Facile synthesis of phase-adjustable CsPbBr<sub>3</sub>-Cs<sub>4</sub>PbBr<sub>6</sub> composite nanocrystals and <i>in-situ</i> study of phase transformation process

All-inorganic cesium lead halide perovskites have shown great potential applications in optoelectronic field due to their fascinating optical properties. Although perovskite materials have achieved great success in various fields, their inherent ionic properties and high dynamic surface properties have led to their poor stability, hindering their applications. The preparation of CsPbBr₃-Cs₄PbBr₆ nanocrystals has proven to be an effective strategy to enhance their photoluminescence properties and stability. Herein, we report an easy synthesis of CsPbBr₃-Cs₄PbBr₆ nanocrystals with a diphase structure at room temperature by using Cs-OA, Pb-OA and TOABr as precursors in toluene. It is found that the phase transformation and the relative composition between CsPbBr₃ and Cs₄PbBr₆ are dependent on the concentration of TOABr and the ratio of Cs/Pb. The <i>in-situ</i> PL experiments reveal that the formation of ~12 nm CsPbBr₃ nanocubes experiences the fast nucleation, the focusing growth of size-distribution in early growth stage and Ostwald ripening growth in the later stage at a TOABr concentration of 0.16 mmol. With the increase of concentration of TOABr or molar ratio of Cs/Pb > 1 (Cs/Pb < 1), [PbBr₄]^2– complex and [PbBr₃]^– complex can coexist and compete with each other in toluene, and the CsPbBr₃ nucleations dominate in the early stage, then CsPbBr_3-Cs₄PbBr₆ nanocomposites are gradually formed on CsPbBr₃ nucleations as photoluminescence centers due to the continuous generation of [PbBr₄]^2– complex between TOABr and Pb²⁺. The relative composition of Cs₄PbBr₆ in CsPbBr_3-Cs₄PbBr₆ nanocomposites can be improved from 4% to 85% with the concentration of TOABr increasing or Cs/Pb < 1. The optimized CsPbBr₃-Cs₄PbBr₆ composite nanocrystals possess high PLQY and stability. Our work provides an understanding of the mechanism of phase transformation in cesium lead halide perovskite materials.