Theory of Band Warping and its Effects on Thermoelectronic Transport Properties

TL;DR

This paper develops a comprehensive theory of band warping in electronic band structures, enabling accurate analysis of its effects on transport and thermoelectric properties, especially in complex materials like silicon.

Contribution

It introduces a radial expansion-based theory and defines angular effective mass, distinguishing band warping from non-parabolicity and anisotropy, with practical evaluation procedures.

Findings

Analyzed valence band warping in silicon using first-principles calculations.

Derived tensorial transport coefficients for warped and quadratically expandable bands.

Identified transport-equivalent ellipsoidal bands at critical points.

Abstract

Optical and transport properties of materials depend heavily upon features of electronic band structures in proximity to energy extrema in the Brillouin zone (BZ). Such features are generally described in terms of multi-dimensional quadratic expansions and corresponding definitions of effective masses. Multi-dimensional expansions, however, are permissible only under strict conditions that are typically violated by degenerate bands and even some non-degenerate bands. Suggestive terms such as "band warping" or "corrugated energy surfaces" have been used to refer to such situations and ad hoc methods have been developed to treat them. While numerical calculations may reflect such features, a complete theory of band warping has not been developed. We develop a generally applicable theory, based on radial expansions, and a corresponding definition of angular effective mass. Our theory also accounts for effects of band non-parabolicity and anisotropy, which hitherto have not been precisely distinguished from, if not utterly confused with, band warping. Based on our theory, we develop precise procedures to evaluate band warping quantitatively. As a benchmark demonstration, we analyze the warping features of valence bands in silicon using first-principles calculations and we compare those with previous semi-empirical models. We use our theory and angular effective masses to generalize derivations of tensorial transport coefficients for cases of either single or multiple electronic bands, with either quadratically expansible or warped energy surfaces. From that theory we discover the formal existence at critical points of transport-equivalent ellipsoidal bands that yield identical results from the standpoint of any transport property. Additionally, we illustrate the drastic effects that band warping can induce on thermoelectric properties using multi-band models.