Electronic Structure and Optical Properties of Silicon Nanocrystals along their Aggregation Stages

TL;DR

This computational study investigates how the electronic states and optical properties of silicon nanocrystals evolve during their aggregation, using a new efficient atomistic electronic structure method capable of handling large, irregular nanostructures.

Contribution

A novel pseudopotential-based computational tool is developed to analyze large, irregular silicon nanocrystal aggregates and their electronic and optical evolution during aggregation stages.

Findings

Electronic states develop binding and anti-binding counterparts during aggregation

Optical absorption spectra evolve with aggregation, reflecting changes in electronic structure

The method enables realistic modeling of large nanocrystal systems

Abstract

The structural control of silicon nanocrystals is an important technological problem. Typically a distribution of nanocrystal sizes and shapes emerges under the uncontrolled aggregation of smaller clusters. The aim of this computational study is to investigate the evolution of the nanocrystal electronic states and their optical properties throughout their aggregation stages. To realistically tackle such systems, an atomistic electronic structure tool is required that can accommodate about tens of thousand nanocrystal and embedding lattice atoms with very irregular shapes. For this purpose, a computationally-efficient pseudopotential-based electronic structure tool is developed that can handle realistic nanostructures based on the expansion of the wavefunction of the aggregate in terms of bulk Bloch bands of the constituent semiconductors. With this tool, the evolution of the electronic states as well as the polarization-dependent absorption spectra correlated with the oscillator strengths over their aggregation stages are traced. The low-lying aggregate nanocrystal states develop binding and anti-binding counterparts of the isolated states. Such information may become instrumental with the maturity of the controlled aggregation of these nanocrystals.