The electrodeposition of copper has recently become a "hot topic" due to its extensive application to the fabrication of interconnects in the integrated circuits (IC) manufacturing process. However, the proper composition of the electrochemical deposition (ECD) bath, and in particular the selection of the levelling agent, represents one of the crucial factors for an effective transition of Cu ECD towards the most advanced technology nodes. In this paper we report on the electrodeposition of Cu from acidic sulphate baths containing a potential innovative polymeric leveller: a benzyl-phenyl modified polyethyleneimine (BPPEI). This investigation was carried out by: (i) cyclic voltammetry (CV) at a rotating-disk electrode, (ii) in situ surface-enhanced Raman spectroscopy (SERS) during electrodeposition and (iii) scanning electron microscopy (SEM). CV results show that BPPEI acts as an inhibitor of the electrodeposition process, since it reduces the exchange current density and increases the cathodic Tafel slope. Mass transport limitations to the Cu(II) reduction process are essentially unaffected by the presence of BPPEI. SERS spectra show that BPPEI is adsorbed at the growing Cu cathode at all potentials of interest for electroplating. SEM micrographs prove that BPPEI acts as an efficient grain-refiner and suppressor of unstable 3D growth. Cathodic reactivity of BPPEI was proved by the analysis of CV features and potential-dependent SERS spectral changes. (c) 2007 Elsevier Ltd. All rights reserved.