Oxygen and hydrogen defects in zirconia and hafnia: density functional
molecular dynamics approach.
Jacob L. Gavartin (

), A. S. Foster,
V. B. Sulimov, F. Lopez Gejo, and A. L. Shluger
Department of Physics and Astronomy, University College London,
Gower Street, WC1E 6BT, London, UK
Zirconium and hafnium oxide films are being extensively studied asalternative
gate dielectrics for field effect transistors.
Dielectric properties of currently produced films strongly depend on
deposition techniques, suggesting importance of electronic defects in
these materials. In particular, shallow electron traps whose occupancy
may change under small variations of external potential, are likely to
contribute to the leakage currents.
In this paper we investigate the r\`{o}le of oxygen and hydrogen defects
on degradation of dielectric properties of monoclinic zirconia and
hafnia. We apply plane wave density functional theory to model
structure, ionisation energies and electron affinities of the oxygen vacancy
and interstitial defects as well as hydrogen contained defects in different
charge states. Since unambiguous characterisation of hydrogen defects can only
be achieved by means of infrared spectroscopy, we use
{\it ab initio} molecular dynamics to calculate vibrational properties and
diffusion mechanisms of water and hydrogen species in $ZrO_2$.
We discuss the properties of the defects studied in light of their
possible contribution to the leakage currents and films degradation.
The question of reliability of the density functional
methods for calculations of shallow trap centers in oxides will also
be addressed.