Understanding the Interface Reactions of Rutile TiO2 Grown by Atomic Layer Deposition on Oxidized Ruthenium

Abstract

The atomic layer deposition of titanium oxide TiO2 on ruthenium and oxidized ruthenium with titanium methoxide as metal precursor and H2O and O3 as oxidant was investigated by Rutherford backscattering (RBS) and time of flight secondary ion mass spectrometry (TOFSIMS). An ultra-thin layer of TiO2 deposited a priori with H2O plays the role of protection of Ru(Ox) substrates against etching by O3. Information about thin films (∼3 nm) interfacial reactions, thickness and structure was brought by Medium Energy Ion Scattering Spectroscopy (MEIS) and X-ray absorption spectroscopy (XAS) measurements. The growth enhancements observed in the first stages of the deposition depends on the pre-treatment (pre-oxidation, H2O based interlayer thickness) of the Ru substrate. Thick films (∼14 nm) were analyzed by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The as deposited TiO2 films are crystalline with rutile structure, as resulted from structural analyzes. However, the presence of small amounts of anatase was detected by soft X-ray absorption spectroscopy (XAS) and is strongly influenced by the surface pre-treatment of the Ru substrate. The electrical properties (equivalent oxide thickness and leakage current density) correlate with a different rutile/anatase ratio present in the films.