Here, we have explored the thermal stability of α-(Al,Ga)2O3 grown by the molecular-beam epitaxy on m-plane sapphire under high-temperature annealing conditions for various Al compositions (i.e., 0%, 46%, and 100%). Though uncapped α-Ga2O3 undergoes a structural phase transition to the thermodynamically stable β-phase at high temperatures, we find that an aluminum oxide cap grown by atomic layer deposition preserves the α-phase. Unlike uncapped α-Ga2O3, uncapped α-(Al,Ga)2O3 at 46% and 100% Al content remain stable at high temperatures. We quantify the evolution of the structural properties of α-Ga2O3, α-(Al,Ga)2O3, and α-Al2O3 and the energy bandgap of α-Ga2O3 up to 900 °C. Throughout the anneals, the α-Ga2O3 capped with aluminum oxide retains its high crystal quality, with no substantial roughening.
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