The spontaneous deposition of Ni on Si(100) surface in aqueous alkaline solution was investigated under various conditions. In a 0.1 M NiSO4 solution containing 0.2-0.5 M (NH4)2SO4, the optimum pH for the homogeneous deposition at 60-80°C at each set of operating conditions shifted in the high-pH direction as both (NH 4)2SO4 concentration and the operating temperature were decreased. The potential at which the deposition terminates and the deposition duration were determined from electrochemical open-circuit potential profiles. The different behaviors, observed at different pH levels, are discussed in terms of these potential measurements. Ultraviolet-visible absorption spectra of various Ni solutions used indicated that the deposition behavior was strongly affected by the composition of the Ni complex and the reactivity of Si surface. The deposition reaction efficiently proceeded when the Ni complex was present in a specific composition. The anodic reaction rate of Si decreased steeply when the solution temperature was lowered. The optimum condition for the homogeneous deposition was greatly affected by the reactivity of the Si surface rather man the composition of the complex, the higher pH favoring the overall reaction. © 2004 The Electrochemical Society. All rights reserved.