Role of Acid–Base Equilibria in the Size, Shape, and Phase Control of Cesium Lead Bromide Nanocrystals

A binary ligand system composed of aliphatic carboxylic acids and primary amines of various chain lengths is commonly employed in diverse synthesis methods for CsPbBr3 nanocrystals (NCs). In this work, we have carried out a systematic study examining how the concentration of ligands (oleylamine and oleic acid) and the resulting acidity (or basicity) affects the hot-injection synthesis of CsPbBr3 NCs. We devise a general synthesis scheme for cesium lead bromide NCs which allows control over size, size distribution, shape, and phase (CsPbBr3 or Cs4PbBr6) by combining key insights on the acid-base interactions that rule this ligand system. Furthermore, our findings shed light upon the solubility of PbBr2 in this binary ligand system, and plausible mechanisms are suggested in order to understand the ligand-mediated phase control and structural stability of CsPbBr3 NCs.