Surface Charges on CdSe-Dot/CdS-Rod Nanocrystals: Measuring and Modeling the Diffusion of Exciton-Fluorescence Rates and Energies

TL;DR

This study combines cryogenic single-particle spectroscopy and modeling to understand how surface charges influence exciton fluorescence rates and energies in CdSe/CdS nanocrystals, revealing the role of migrating surface charges.

Contribution

It introduces a combined experimental and theoretical approach to correlate surface charge dynamics with optical properties in core/shell nanocrystals, highlighting the impact of surface charges on exciton behavior.

Findings

Fluorescence decay rate is nearly linearly related to emission energy.

Surface charges, especially negative ones near the core, significantly shift emission properties.

Surface charges predominantly affect hole wave functions while preserving the core's type-I band alignment.

Abstract

By performing spectroscopic single-particle measurements at cryogenic temperatures over the course of hours we study %By performing spectroscopic longtime single-particle measurements at cryogenic temperatures we study both the spectral diffusion as well as the diffusion of the decay rates of the fluorescence emission of core/shell CdSe/CdS dot/rod nanoparticles. A special analysis of the measurements allow for a correlation of data for single neutral excitons only, undisturbed by the possible emission of other excitonic complexes. We find a nearly linear dependency of the fluorescence decay rate on the emission energy. The experimental data is compared to self-consistent model calculations within the effective-mass approximation, in which migrating point charges set onto the surface of the nanoparticles have been assumed to cause the temporal changes of optical properties. These calculations reveal a nearly linear relationship between the squared electron-hole wave function overlap, which is linked to the experimentally determined fluorescence rate, and the exciton emission energy. Within our model single migrating surface charges are not sufficient to fully explain the measured rather broad ranges of emission rates and energies, while two -- and in particular negative -- surface charges close to the core of the DR induce large enough shifts. Importantly, for our nanoparticle system, the surface charges more strongly affect the hole wave function than the electron wave function and both wave functions are still localized within the dot-like core of the nanoparticle, showing that the type-I character of the band alignment between core and shell is preserved.