Band gap analysis and carrier localization in cation-disordered ZnGeN$_2$

TL;DR

This study investigates how cation site disorder affects the electronic properties and band gap of ZnGeN$_2$, revealing that disorder introduces localized states and reduces the band gap, impacting its optical applications.

Contribution

It provides a detailed analysis of the effects of partial disorder on ZnGeN$_2$'s electronic structure using advanced computational methods, filling a gap in current research.

Findings

Disorder reduces the band gap significantly.

Localized defect states form above the valence band.

Disorder complicates optical device integration.

Abstract

Cation site disorder provides a degree of freedom in the growth of ternary nitrides for tuning the technologically relevant properties of a material system. For example, the band gap of ZnGeN$_2$ changes when the ordering of the structure deviates from that of its ground state. By combining the perspectives of carrier localization and defect states, we analyze the impact of different degrees of disordering on electronic properties in ZnGeN$_2$, addressing a gap in current studies which focus on dilute or fully disordered systems. The present study demonstrates changes in the density of states and localization of carriers in ZnGeN$_2$ calculated using band gap-corrected density functional theory and hybrid calculations on partially disordered supercells generated using the Monte Carlo method. We use localization and density of states to discuss the ill-defined nature of a band gap in a disordered material, comparing multiple definitions of the energy gap in the context of theory and experiment. Decreasing the order parameter results in a large reduction of the band gap in disordered cases. The reduction in band gap is due in part to isolated, localized states that form above the valence band continuum and are associated with nitrogen coordinated by more zinc than germanium. The prevalence of defect states in all but the perfectly ordered structure creates challenges for incorporating disordered ZnGeN$_2$ into optical devices, but the localization associated with these defects provides insight into mechanisms of electron/hole recombination in the material.