Through-chip electrodes for three-dimensional packaging can offer short interconnection and reduced signal delay. Formation of suitable vias by electrodeposition into cavities presents a filling problem similar to that encountered in the damascene process. Because via dimensions for through-chip filling are larger and have a higher aspect ratio relative to features in damascene, process optimization requires modification of existing superconformal plating baths and plating parameters. In this study, copper filling of high-aspect-ratio through-chip vias was investigated and optimized with respect to plating bath composition and applied current wavetrain. Void-free vias 70 mu m deep and 10 mu m wide were formed in 60 min using additives in combination with pulse-reverse current and dissolved-oxygen enrichment. The effects of reverse current and dissolved oxygen on the performance of superfilling additives is discussed in terms of their effects on formation, destruction, and distribution of a Cu(I) thiolate accelerant. (c) 2005 The Electrochemical Society. All rights reserved.