In situ EC-STM studies of MPS, SPS, and chloride on Cu100: structural studies of accelerators for dual damascene electrodeposition

Electrochemical, differential capacitance, and in situ electrochemical scanning tunneling microscopy (EC-STM) methods are used to examine the interaction of bis(3-sulfopropyl)-disulfide (SPS) and mercaptopropylsulfonic acid (MPS) with Cu(100) surfaces both in the absence and presence of chloride. Both electrochemical and differential capacitance results are weakly perturbed by the addition of either MPS or SPS in the potential region between -0.2 and -0.5 V versus Ag/AgCl relative to the additive-free case. EC-STM images obtained from solutions of MPS alone exhibit a c(2 x 2) adlattice whereas those from SPS alone yield only the (1 x 1) structure. In the presence of Cl-, both adsorbates evince only a c(2 x 2) adlattice on the Cu(100) surface. The desorption potential of these structure is identical to that found with Cl- alone. These results show that neither MPS nor SPS adsorbs strongly on Cu(100) in the presence of Cl-.