PEALD of HfO2 Thin Films: Precursor Tuning and a New Near-Ambient-Pressure XPS Approach to in Situ Examination of Thin-Film Surfaces Exposed to Reactive Gases

A bottom-up approach starting with the development of new Hf precursors for plasma-enhanced atomic layer deposition (PEALD) processes for HfO2 followed by in situ thin-film surface characterization of HfO2 upon exposure to reactive gases via near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) is reported. The stability of thin films under simulated operational conditions is assessed, and the successful implementation of HfO2 dielectric layers in metal–insulator–semiconductor (MIS) capacitors is demonstrated. Among the series of newly synthesized mono-guanidinato-tris-dialkyl-amido class of Hf precursors, one of them, namely, [Hf{η2-(iPrN)2CNEtMe}(NEtMe)3], was representatively utilized with oxygen plasma, resulting in a highly promising low-temperature PEALD process at 60 °C. The new precursors were synthesized in the multigram scale and thoroughly characterized by thermogravimetric analyses, revealing high and tunable volatility reflected by appreciable vapor pressures and accompanied by the...