The growth of HfO2 thin films on a HF-dipped p-Si(100) substrate at 200 °C by atomic-layer deposition (ALD) using Hf[N(C2H5)(CH3)]4 and H2O vapor as precursors is demonstrated. Uniform HfO2 thin films are obtained on a 4-in. silicon wafer, and the energy-band gap and band offset are determined by x-ray photoelectron spectroscopy analysis. The as-deposited HfO2 thin film is amorphous and able to crystallize at 500 ∼ 600 °C with only the monoclinic phase. As for the electrical performance of Au–Ti–HfO2–Si metal oxide semiconductor capacitors, a dielectric constant of ∼17.8 and an equivalent oxide thickness value of ∼1.39 nm are obtained from the 40-cycle ALD film after annealing at 500 °C. In addition, the breakdown field is in the range of 5 ∼ 5.5 MV/cm, and the fixed charge density is on the order of 1012 cm−2, depending on the annealing temperatures. The interface quality of HfO2 thin films on silicon is satisfactory with an interface-trap charge density of ∼3.7 × 1011 cm−2 eV−1.