The effect of microstructure and purity on the native oxidation of Cu was studied by using angle-resolved X-ray photoelectron spectroscopy (AR-XPS) and spectroscopic ellipsometry (SE). A high quality copper film prepared by ion beam deposition under a substrate bias voltage of -50 V (IBD Cu film at V-s = -50 V) showed an oxidation resistance as high as an ultra high purity copper (UHP Cu) bulk, whereas a Cu film deposited without substrate bias voltage (IBD Cu film at V-s = 0 V) showed lower oxidation resistance. The growth of Cu2O layer on the UHP Cu bulk and both types of the films obeyed in principle a logarithmic rate law. However, the growth of oxide layer on the IBD Cu films at V-s = 0 and -50 V deviated upward from the logarithmic rate law after the exposure time of 320 and 800 h, respectively. The deviation from the logarithmic law is due to the formation of CuO on the Cu2O layer after a critical time. (c) 2006 Elsevier B.V. All rights reserved.