The influence of temperature on the electrodeposition of copper on alkaneth
iolate-covered Au(lll) was studied by means of cyclic voltammetry and in si
tu scanning tunneling microscopy (STM) in the temperature range from 300 to
345 K. We show that thermally induced defects allow for copper electrodepo
sition to occur much faster than at 300 K. Only at elevated temperatures ca
n smooth copper layers be grown on the thiolated electrodes, independent of
the thiolate chain length. The layerwise growth is mediated by a surfactan
t-libe action of the thiolate.