The influence of thiourea on copper electrodeposition: adsorbate identification and effect on electrochemical nucleation

Abstract

The effect of thiourea on copper deposition onto a copper seed layer from an electrolyte composed of CuSO4, H2SO4, deionized water, and thiourea was investigated. Even in the presence of very low concentrations of thiourea, extremely smooth and bright copper deposits were obtained. From the results of X-ray photoelectron spectroscopy, Auger electron spectroscopy, and electrochemical analyses, thiourea was found to react with copper or copper ions leading to the generation of CuS. CuS adsorption onto the copper seed layer seemed to inhibit the initial nucleation of the copper adions, resulting in the formation of smaller Cu grains compared to those forming in the absence of thiourea. CuS was observed to cover all active sites of the 1 cm2 copper seed layer above 0.017 g/L thiourea. The surface roughness as well as the mean grain size of the deposits also approached minimum values above this thiourea concentration. Adsorbed CuS was incorporated into the deposits during electroplating, which was believed to be the major factor for the increased resistivity of the deposits.