Electroless silver deposition onto p-silicon (1 1 1) from 0.005 mol l(-1) AgNO3 solutions with different HF concentration was investigated by using an electrochemical direct current polarization method and open circuit potential-time (Ocp-t) technique. The fact that three-dimensional (3D) growth of silver onto silicon is favored with increasing the HF concentration was ascribed to the drop of the surface energy and approved by electrochemical direct current polarization, Ocp-t technique and atomic force microscopy (AFM). The drop slope of open-circuit potential, K-Delta E(OCP)/t, was educed from the mixed-potential theory. K-Delta E(OCP)/t as well as the deposition rate determined by an inductively coupled plasma atomic emission spectrometry (ICP-AES), increased with the HF concentration, yet was not a linear function. Results were explained by the stress generation and relaxation mechanisms. (c) 2006 Elsevier B.V. All rights reserved.