The nucleation and electrodeposition of copper from a pyrophosphate electrolyte onto anodized thin-film aluminum was used to provide well-adhering electroforms in high aspect-ratio resist molds made by X-ray lithography. Cyclic voltammetry and chronoamperometry methods were employed to characterize the impact of process variables on initiating copper deposition onto an anodized aluminum film. Adhesion of the electroplated films was evaluated using a 90 S peel test. Several aluminum films were studied to elucidate the influence that specific alloying elements have on the electrodeposition after anodization. The alloy content of the aluminum, specifically, small amounts of copper (1-4%), was found to significantly enhance nucleation. Under certain anodization conditions, small amounts of copper in the original aluminum film provided facile nucleation while aluminum alloys without copper could not be electroplated. The addition of copper to the aluminum alloys anodized at room temperature reduced the nucleation overpotential by more than 300 mV and increased the nuclei densities by two orders of magnitude. With sufficient adhesion of the electrodeposited metal to withstand both plated-metal stresses and planarization, through-mold electrodeposits were fabricated within resist molds ranging in height from 250 to 2800 mu m, possessing features having lateral dimensions down to 10 mu m. (c) 2006 The Electrochemical Society.