Fine structure and size dependence of exciton and bi-exciton optical spectra in CdSe nanocrystals

TL;DR

This paper presents a detailed theoretical study of exciton and bi-exciton optical spectra in CdSe nanocrystals, revealing size-dependent fine structures and the transition of bi-exciton binding energy from negative to positive.

Contribution

It introduces an atomistic tight-binding and configuration-interaction approach to analyze exciton spectra and their size dependence in CdSe nanocrystals, highlighting fine structure effects.

Findings

Low-energy electron spectrum forms shells (s, p, ...).

Bi-exciton spectrum exhibits fine structure due to hole state degeneracy.

Bi-exciton binding energy changes sign at a critical size.

Abstract

Theory of electronic and optical properties of exciton and bi-exciton complexes confined in CdSe spherical nanocrystals is presented. The electron and hole states are computed using atomistic $sp^3d^5s^*$ tight binding Hamiltonian including an effective crystal field splitting, spin-orbit interactions, and model surface passivation. The optically excited states are expanded in electron-hole configurations and the many-body spectrum is computed in the configuration-interaction approach. Results demonstrate that the low-energy electron spectrum is organized in shells ($s$, $p$, ...), whilst the valence hole spectrum is composed of four low-lying, doubly degenerate states separated from the rest by a gap. As a result, the bi-exciton and exciton spectrum is composed of a manifold of closely lying states, resulting in a fine structure of exciton and bi-exciton spectra. The quasi-degenerate nature of the hole spectrum results in a correlated bi-exciton state, which makes it slowly convergent with basis size. We carry out a systematic study of the exciton and bi-exciton emission spectra as a function of the nanocrystal diameter and find that the interplay of repulsion between constituent excitons and correlation effects results in a change of the sign of bi-exciton binding energy from negative to positive at a critical nanocrystal size.