In-Situ Infrared Spectroscopy and Density Functional Theory Modeling of Hafnium Alkylamine Adsorption on Si−OH and Si−H Surfaces

In-situ attenuated total internal reflection infrared spectroscopy has been used to examine initial adsorption and reaction steps in atomic layer deposition of HfO 2 from tetrakis(diethylamino) hafnium (TDEAHf) on SiO 2 and hydrogen-terminated Si(100) surfaces. At low deposition temperatures (25−250 °C), TDEAHf directly reacts with the Si−H surface, resulting in partial removal of Si−H bonds and formation of a four-membered Si−O−Hf−Si bonding structure that can rapidly oxidize. The hydrogen removal process is observed to continue through many cycles of TDEAHf/H 2 O exposure, signifying continued reactivity of the Hf precursor with the silicon surface. Density functional theory calculations have been performed for various reactions between tetrakis(dimethylamino) hafnium and Si−H surfaces, and several possible reaction pathways for hydrogen removal have been identified and analyzed. The calculations suggest that hydrogen removal proceeds by H abstraction by an amine ligand of the Hf precursor and that the abstraction reaction is made more facile by the presence of OH on the otherwise H-terminated Si surface.