Selective Atomic Layer Deposition Mechanism for Titanium Dioxide Films with (EtCp)Ti(NMe₂)₃: Ozone versus Water

Abstract

The need for the conformal deposition of TiO2 thin films in device fabrication has motivated a search for thermally robust titania precursors with noncorrosive byproducts. Alkylamido-cyclopentadienyl precursors are attractive because they are readily oxidized, yet stable, and afford environmentally mild byproducts. We have explored the deposition of TiO2 films on OH-terminated SiO2 surfaces by in situ Fourier transform infrared spectroscopy using a novel titanium precursor [(EtCp)Ti(NMe2)3 (1), Et = CH2CH3] with either ozone or water. This precursor initially reacts with surface hydroxyl groups at ≥150 °C through the loss of its NMe2 groups. However, once the precursor is chemisorbed, its subsequent reactivities toward ozone and water are very different. There is a clear reaction with ozone, characterized by the formation of monodentate formate and/or chelate bidentate carbonate surface species; in contrast, there is no detectable reaction with water. For the ozone-based ALD process, the surface formate/carbonate species react with the NMe2 groups during the subsequent pulse of 1, forming Ti—O—Ti bonds. Ligand exchange is observed within the 250–300 °C ALD window. X-ray photoelectron spectroscopy confirms the deposition of stoichiometric TiO2 films with no detectable impurities. For the water-based process, ligand exchange is not observed. Once 1 is adsorbed, there is no spectroscopic evidence for further reaction. However, there is still TiO2 deposition under typical ALD conditions. Co-adsorption experiments with controlled vapor pressures of water and 1 indicate that deposition arises solely from 1/water gas-phase reactions. This striking lack of reactivity between chemisorbed 1 and water is attributed to the electronic and steric effects of the EtCp group and facilitates the observation of gas-phase reactions.