Investigating the ranges of (meta)stable phase formation in (InxGa1-x)2O3: Impact of the cation coordination

TL;DR

This study combines computational and experimental methods to explore the phase diagram of (InxGa1-x)2O3, revealing how cation coordination influences phase stability, solubility limits, and metastable ranges relevant for material synthesis.

Contribution

It provides a detailed phase diagram of (InxGa1-x)2O3 considering cation coordination effects, combining DFT, cluster expansion, and TEM measurements to understand metastable phase ranges.

Findings

Indium prefers six-fold coordination, influencing phase ordering.

Limited solubility of gallium and indium in ground state phases.

Wide metastable ranges at realistic growth temperatures.

Abstract

We investigate the phase diagram of the heterostructural solid solution (InxGa1-x)2O3 both computationally, by combining cluster expansion and density functional theory, and experimentally, by means of TEM measurements of pulsed laser deposited (PLD) heteroepitaxial thin films. The shapes of the Gibbs free energy curves for the monoclinic, hexagonal and cubic bixbyite alloy as a function of composition can be explained in terms of the preferred cation coordination environments of indium and gallium. We show by atomically resolved STEM that the strong preference of indium for six-fold coordination results in ordered monoclinic and hexagonal lattices. This ordering impacts the configurational entropy in the solid solution and thereby the (InxGa1-x)2O3 phase diagram. The resulting phase diagram is characterized by very limited solubilities of gallium and indium in the monoclinic, hexagonal and cubic ground state phases respectively but exhibits wide metastable ranges at realistic growth temperatures. On the indium rich side of the phase diagram a wide miscibility gap is found, which results in phase separated layers. The experimentally observed indium solubilities in the PLD samples are in the range of x=0.45 and x=0.55 for monoclinic and hexagonal single-phase films, while for phase separated films we find x=0.5 for the monoclinic phase, x=0.65-0.7 for the hexagonal phase and x>0.9 for the cubic phase. These values are consistent with the computed metastable ranges for each phase.