To inhibit the detrimental diffusion of copper into silicon devices, an effective barrier is strongly demanded. In this study, copper( rhenium) alloy films were successfully electroless- and electroplated on silicon substrates for self-forming an ultrathin rhenium barrier layer. In pure copper films, the interdiffusion of copper and silicon already occurred at 400 degrees C, forming silicides and increasing the electrical resistivity of the films. In comparison, not any silicide formation was observed in the electroless- and electroplated copper(rhenium) alloy films with minor incorporations of rhenium for 0.10 and 0.39 at% until 600 and 500 degrees C, respectively, attributed to the prior segregation of rhenium and the self-formation of rhenium barrier layer at the copper/silicon interface at 400 degrees C. A zero solubility of rhenium in copper and a small solubility in palladium catalysts facilitate the separation of rhenium from copper. The kinetics of rhenium segregation follows uphill diffusion, and the diffusivity of rhenium in copper at 400 degrees C is estimated to be 1.5 x 10(-17) cm(2)/s. (C) The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. All rights reserved.