Understanding and controlling the work function of perovskite oxides using Density Functional Theory

TL;DR

This study uses Density Functional Theory to predict and analyze the work functions of perovskite oxides, revealing trends and identifying SrVO3 as a promising low work function, highly conductive material for electronic applications.

Contribution

The paper provides the first systematic prediction of work function trends in perovskite oxides using DFT, linking work function to electronic structure and surface properties.

Findings

Work functions range from 1.60-3.57 eV for AO surfaces and 2.99-6.87 eV for $BO_2$ surfaces.

Linear correlation between work function and oxygen 2p band center (R^2 0.77-0.86).

SrVO3 identified as a stable, low work function, highly conductive material.

Abstract

Perovskite oxides containing transition metals are promising materials in a wide range of electronic and electrochemical applications. However, neither their work function values nor an understanding of their work function physics have been established. Here, we predict the work function trends of a series of perovskite ($ABO_3$ formula) materials using Density Functional Theory, and show that the work functions of (001)-terminated AO- and $BO_2$-oriented surfaces can be described using concepts of electronic band filling, bond hybridization, and surface dipoles. The calculated range of AO ($BO_2$) work functions are 1.60-3.57 eV (2.99-6.87 eV). We find an approximately linear correlation ($R^2$ between 0.77-0.86, depending on surface termination) between work function and position of the oxygen 2p band center, which correlation enables both understanding and rapid prediction of work function trends. Furthermore, we identify $SrVO_3$ as a stable, low work function, highly conductive material. Undoped (Ba-doped) $SrVO_3$ has an intrinsically low AO-terminated work function of 1.86 eV (1.07 eV). These properties make $SrVO_3$ a promising candidate material for a new electron emission cathode for application in high power microwave devices, and as a potential electron emissive material for thermionic energy conversion technologies.