In order to improve the resistive switching reliability of devices made using TiO2 grown by atomic layer deposition at 130 degrees C, a thin Si layer was inserted between the Pt top electrode and the TiO2 thin films. The annealing of the Pt/Si(O)/TiO2/Pt structures at 300 degrees C in N-2 ambient produced Pt/Pt3Si/PtSi particle-embedded SiO2/Ti-silicate/TiO2/Pt multistructures, as confirmed by x-ray diffraction, x-ray photoelectron spectroscopy, and high resolution transmission electron microscopy. The as-annealed multistructures showed enhanced adhesion properties and significantly improved resistive switching performances, especially in terms of the number of the switching cycles and device yield. Based on the analyses, the authors proposed that the interfacial formation of Pt3Si and Ti silicate is responsible for the enhanced adhesion and the improved resistive switching reliability of TiO2 devices result from the enhanced mechanical stability as well as the presence of Ti silicate, which acts as source and sink for defects. (C) 2009 American Vacuum Society. [DOI:10.1116/1.3207744]