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Title: Electronic Structure Differences in ZrO2 vs. HfO2

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 unveilmore » significant differences in the electronic structures of ZrO2 and HfO2.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
876942
Report Number(s):
PNNL-SA-45791
Journal ID: ISSN 1089-5639; JPCAFH; 3568; KC0302010; TRN: US200608%%24
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory; Journal Volume: 109; Journal Issue: 50
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ELECTRONIC STRUCTURE; PHOTOELECTRON SPECTROSCOPY; ZIRCONIUM OXIDES; HAFNIUM OXIDES; Environmental Molecular Sciences Laboratory

Citation Formats

Zheng, Weijun, Bowen Jr., K.H., Li, Jun, Dabkowska, Iwona, and Gutowski, Maciej S. Electronic Structure Differences in ZrO2 vs. HfO2. United States: N. p., 2005. Web. doi:10.1021/jp053593e.
Zheng, Weijun, Bowen Jr., K.H., Li, Jun, Dabkowska, Iwona, & Gutowski, Maciej S. Electronic Structure Differences in ZrO2 vs. HfO2. United States. doi:10.1021/jp053593e.
Zheng, Weijun, Bowen Jr., K.H., Li, Jun, Dabkowska, Iwona, and Gutowski, Maciej S. Thu . "Electronic Structure Differences in ZrO2 vs. HfO2". United States. doi:10.1021/jp053593e.
@article{osti_876942,
title = {Electronic Structure Differences in ZrO2 vs. HfO2},
author = {Zheng, Weijun and Bowen Jr., K.H. and Li, Jun and Dabkowska, Iwona and Gutowski, Maciej S.},
abstractNote = {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.},
doi = {10.1021/jp053593e},
journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
number = 50,
volume = 109,
place = {United States},
year = {Thu Dec 22 00:00:00 EST 2005},
month = {Thu Dec 22 00:00:00 EST 2005}
}
  • We present density functional calculations of the total energies and equations of state of the monoclinic, tetragonal, cubic, orthorhombic-I (Pbca) and orthorhombic-II (cotunnite)-structure phases of zirconia and hafnia in the local density (LDA) and generalized-gradient (GGA) approximations. The accuracy of the LDA approximation is not sufficient and GGA corrections are critical to obtain low-temperature phase transitions under pressure that are consistent with experiment, i.e., (monoclinic‡ orthorhombic-I ‡ cotunnite). The GGA values of the bulk modulus of the cotunnite phase were found to be 251 and 259 GPa for ZrO2 and HfO2, respectively. We developed a new population analysis scheme inmore » which atomic radii are adapted to the actual charge distribution in the material. The results indicate that the effective atomic radius of Hf is smaller than that of Zr, which is a drastic manifestation of the relativistic lanthanide contraction. The population analysis results demonstrate that ionicity: (i) increases from the monoclinic to the cotunnite phase, and (ii) is larger for HfO2 than for ZrO2. This variable ionicity may be the reason why LDA fails to describe the relative stability of different polymorphs. The bandgap and heat of formation are also larger for monoclinic HfO2 than for ZrO2 by 0.6 eV and 0.60 eV/formula unit, respectively. The tetragonal phase, which often exists as a metastable phase at ambient conditions, has a bandgap larger than the monoclinic phase by 0.35 and 0.65 eV for ZrO2 and HfO2, respectively.« less
  • We demonstrate that the three-dimensional (3D) binary monoclinic oxides HfO{sub 2} and ZrO{sub 2} exhibit quasi-2D polaron localization and conductivity, which results from a small difference in the coordination of two oxygen sublattices in these materials. The transition between a 2D large polaron into a zero-dimensional small polaron state requires overcoming a small energetic barrier. These results demonstrate how a small asymmetry in the lattice structure can determine the qualitative character of polaron localization and significantly broaden the realm of quasi-2D polaron systems.
  • We demonstrate that the three-dimensional (3D) binary monoclinic oxides HfO2 and ZrO2 exhibit quasi-2D polaron localization and conductivity, which results from a small difference in the coordination of two oxygen sublattices in these materials. The transition between a 2D large polaron into a zerodimensional small polaron state requires overcoming a small energetic barrier. These results demonstrate how a small asymmetry in the lattice structure can determine the qualitative character of polaron localization and significantly broaden the realm of quasi-2D polaron systems.
  • The gas-phase hydrolysis of MCl4 (M = Zr, Hf) to produce the initial particles on the way to zirconia and hafnia nanoparticles has been studied with electronic structure theory. The potential energy surfaces, the themochemistry of the reaction species, and the reaction paths for the initial steps of MCl4 reacting with H2O have been calculated. The hydrolysis of MCl4 at higher temperatures begins with the formation of oxychlorohydroxides followed by the elimination of HCl instead of the direct production of MOCl2 and HCl or MO2 and HCl due to the substantial endothermicities associated with the formation of gas-phase MO2. Themore » structural properties and heats of formation of the reactants and products are consistent with the available experimental results. A number of metal oxychlorides (oxychlorohydroxides) intermediate clusters have been studied to assess their role in the production of MO2 nanoparticles. The calculated clustering reaction energies of those intermediates are highly exothermic, so they could be readily formed in the hydrolysis process. These intermediate clusters can be formed exothermically from metal oxychlorohydroxides by the elimination of one HCl or H2O molecule. Our calculations show that the mechanisms leading to the formation of MO2 nanoparticles are complicated and are accompanied by the potential production of a wide range of intermediates, as found for the production of TiO2 particles from the high-temperature oxidation of TiCl4.« less