4f-5d hybridization in a high k dielectric

While intra-atomic f-d hybridization is expected, experimental confirmation of f-d hybridization in the photoemission final state leading to 4f band structure has been limited to 5f systems and compound systems with very shallow 4f levels. We demonstrate that core 4f states can contribute to the valence band structure in a wide band gap dielectric, in this case HfO2 in the photoemission final state. In spite of the complications of sample charging, we find evidence of symmetry in the shallow 4f levels and wave vector dependent band dispersion, the latter consistent with the crystal structure of HfO2.