All-order correlation of single excitons in nanocrystals using a $\mathbf{k}\cdot\mathbf{p}$ envelope-function approach: application to lead-halide perovskites

TL;DR

This paper develops and compares many-body approaches within the ffective-mass and nkotp envelope-function formalisms to accurately calculate correlated single excitons in lead-halide perovskite nanocrystals, revealing significant correlation effects on physical observables.

Contribution

It introduces a comprehensive ll-order method framework for exciton correlation in nanocrystals, applying it to lead-halide perovskites and demonstrating improved agreement with experimental data.

Findings

Correlation significantly enhances radiative decay rates.

Numerical results agree with analytical large-size limits.

Calculated absorption cross sections match experimental spectra.

Abstract

We discuss a variety of many-body approaches, within effective-mass and $\mathbf{k}\cdot\mathbf{p}$ envelope-function formalisms, for calculating correlated single excitons in semiconductor nanocrystals (NCs) to all orders in the electron-hole Coulomb interaction. These approaches are applied to NCs of the lead-halide perovskite CsPbBr$_{3}$, which typically present excitons in intermediate confinement with physical observables often strongly renormalized by correlation (e.g., radiative decay rate enhanced by a factor of about 7 relative to a mean-field approach, for a NC of edge length 11 nm). The many-body methods considered include the particle-hole Bethe-Salpeter equation, configuration interaction with single excitations, and the random-phase approximation with exchange (RPAE), which are shown to be closely related to each other but to treat $\mathbf{k}\cdot\mathbf{p}$ corrections differently, with RPAE being the most complete method. The methods are applied to calculate the correlation energy, the radiative lifetime, and the long-range Coulomb contribution to the fine structure of the ground-state exciton. In the limit of large NC sizes, the numerical results are shown to agree well with analytical results for this limit, where these are known. Correlated excited states of the single exciton are used to calculate the one-photon absorption cross section; the shape of the resulting cross-section curve (versus laser wavelength) at threshold and up to an excitation energy of about 1 eV is in good agreement with experimental cross sections. The equations for the methods are explicitly adapted to spherical symmetry (involving radial integrals and angular factors) and in this form permit a rapid computation for systems in intermediate confinement.