Polyelectrolyte-Mediated Assembly of Copper-Phthalocyanine Tetrasulfonate Multilayers and the Subsequent Production of Nanoparticulate Copper Oxide Thin Films

An approach to producing films of nanometer-sized copper oxide particulates, based on polyelectrolyte-mediated assembly of the precursor, copper(II)phthalocyanine tetrasulfonate (CPTS), is described. Multilayered CPTS and polydiallyldimethylammonium chloride (PDADMAC) were alternately assembled on different planar substrates via the layer-by-layer (LbL) procedure. The growth of CPTS multilayers was monitored by UV-visible spectrometry and quartz crystal microbalance (QCM) measurements. Both the UV-visible spectra and the QCM data showed that a fixed amount of CPTS could be attached to the substrate surface for a given adsorption cycle. Cyclic voltammograms at the CPTS/PDADMAC-covered gold electrode exhibited a decrease in peak currents with the layer number, indicating that the permeability of CPTS multilayers on the electrodes had diminished. When these CPTS multilayered films were calcined at elevated temperatures, uniform thin films composed of nanoparticulate copper oxide could be produced. Ellipsometry showed that the thickness of copper oxide nanoparticulate films could be precisely tailored by varying the thickness of CPTS multilayer films. The morphology and roughness of CPTS multilayer and copper oxide thin films were characterized by atomic force microscopy. X-ray diffraction (XRD) measurements indicated that these thin films contained both CuO and Cu₂O nanoparticles. The preparation of such copper oxide thin films with the use of metal complex precursors represents a new route for the synthesis of inorganic oxide films with a controlled thickness.