Methods of forming a roughened metal surface on a substrate are provided, along with structures comprising such roughened surfaces. In preferred embodiments roughened surfaces are formed by selectively depositing metal or metal oxide on a substrate surface to form discrete, three-dimensional islands. Selective deposition may be obtained, for example, by modifying process conditions to cause metal agglomeration or by treating the substrate surface to provide a limited number of discontinuous reactive sites. The roughened metal surface may be used, for example, in the manufacture of integrated circuits.