The decomposition of titanium diisopropoxide dipivaloylmethanato [Ti(O-iPr)(2)(dpm)(2): dpm = bis(2,2,6,6-tetramethyl-3,5-heptanedionato), C11H19O2], a Ti precursor used in metallorganic chemical vapor deposition or in atomic layer deposition processes for producing Ti-containing films, was studied in a high vacuum chamber, maintained at a pressure of 1 x 10(-10) Torr, using temperature-programmed desorption (TPD). The species present on the substrate surface at different temperatures in the TPD experiments were monitored by X-ray photoelectron spectroscopy (XPS). The isopropoxy ligand is dissociated from the Ti precursor, producing acetone and isopropanol by disproportionation at 400 K and only acetone at temperatures higher than 470 K. The dissociation of the isopropoxy ligand is complete at 500 K. The dpm ligand is dissociated to give propylene and propanal at all temperatures above 470 K and the dissociation is complete at about 700 K. The XPS results indicate that titanium oxide is formed on the substrate surface at temperatures above 600 K. The other surface component is carbon, which largely originates from the t-butyl group. The formation of titanium oxide was confirmed by a separate film-deposition experiment at relatively high pressures, similar to 10 Torr, using the same Ti precursor. That is, a film deposited on Pt at high pressures showed an XPS peak for the Ti 2p state, representing titanium oxide, as the major peak when the Ti precursor was decomposed at temperatures higher than 500 K, the temperature range for dissociation of the dpm ligand. (c) 2006 The Electrochemical Society.