Mechanistic Insights into the Photoluminescence Enhancement in Surface Ligand Modified CsPbBr₃ Perovskite Nanocrystals

We report a mechanistic study of the photoluminescence (PL) enhancement in CsPbBr3 perovskite nanocrystals (PNCs) induced by organic/inorganic hybrid ligand engineering. Compared to the as-synthesized oleic acid-oleylamine modified PNCs, the tributylphosphine oxide-CaBr2 modified PNCs can achieve a better passivation effect due to strong P=O-Pb coordination and Br-vacancy remedy, resulting in enhanced PL efficiency. We employ steady-state/time-resolved/temperature-dependent PL and fluence/polarization-dependent ultrafast transient absorption spectroscopy to obtain a mechanistic understanding of such an enhancement effect from both nonradiative and radiative perspectives. As for the dominating nonradiative recombination suppression, we quantitatively evaluate the contributions from channels of exciton dissociation and exciton trapping, which are connected to exciton binding energy and activation energy of exciton trapping to surface defect-induced trap states, respectively. We also look into the radiative recombination enhancement, which is likely due to the increase in electron-hole overlap of photogenerated excitons induced by slight Ca-doping. These mechanistic insights would be of guiding value for perovskite-based light-emitting applications.