Orientation dependence of Pd growth on Au electrode surfaces

The structure of thin Pd films grown on Au(111) and Au(001) electrodes in a solution containing PdCl42- and SO42- has been investigated by surface x-ray scattering. This technique provided structural information on the Pd films in the lateral direction as well as in the surface normal direction. Comparison of Pd/Au(111) and Pd/Au(001) growth modes shows similarity in the first layer deposition. On Au(111) and Au(001) substrates, Pd follows the crystal structure of the substrates and forms a pseudomorphic monolayer. Beyond 2 ML, however, Pd films grown on Au(111) are relaxed, although there are still pseudomorphic layers at the interface. In contrast, Pd films on Au(001) continue to grow pseudomorphically over 10 ML. The difference in the growth mode between (111) and (001) surfaces is not ascribable only to anisotropy in the elasticity of the film. The relationship between a growing surface and an allowed gliding plane in misfit dislocations is presented as a crucial factor determining the critical thickness of the film.