Alloying effects on the optical properties of Ge$_{1-x}$Si$_x$ nanocrystals from TDDFT and comparison with effective-medium theory

TL;DR

This study investigates the optical properties of Ge$_{1-x}$Si$_x$ alloy nanocrystals using TDDFT and compares the results with classical effective-medium theory, revealing how composition influences excitations and absorption spectra.

Contribution

It provides a detailed TDDFT analysis of alloy nanocrystals' optical spectra and demonstrates the effectiveness of classical models in capturing depolarization effects.

Findings

Absorption spectra vary smoothly with composition.

Classical effective-medium theory accurately models depolarization effects.

Emission spectra show weak transitions below absorption onset.

Abstract

We present the optical spectra of Ge$_{1-x}$Si$_x$ alloy nanocrystals calculated with time-dependent density-functional theory in the adiabatic local-density ap proximation (TDLDA). The spectra change smoothly as a function of the compositio n $x$. On the Ge side of the composition range, the lowest excitations at the ab sorption edge are almost pure Kohn-Sham independent-particle HOMO-LUMO transitio ns, while for higher Si contents strong mixing of transitions is found. Within T DLDA the first peak is slightly higher in energy than in earlier independent-par ticle calculations. However, the absorption onset and in particular its composit ion dependence is similar to independent-particle results. Moreover, classical depolarization effects are responsible for a very strong suppression of the abs orption intensity. We show that they can be taken into account in a simpler way using Maxwell-Garnett classical effective-medium theory. Emission spectra are in vestigated by calculating the absorption of excited nanocrystals at their relaxe d geometry. The structural contribution to the Stokes shift is about 0.5 eV. Th e decomposition of the emission spectra in terms of independent-particle transit ions is similar to what is found for absorption. For the emission, very weak tra nsitions are found in Ge-rich clusters well below the strong absorption onset.