Scalable synthesis of colloidal CsPbBr3 perovskite nanocrystals with high reaction yields through solvent and ligand engineering

Abstract

The ligand assisted reprecipitation (LARP) technique is an accessible and facile method that can synthesize metal halide perovskite nanocrystals (PNCs) under ambient conditions. However, low product yields of less than 30% for LARP and its contemporary methods are indicative of highly inefficient reactions. In this work we apply the principles of green chemistry to the LARP technique for synthesizing CsPbBr₃ PNCs and help address this issue. Through these efforts, high product yields of ∼70% are achieved using stochiometric Cs : Pb precursor ratios. This is realized by (i) substituting the conventional toluene (TOL) anti-solvent with ethyl acetate (EA) and (ii) replacing the conventionally used unsaturated oleylamine ligand with the shorter saturated octylamine ligand. These changes also result in a 60% molar reduction in total ligand concentration and a 62.5% reduction in solvent waste during purification. The synthesized PNCs are comparable to the TOL-LARP reference in crystal quality, morphology and phase, with their photoluminescence quantum yields being readily enhanced to over 80% through additions of RNH₃Br ligands. The spectral versatility of these materials is demonstrated through post-synthetic chloride and iodide halide anion exchange, which readily yields tunable CsPbX₃ derivatives across the visible spectrum. Our EA-LARP protocol is further shown to be readily upscaled to ∼0.5 L, while maintaining good nanocrystal properties and a product yield of 60%.