Selective tracking of charge carrier dynamics in CuInS2 quantum dots

TL;DR

This study investigates charge carrier dynamics in CuInS2 quantum dots, revealing that Cu-deficiency improves properties through increased crystallinity rather than Cu2+ formation, and demonstrates ultrafast hole transfer to ligands.

Contribution

It provides new insights into the charge carrier behavior and the effects of stoichiometry in CuInS2 quantum dots using advanced ultrafast X-ray and optical spectroscopies.

Findings

No evidence of native Cu2+ states in Cu-deficient samples

Holes transfer from Cu atoms to ligands in sub-picosecond timescales

Cu-deficient samples resist photothermal heating better than stoichiometric ones

Abstract

CuInS2 quantum dots have been studied in a broad range of applications, but despite this, the fine details of their charge carrier dynamics remain a subject of intense debate. Two of the most relevant points of discussion are the hole dynamics and the influence of Cu:In synthesis stoichiometry on them. It has been proposed that Cu-deficiency leads to the formation of Cu2+, affecting the localization of holes into Cu defects. Importantly, it is precisely these confined hole states which are used to explain the interesting photoluminescence properties of CuInS2 quantum dots. We use static X-ray spectroscopy to reveal no evidence for a measurable amount of native Cu2+ states in Cu-deficient samples. Instead, the improved properties of these samples are explained by an increase of crystallinity, reducing the concentration of mid gap states. Furthermore, to understand the charge carrier dynamics, herein we employ ultrafast optical transient absorption, and fluorescence up-conversion spectroscopies in combination with ultrafast X-ray absorption spectroscopy using a hard X-ray free electron laser. We demonstrate that in non-passivated samples, holes are transferred from Cu atoms in sub-picosecond timescales. We assign this transfer to occur towards the thiol-based ligands. Finally, we observe that Cu-deficient samples are more robust against the photothermal heating effects of using higher laser fluences. This is not the case for the stoichiometric sample, where heating effects on the structure are directly observed.