The rise time of the alternating current (ac) surface photovoltage (SPV) of n-type silicon (Si) contaminated by Fe and/or Cu aqueous solutions was investigated. After a rinse time of about 1000 min in Fe contaminated water, three monolayers (0.59 nm) of oxide were formed, with a resulting incorporation of Fe. The variation of ac SPV signals indicated the appearance of a negative charge corresponding to the increasing concentration of Fe on surface of the Si wafer. This negative charge can be accounted for by postulating a bridging mechanism between trivalent Fe ions, Fe3+, and quadrivalent Si ions, Si4+, forming an (FeOSi)(-) network in the native oxide. In contrast to Fe, Cu was deposited at the beginning of the rinsing on partially hydrophobic n-type Si surfaces as an Cu atomic layer or Cu particles (maximum Cu concentration: around 1 x 10(14) atoms/cm(2)), resulting in a Cu-Si contact. Because the reduction potential of Cu2+ is larger than that of Si, the process was accomplished through electron capture. It is postulated that theCu-Si contact may have formed a Schottky barrier between the Cu and n-type Si, resulting in the occurrence a so-called barrier-type ac SPV. This may prove to be a promising method for fabricating atomic layer Schottky devices. (C) 2003 The Electrochemical Society.