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Iron-oxygen vacancy defect association in polycrystalline iron-modified PbZrO3 antiferroelectrics: Multifrequency electron paramagnetic resonance and Newman superposition model analysis

Meštrić, Hrvoje and Eichel, Rüdiger-A. and Dinse, Klaus-Peter and Ozarowski, Andrew and van Tol, Johan and Brunel, Louis and Kungl, Hans and Hoffmann, Michael and Schönau, Kristin and Knapp, Michael and Fuess, Hartmut (2006):
Iron-oxygen vacancy defect association in polycrystalline iron-modified PbZrO3 antiferroelectrics: Multifrequency electron paramagnetic resonance and Newman superposition model analysis.
In: Physical Review B, pp. 184105-1-184105-10, 73, (18), ISSN 1098-0121, [Online-Edition: http://dx.doi.org/10.1103/PhysRevB.73.184105],
[Article]

Abstract

By utilizing multifrequency electron paramagnetic resonance (EPR) spectroscopy, the iron functional center in Fe3+-modified polycrystalline lead zirconate (PbZrO3) was studied. The single phase polycrystalline sample remained orthorhombic and antiferroelectric down to 20 K as confirmed by high-resolution synchrotron powder diffraction. The Fe3+ ions were identified as substituting for Zr4+ at the B-site of the perovskite ABO3 lattice. Similarly as found for Fe3+:PbTiO3 [Meštrić et al., Phys. Rev. B 71, 134109 (2005)], the value of the fine-structure (FS) parameter B20 is only consistent with a model in which a charged (FeZr′–VO••)• defect associate is formed. In contrast to a well defined iron functional center in lead titanate (PbTiO3) with FS parameters exhibiting variances of less than 3%, a strong broadening of the EPR powder pattern was observed in lead zirconate, indicating a much larger variance of FS parameters. It is suggested that the apparent broad distribution of fine-structure parameters arises from the system’s capability to realize different oxygen vacancy positions in the first coordination shell around the iron site. This proposed model of a small number of distinct iron-oxygen vacancy sites is supported by the observation that corresponding B20 and orthorhombic B22 FS parameters of these sites are anticorrelated, a property not expected for random distributions of fine-structure parameters.

Item Type: Article
Erschienen: 2006
Creators: Meštrić, Hrvoje and Eichel, Rüdiger-A. and Dinse, Klaus-Peter and Ozarowski, Andrew and van Tol, Johan and Brunel, Louis and Kungl, Hans and Hoffmann, Michael and Schönau, Kristin and Knapp, Michael and Fuess, Hartmut
Title: Iron-oxygen vacancy defect association in polycrystalline iron-modified PbZrO3 antiferroelectrics: Multifrequency electron paramagnetic resonance and Newman superposition model analysis
Language: English
Abstract:

By utilizing multifrequency electron paramagnetic resonance (EPR) spectroscopy, the iron functional center in Fe3+-modified polycrystalline lead zirconate (PbZrO3) was studied. The single phase polycrystalline sample remained orthorhombic and antiferroelectric down to 20 K as confirmed by high-resolution synchrotron powder diffraction. The Fe3+ ions were identified as substituting for Zr4+ at the B-site of the perovskite ABO3 lattice. Similarly as found for Fe3+:PbTiO3 [Meštrić et al., Phys. Rev. B 71, 134109 (2005)], the value of the fine-structure (FS) parameter B20 is only consistent with a model in which a charged (FeZr′–VO••)• defect associate is formed. In contrast to a well defined iron functional center in lead titanate (PbTiO3) with FS parameters exhibiting variances of less than 3%, a strong broadening of the EPR powder pattern was observed in lead zirconate, indicating a much larger variance of FS parameters. It is suggested that the apparent broad distribution of fine-structure parameters arises from the system’s capability to realize different oxygen vacancy positions in the first coordination shell around the iron site. This proposed model of a small number of distinct iron-oxygen vacancy sites is supported by the observation that corresponding B20 and orthorhombic B22 FS parameters of these sites are anticorrelated, a property not expected for random distributions of fine-structure parameters.

Journal or Publication Title: Physical Review B
Volume: 73
Number: 18
Divisions: 07 Department of Chemistry > Physical Chemistry
Zentrale Einrichtungen
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > A - Synthesis
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > A - Synthesis > Subproject A2: Manufacturing and characterization of PZT-ceramics with defined defect chemistry
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > B - Characterisation
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > B - Characterisation > Subproject B1: EPR-Investigations of defects in ferroelectric ceramic material
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > B - Characterisation > Subproject B3: Structure Characterization of Piezoelectric Ceramics With Respect to Electrical Fatigue
07 Department of Chemistry
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres
DFG-Collaborative Research Centres (incl. Transregio)
Date Deposited: 27 Jul 2011 12:39
Official URL: http://dx.doi.org/10.1103/PhysRevB.73.184105
Additional Information:

SFB 595 Cooperation A2, B1, B3

Identification Number: doi:10.1103/PhysRevB.73.184105
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