Quantitative Modeling of Point Defects in $\beta$-Ga2O3 Combining Hybrid Functional Energetics with Semiconductor and Processes Thermodynamics

TL;DR

This paper presents a comprehensive quantitative model for native and impurity point defects in B-Ga2O3, integrating hybrid functional DFT energetics with thermodynamics to predict defect behavior during crystal growth and processing.

Contribution

It introduces the KROGER framework that combines defect formation energies with thermodynamic effects, enabling accurate defect modeling in B-Ga2O3 and other materials.

Findings

Including temperature-dependent bandgap effects improves defect predictions.

The model explains experimental conductivity and insulation changes in doped B-Ga2O3.

KROGER accurately captures defect equilibria during growth and annealing processes.

Abstract

B-gallium oxide (B-Ga2O3) is of high interest for power electronics because of its unique combination of melt growth, epitaxial growth, n-type dopability, ultrawide bandgap, and high critical field. Optimization of crystal growth processes to promote beneficial defects and suppress harmful ones requires accurate quantitative modelling of both native and impurity defects. Here we quantitatively model defect concentrations as a function of bulk crystal growth conditions and demonstrate the necessity of including effects such as bandgap temperature dependence, chemical potentials from thermochemistry, and defect vibrational entropy in modelling based on defect formation energies computed by density functional theory (DFT) with hybrid functionals. Without these contributions, grossly-erroneous and misleading predictions arise, e.g. that n-type doping attempts would be fully compensated by Ga vacancies. Including these effects reproduces the experimental facts that melt-grown Sn-doped B-Ga2O3 crystals are conductive with small compensation while annealing the same crystals in O2 at intermediate temperatures renders them insulating. To accomplish this modeling, we developed a comprehensive modelling framework (KROGER) based on calculated defect formation energies and flexible thermodynamic conditions. These capabilities allow KROGER to capture full and partial defect equilibria amongst native defects and impurities occurring during specific semiconductor growth or fabrication processes. We use KROGER to model 873 charge-states of 259 defects involving 19 elements in conditions representing bulk crystal growth by edge-fed growth (EFG) and annealing in O2. Our methodology is transferrable to a wide range of materials beyond B-Ga2O3. Integration of thermodynamic and first-principles modelling of point defects provides insight into optimization of point defect populations in growth and processing.