Thermal structural changes of TiOx films built on a Si(001) surface were investigated at the nanometer scale with scanning tunneling microscopy. Electronic properties of individual clusters were classified by means of scanning tunneling spectroscopy. The differential conductance (dI/dV) near the Fermi energy showed that nano-clusters were transformed from semiconducting Ti-silicates into metallic Ti-silicides after heating to 970 K. Peaks of normalized differential conductance (dI/dV/(I/V)) of the clusters shifted after heating to about 1070 K, indicating exclusion of oxygen from the clusters. (C) 2010 Elsevier B.V. All rights reserved.