Control of TiN oxidation upon atomic layer deposition of oxides

The interfaces of a physical-vapor deposited (PVD)-TiN electrode with atomic-layer deposited (ALD) HfO2 layers were studied using photoelectron spectroscopy with high kinetic energies of photoelectrons enabling nondestructive in-depth chemical profiling and phase analysis. Our results reveal the presence of only TiNxOy at the TiN/ALD-HfO2 interface with no measurable traces of the TiO2 phase. By contrast, the interface formed by ALD of HfO2 on top of PVD TiN contains both TiO2 and TiNxOy compounds and may be compared to an HfO2/TiN interface with intentional ALD TiO2 interlayer (IL) formation prior to HfO2 growth. Pre-growth of ALD Al2O3 IL drastically reduces the TiO2 and TiNxOy amounts present at the HfO2/TiN interface, which can be ascribed to oxygen scavenging from the initially oxidized TiN surface by energetically more favorable Al-O bonds. The present study demonstrates that the amount of TiO2 phase can be effectively controlled, i.e., increased or decreased, during the ALD process enabling engineering of vacancy-mediated processes.