Hole conductivity through a defect band in $\rm ZnGa_2O_4$

TL;DR

This study uses computational methods to analyze the electronic and defect properties of ZnGa2O4, revealing its potential for n-type conductivity and challenges for p-type doping due to defect formation energies and polaron effects.

Contribution

It provides a detailed theoretical investigation of defect-induced conductivity in ZnGa2O4, highlighting the role of antisite defects and alloying in enabling p-type and n-type conduction.

Findings

Ga_Zn antisite is the lowest energy donor defect.

p-type conductivity is hindered by high acceptor defect formation energy.

Alloying with excess Zn introduces an intermediate valence band facilitating p-type conductivity.

Abstract

Semiconductors with wide band gap (3.0 eV), high dielectric constant (> 10), good thermal dissipation, and capable of $n$- and $p$-type doping are highly desirable for high-energy power electronic devices. Recent studies indicate that $\rm ZnGa_2O_4$ may be suitable for these applications, standing out as an alternative to $\rm Ga_2O_3$. The simple face centered cubic spinel structure of $\rm ZnGa_2O_4$ results in isotropic electronic and optical properties, in contrast to the large anisotropic properties of the $\beta$-monoclinic $\rm Ga_2O_3$. In addition, $\rm ZnGa_2O_4$ has shown, on average, better thermal dissipation and potential for $n$- and $p$-type conductivity. Here we use density functional theory and hybrid functional calculations to investigate the electronic, optical, and point defect properties of $\rm ZnGa_2O_4$, focusing on the possibility for $n$- and p-type conductivity. We find that the cation antisite $\rm Ga_{Zn}$ is the lowest energy donor defect that can lead to unintentional $n$-type conductivity. The stability of self-trapped holes (small hole polarons) and the high formation energy of acceptor defects make it difficult to achieve $p$-type conductivity. However, with excess of Zn, forming $\rm Zn_{(1+2x)}Ga_{2(1-x)}O_4$ alloys display an intermediate valence band, facilitating $p$-type conductivity. Due to the localized nature of this intermediate valence band, $p$-type conductivity by polaron hopping is expected, explaining the low mobility and low hole density observed in recent experiments.