Complete band offset characterization of the HfO2/SiO2/Si stack using charge corrected x-ray photoelectron spectroscopy

The HfO2-Si valence and conduction band offsets (VBO and CBO, respectively) of technologically relevant HfO2/SiO2/Si film stacks have been measured by several methods, with several groups reporting values within a range of similar to 1 eV for both quantities. In this study we have used a combination of x-ray photoemission spectroscopy (XPS) and spectroscopic ellipsometry to measure the HfO2-Si VBO and CBO of both as-deposited and annealed stacks. Unlike previous XPS based measurements of the HfO2-Si VBO, we have corrected for the effect of charging in the XPS measurement. We find that after correction for charging, the HfO2-Si VBOs are decreased from their typical XPS-measured values, and agree better with values measured by UV photoemission spectroscopy and internal photoemission. We also report values for the rarely reported HfO2-SiO2 and SiO2-Si VBOs and CBOs in HfO2/SiO2/Si stacks. In addition to the band offsets, XPS was used to measure the band bending in the Si substrate of HfO2/SiO2/Si film stacks. Unannealed HfO2 stacks showed downward Si band bending of 0.4-0.5 eV, while annealed HfO2 stacks showed negligible band bending. Finally, we investigated the composition of the SiO2 layer in SiO2/Si and HfO2/SiO2/Si. By decomposing the Si 2p spectra into the spin orbit partner lines of its five oxidation states we observed that the growth of the HfO2 films resulted in the growth of the SiO2 underlayer and an increase by a factor of similar to 2.3 in the density of suboxide species of SiO2. Based on the relatively high binding energy of the Si 2p(4+) level with respect to the Si 2p(0) level and a survey of results from literature, we conclude that the SiO2 layer in the HfO2/SiO2/Si samples we measured does not undergo significant intermixing with HfO2.