Ab initio structure modeling of complex thin-film oxides: thermodynamical stability of TiC/thin-film alumina

TL;DR

This paper introduces a computational method using ab initio calculations to identify and analyze stable and metastable thin-film oxide structures, demonstrated on alumina on TiC.

Contribution

The paper presents a novel approach to predict and analyze thin-film oxide structures based on bulk oxide motifs and DFT relaxations.

Findings

Identified stable and metastable thin-film configurations.

Provided insights into atomic structure relaxations.

Applied method to alumina on TiC system.

Abstract

We present an efficient and general method to identify promising candidate configurations for thin-film oxides and to determine structural characteristics of (metastable) thin-film structures using ab initio calculations. At the heart of this method is the complexity of the oxide bulk structure, from which a large number of thin films with structural building blocks, that is motifs, from metastable bulk oxide systems can be extracted. These span a coarse but well-defined network of initial configurations for which density functional theory (DFT) calculations predict and implement dramatic atomic relaxations in the corresponding, resulting thin-film candidates. The network of thin-film candidates (for various film thicknesses and stoichiometries) can be ordered according to their variation in ab initio total energy or in ab initio equilibrium Gibbs free energy. Analysis of the relaxed atomic structures for the most favored structures gives insight into the nature of stable and metastable thin-film oxides. We investigate ultrathin alumina nucleated on TiC as a model system to illustrate this method.