The adsorption of copper deposited from an effusion cell in ultra high vacuum and electrodeposited from aqueous solution on As-terminated GaAs(001) is investigated by scanning tunneling microscopy, X-ray diffraction, as well as X-ray standing waves in combination with X-ray fluorescence spectroscopy. The analysis of the adsorbate is performed in situ with the samples either in ultra high vacuum or in aqueous electrolyte under potential control. Deposited as Cu ions from sulphuric acid solution, submonolayer coverages of Cu diffuse into the GaAs interface region assumimg predominantly Ga substitutional positions. Different positions with lower symmetry are occupied by Cu if submonolayer are deposited at room temperature in ultra high vacuum. At higher coverage, epitaxial Cu clusters grow by electrodeposition on the As-terminated GaAs(001), but with the Cu lattice of the islands rotated and inclined with respect to the GaAs substrate lattice, leading in total to eight equivalent domains. At comparable coverage, no epitaxial growth was observed for Cu deposited in ultra high vacuum.
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