The interaction between chloride and thiourea in copper electrode position in a sulfate-plating bath was investigated. The sole addition of thiourea to the bath increased the polarization of the electrode potential during copper deposition, leading to very fine and smoothly structured deposit but with microscopic nodules distributed over the surface. When chloride was added to a plating solution containing thiourea, the copper deposition mechanism was changed, showing a depolarization of the electrode potentia, and the copper deposits were found to have a relatively rougher microstructure, but without the formation of microscopic nodules However, rough deposit surfaces having no distinct pattern were formed at the macroscopic scale. Observations of roughening evolution show that the rough surface was initiated from small holes formed across the deposit surface during the initial stage of deposition that eventually developed into visibly rough deposits. The copper deposition inside these holes and at other areas was expected to undergo different deposition mechanisms. Copper deposition in the areas that ultimately developed into holes was almost totally inhibited by the thiourea-Cu(I)-chloride complex film, not just in the grain growth process, but over practically the entire electrodeposition process. Conversely, copper deposition occurred in other areas under conditions where nucleation preceded, but grain growth was inhibited to produce a fine, homogeneous microstructure. An uneven deposit surface that had different microscopic structures in different areas was then formed. The structure of the thiourea-Cu(I)-chloride film was strongly affected by the current density and appeared to break down completely if sufficiently high current density was applied to yield a fine and homogeneous microstructure that was also macroscopically smooth. (C) 2009 Elsevier Ltd. All rights reserved.