However, Cr3+ cation-doped perovskite nanocrystals display a reduced crystallinity of ∼67% compared to pristine counterpart with ∼75% crystallinity with an improved contact angle of ∼72° against water in thin films. Besides, as-grown perovskite nanocrystals produced crystallite size of ∼48 nm and a full-width-at-half-maximum (FWHM) of ∼0.19° with an enhanced lattice-strain of ∼4.52 × 10−4 with a dislocation-density of ∼4.24 × 1014 lines per m2 compared to pristine perovskite nanocrystals, as extracted from the Williamson–Hall plots. The as-obtained stable perovskite materials might be promising light-harvesting candidates for optoelectronic applications in the future.