The growth, thermal annealing behaviors, and electrical properties of Al2O3 thin films grown by atomic layer deposition (ALD) on bare (100)Si and various oxidized Si wafers, by in situ O3 oxidation at 400°C and ex situ rapid thermal annealing (RTA) under O2 atmosphere at 900°C, were investigated. The ALD process was performed using Al(CH3)3 and high concentration of O3(400gm3). The high oxidation potential of O3 oxidized the Si surface at a very early stage of film growth and eliminated the incubation period even on a bare Si surface. The as-grown Al2O3 films had excess oxygen in the films, which diffused to the film Si interface and increased the interfacial layer by oxidizing the Si substrates during postannealing. The Al2O3 films grown on a bare Si substrate had the highest concentration of excess oxygen which resulted in the largest increase in the interfacial layer thickness during postannealing. As a result, the initial oxidation of the Si wafer did not significantly decrease the capacitance density compared to the films grown on a nonoxidized Si wafer at the as-deposited and postannealed states. Therefore, the Al2O3 layers grown using a high concentration of O3 oxidant on the in situ O3 oxidized Si wafers showed real high-k gate dielectric performance although the dielectric constants of the Al2O3 films were rather small (∼9) compared to other high-k gate dielectric films.