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Ellipsometry and van der Pauw measurements confirmed that the crystalline films have optical and electrical properties close to bulk gallium oxide. The film grown at 277 °C was determined to have superior properties among as-deposited films. Using TEM to locate α-Ga2O3 and β-Ga2O3 domains in the as-deposited crystalline films, we proposed a short annealing scheme to limit the development of α-Ga2O3 domains in the film and produce pure β-Ga2O3 films via an energy-efficient process. A pure β-Ga2O3 phase on sapphire with β-Ga2O3 (2̅01)∥α-Al