Atomistic $k.p$ theory

TL;DR

The paper introduces atomistic $k ext{·}p$ theory, a novel method that combines the advantages of traditional $k ext{·}p$ models with atomistic precision, enabling detailed electronic structure calculations in crystalline solids.

Contribution

It presents the first new $k ext{·}p$ method in decades, deriving parameters directly from experimental data or ab initio calculations, and extends $k ext{·}p$ theory to atomistic problems.

Findings

Equivalent to $sp^3$ tight-binding model for diamond/zincblende crystals.

Computed band structures for all III-V semiconductors without nitrogen or boron.

Demonstrated applicability to impurities, alloys, polytypes, and interfaces.

Abstract

Pseudopotentials, tight-binding models, and $k\cdot p$ theory have stood for many years as the standard techniques for computing electronic states in crystalline solids. Here we present the first new method in decades, which we call atomistic $k\cdot p$ theory. In its usual formulation, $k\cdot p$ theory has the advantage of depending on parameters that are directly related to experimentally measured quantities, however it is insensitive to the locations of individual atoms. We construct an atomistic $k\cdot p$ theory by defining envelope functions on a grid matching the crystal lattice. The model parameters are matrix elements which are obtained from experimental results or {\it ab initio} wave functions in a simple way. This is in contrast to the other atomistic approaches in which parameters are fit to reproduce a desired dispersion and are not expressible in terms of fundamental quantities. This fitting is often very difficult. We illustrate our method by constructing a four-band atomistic model for a diamond/zincblende crystal and show that it is equivalent to the $sp^3$ tight-binding model. We can thus directly derive the parameters in the $sp^3$ tight-binding model from experimental data. We then take the atomistic limit of the widely used eight-band Kane model and compute the band structures for all III-V semiconductors not containing nitrogen or boron using parameters fit to experimental data. Our new approach extends $k\cdot p$ theory to problems in which atomistic precision is required, such as impurities, alloys, polytypes, and interfaces. It also provides a new approach to multiscale modeling by allowing continuum and atomistic $k\cdot p$ models to be combined in the same system.