A method of forming a high dielectric constant (high-k) dielectric layer by atomic layer deposition includes the following steps. Cycles are performed one after another, and each of the cycles sequentially includes performing a first oxygen precursor pulse to supply an oxygen precursor to a substrate disposed in a reactor; performing a first oxygen precursor purge after the first oxygen precursor pulse; performing a chemical precursor pulse to supply a chemical precursor to the substrate after the first oxygen precursor purge; and performing a chemical precursor purge after the chemical precursor pulse. The first oxygen precursor pulse, the first oxygen precursor purge, the chemical precursor pulse, and the chemical precursor purge are repeated by at least 3 cycles. A second oxygen precursor pulse is performed to supply an oxygen precursor to the substrate after the cycles. A second oxygen precursor purge is performed after the second oxygen precursor pulse.