PNNL

Abstract

While ZrO2 and HfO2 are, for the most part, quite similar chemically, subtle differences in their electronic structures appear to be responsible for differing MO2/Si (M = Zr, Hf) interface stabilities. In order to shed light on the electronic structure differences between ZrO2 and HfO2, we have conducted joint experimental/theoretical studies. Since electron affinities are a sensitive probe of electronic structure, we have measured them by conducting photoelectron spectroscopic experiments on ZrO2- and HfO2-. The electron affinity of HfO2 was determined to be 2.14? 0.03 eV, while that of ZrO2 was determined to be 1.64 ? 0.03 eV. Concurrently, electronic structure calculations were conducted to determine electron affinities, vibrational frequencies, and geometries of these systems. The calculated electron affinities of HfO2 and ZrO2 were found to be 2.05 and 1.62 eV, respectively. The molecular results confirm earlier predictions from solid phases that HfO2 is more ionic than ZrO2. The excess electron in MO2- occupies an sd-type hybrid orbital localized on the M atom (M=Zr, Hf). The structural parameters of ZrO2 and HfO2 were found to be very similar. The difference in geometries between the neutral and the anion is along the symmetrical stretching and bending modes. Together, these studies unveil significant differences in the electronic structures of ZrO2 and HfO2.