This research has studied remote plasma enhanced atomic layer deposited Ga2O3 thin films with gallium acetylacetonate (Ga(acac)3) as Ga precursor and remote inductively coupled oxygen plasma as oxidizer. The Ga2O3 thin films were mainly considered as passivation layers on GaN. Growth conditions including Ga(acac)3 precursor pulse time, O2 plasma pulse time, N2 purge time and deposition temperature were investigated and optimized on phosphorus doped Si (100) wafer to achieve a saturated self-limiting growth. A temperature growth window was observed between 150 ℃ and 320 ℃. Ga precursor molecules can saturate on the substrate surface in 0.6 s in one cycle and the plasma power saturates at 150 W. A growth rate of 0.31 Å/cycle was observed for PEALD Ga2O3. Since the study is devoted towards Ga2O3 working as passivation layer on GaN, the band alignment of Ga2O3 on GaN were further determined with X-ray Photoemission Spectroscopy and Ultraviolet Photoemission Spectroscopy. Two models are often used to decide the band alignment of a heterojunction: the electron affinity model assumes the heterojunction aligns at the vacuum level, and the charge neutrality level model (CNL) which considers the presence of an interface dipole. The conduction band offset (CBO), valence band offset (VBO) and band bending (BB) of PEALD Ga2O3 thin films on GaN were 0.1 ±0.2 eV, 1.0±0.2 eV and 0.3 eV respectively. Type-I band alignments were determined. Further study including using PEALD Ga2O3 as passivation layer on GaN MOS gate and applying atomic layer etching to GaN was described.