Band alignment and crystal stability of Y3Al5−xGaxO12 garnets using density functional theory with hybrid functional

Abstract

In this study, the dependence of band gap, band alignment, and structural stability of Y3Al5−xGaxO12 garnet (YAGG) solid solutions on Ga content (x) have been investigated using density functional theory (DFT) with PBE0 hybrid functional. The most stable model of YAGG for each x is identified using evolutionary algorithm-based USPEX method. The band alignment was determined by connecting valence band maximum (VBM) and conduction band minimum (CBM) to vacuum level via macroscopic average electrostatic potential of the slab model. Solid solution formation energy as a function of x indicates that YAGG with x = 3.0 (Y3Al2Ga3O12) exhibits remarkable structural stability. At x = 3.0, the analysis of the formation energy contribution shows a dominant contribution from electronic charge redistribution energy while there is no contribution from distortion energy. Bader charge, electron localization function, as well as the projected density of state analysis reveal a strong covalent character of Ga under oxygen tetragonal environment. The calculated PBE0 band gap as a function of x agrees well with the experimental results. Ga admixing significantly lowers the CBM, which exhibits a potential to envelop the shallow electron traps from the forbidden gap. The YAGG band alignment calculated using the proposed vacuum-connecting method is consistent with VRBE results from experiment. The proposed methods used to model site-preferred solid solution and calculate the vacuum-connected band alignment are viable in predicting structural stability and band edge modification via compositional engineering of garnet solid solutions. We expect that this work provides a promising strategy for material design through compositional engineering in obtaining high stability and enhanced performance in garnet compounds.