Hot Carrier Transfer from CsPbBr3 Nanocrystal to Au25 Cluster: The Pivotal Role of Ligand-Controlled Diffusion

Abstract

Efficient hot carrier extraction from lead halide perovskite is the key to overcoming its Shockley-Queisser limit. The interaction of the perovskite surface with the acceptors plays a vital role in controlling the charge transfer process. Here, we have investigated the charge transfer from CsPbBr3 nanocrystals to Au25 clusters. Ultrafast pump-probe spectroscopy confirms that the Au25 cluster can efficiently extract hot carriers from the CsPbBr3 nanocrystal. The effect of ligand environment on the hot carrier transfer is studied by taking oleic acid/oleylamine (pristine) and trioctylphosphine-capped CsPbBr3 nanocrystals of similar size. The experimental data show that the ligand-controlled diffusion mechanism governs the charge transfer process rather than anchoring. The hot carrier transfer process is found to be dependent on the effective interaction distance between the nanocrystal surface and Au25 controlled by the ligand environment. The hot carrier transfer rate to the Au25 cluster is estimated to be almost double for trioctylphosphine-capped CsPbBr3 nanocrystals (9.53×1011 s-1) compared to that of pristine nanocrystals (5.47×1011 s-1). Thus, optimizing the ligand environment of the perovskite nanocrystals is essential for Au25 to harvest the hot carriers.