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Heat Effects upon Electrochemical Copper Deposition on Polycrystalline Gold
Author(s) -
Etzel Kai D.,
Bickel Katrin R.,
Schuster Rolf
Publication year - 2010
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200900981
Subject(s) - electrochemistry , deposition (geology) , copper , chemistry , inorganic chemistry , monolayer , crystallite , electrolyte , underpotential deposition , electrode , layer (electronics) , analytical chemistry (journal) , cyclic voltammetry , crystallography , organic chemistry , paleontology , biochemistry , sediment , biology
Abstract Heat effects upon Cu deposition on polycrystalline Au surfaces from sulphuric acid electrolytes were calorimetrically measured. By combination of pyroelectric temperature detection at the backside of a thin electrode foil with pulsed electrochemistry, sensitivities to electrochemical conversions of a few percent of a Cu monolayer (ML), corresponding to about 1 μJ cm −2 were achieved. We compared the heat evolution upon Cu under potential deposition (UPD), Cu deposition onto a fully developed Cu UPD layer and bulk Cu deposition onto a 300 ML thick Cu layer on Au. The heat effects were measured dependent on the amplitudes of the applied potential steps, that is, the driving forces of the respective reactions. From the differences of the heat effects among the Cu deposition processes, we deduced implications on the reaction mechanisms. For Cu UPD, the heat effects were explicable by the deposition of 1.3 Cu atoms per two electrons flowing to the electrode accompanied by sulphate coadsorption, similar to Cu UPD from sulphuric acid solutions on Au(111). Upon Cu deposition on a Cu UPD layer the heat effects signal considerable anion coadsorption up to the deposition of about 0.5 ML of Cu. At higher conversions the deposition mechanism gradually changes towards bulk Cu deposition, accompanied by reduction of the sulphate coverage.