Influence of different oxidants on band alignment of HfO₂ films deposited by atomic layer deposition

Based on X-ray photoelectron spectroscopy (XPS), influences of different oxidants on band alignment of HfO₂ films deposited by atomic layer deposition (ALD) are investigated in this paper. The measured valence band offset (VBO) value for H₂O-based HfO₂ increases from 3.17 eV to 3.32 eV after annealing, whereas the VBO value for O₃-based HfO₂ decreases from 3.57 eV to 3.46 eV. The research results indicate that the silicate layer changes in different ways for H₂O-based and O₃-based HfO₂ films after annealing process, which plays a key role in generating the internal electric field formed by the dipoles. The variations of the dipoles at the interface between the HfO₂ and SiO₂ after annealing may lead the VBO values of H₂O-based and O₃-based HfO₂ to vary in different ways, which is in agreement with the varition of flat band (V_FB) voltage.