Atomic layer deposition (ALD) has emerged as a promising technology for the development of the next generation of low-power semiconductor electronics. The wafer-scaled growth of two-dimensional (2D) crystalline nanostructures is a fundamental step toward the development of advanced nanofabrication technologies. Ga2O3 is an ultra-wide bandgap metal oxide semiconductor for application in electronic devices. The polymorphous Ga2O3 with its unique electronic characteristics and doping capabilities is a functional option for heterointerface engineering at metal-semiconductor 2D heterojunctions for application in nanofabrication technology. Plasma-enhanced atomic layer deposition (PE-ALD) enabled the deposition of ultra-thin nanostructures at low-growth temperatures. The present study used the PE-ALD process for the deposition of atomically thin crystalline ß-Ga2O3 films for heterointerface engineering at 2D metal-semiconductor heterojunctions. Via the control of plasma gas composition and ALD temperature, the wafer-scaled deposition of ~5.0 nm thick crystalline ß-Ga2O3 at Au/Ga2O3-TiO2 heterointerfaces was achieved. Material characterization techniques showed the effects of plasma composition and ALD temperature on the properties and structure of Ga2O3 films. The following study on the electronic characteristics of Au/Ga2O3-TiO2 2D heterojunctions confirmed the tunability of this metal/semiconductor polarized junction, which works as functional electron channel layer developed based on tunable p-n junctions at 2D metal/semiconductor interfaces.