First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions

Qi, Tingting; Curnan, Matthew T.; Kim, Seungchul; Bennett, Joseph W.; Grinberg, Ilya; Rappe, Andrew M.

doi:10.1103/PhysRevB.84.245206

Title: First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions

Abstract

Oxygen vacancies in perovskite oxide solid solutions are fundamentally interesting and technologically important. However, experimental characterization of the vacancy locations and their impact on electronic structure is challenging. We have carried out first-principles calculations on two Zr-modified solid solutions, Pb(Zn_1/3Nb_2/3)O₃ and Pb(Mg_1/3Nb_2/3)O₃, in which vacancies are present. We find that the vacancies are more likely to reside between low-valent cation-cation pairs than high-valent cation-cation pairs. Based on the analysis of our results, we formulate guidelines that can be used to predict the location of oxygen vacancies in perovskite solid solutions. Our results show that vacancies can have a significant impact on both the conduction and valence band energies, in some cases lowering the band gap by ≈0.5 eV. The effects of vacancies on the electronic band structure can be understood within the framework of crystal field theory.

Authors:: Qi, Tingting; Curnan, Matthew T.; Kim, Seungchul; Bennett, Joseph W.; Grinberg, Ilya; Rappe, Andrew M.

Publication Date:: Thu Dec 15 00:00:00 EST 2011

Sponsoring Org.:: USDOE

OSTI Identifier:: 1098415

Resource Type:: Publisher's Accepted Manuscript

Journal Name:: Physical Review. B, Condensed Matter and Materials Physics

Additional Journal Information:: Journal Name: Physical Review. B, Condensed Matter and Materials Physics Journal Volume: 84 Journal Issue: 24; Journal ID: ISSN 1098-0121

Publisher:: American Physical Society

Country of Publication:: United States

Language:: English

Citation Formats


                    Qi, Tingting, Curnan, Matthew T., Kim, Seungchul, Bennett, Joseph W., Grinberg, Ilya, and Rappe, Andrew M. First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions.  United States: N. p., 2011. 
Web.  doi:10.1103/PhysRevB.84.245206.

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                    Qi, Tingting, Curnan, Matthew T., Kim, Seungchul, Bennett, Joseph W., Grinberg, Ilya, & Rappe, Andrew M. First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions.  United States.  https://doi.org/10.1103/PhysRevB.84.245206

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                    Qi, Tingting, Curnan, Matthew T., Kim, Seungchul, Bennett, Joseph W., Grinberg, Ilya, and Rappe, Andrew M. Thu .  
"First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions".  United States.  https://doi.org/10.1103/PhysRevB.84.245206.

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@article{osti_1098415,

  title        = {First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions},

  author       = {Qi, Tingting and Curnan, Matthew T. and Kim, Seungchul and Bennett, Joseph W. and Grinberg, Ilya and Rappe, Andrew M.},

  abstractNote = {Oxygen vacancies in perovskite oxide solid solutions are fundamentally interesting and technologically important. However, experimental characterization of the vacancy locations and their impact on electronic structure is challenging. We have carried out first-principles calculations on two Zr-modified solid solutions, Pb(Zn1/3Nb2/3)O₃ and Pb(Mg1/3Nb2/3)O₃, in which vacancies are present. We find that the vacancies are more likely to reside between low-valent cation-cation pairs than high-valent cation-cation pairs. Based on the analysis of our results, we formulate guidelines that can be used to predict the location of oxygen vacancies in perovskite solid solutions. Our results show that vacancies can have a significant impact on both the conduction and valence band energies, in some cases lowering the band gap by ≈0.5 eV. The effects of vacancies on the electronic band structure can be understood within the framework of crystal field theory.},

  doi          = {10.1103/PhysRevB.84.245206},

  journal      = {Physical Review. B, Condensed Matter and Materials Physics},

  number       = 24,

  volume       = 84,

  place        = {United States},

  year         = {Thu Dec 15 00:00:00 EST 2011},

  month        = {Thu Dec 15 00:00:00 EST 2011}

}

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Title: First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions

Abstract

Citation Formats

Structural and dynamic properties of oxygen vacancies in perovskite oxides—analysis of defect chemistry by modern multi-frequency and pulsed EPR techniques journal, January 2011

Influence of long-range cation order on relaxor properties of doped Pb ( Mg 1 / 3 Nb 2 / 3 ) O 3 ceramics journal, April 2009

Generalized Gradient Approximation Made Simple journal, October 1996

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Predicting morphotropic phase boundary locations and transition temperatures in Pb- and Bi-based perovskite solid solutions from crystal chemical data and first-principles calculations journal, November 2005

Fatigue and switching in ferroelectric memories: Theory and experiment journal, December 1990

A model for fatigue in ferroelectric perovskite thin films journal, February 2000

Post density functional theoretical studies of highly polar semiconductive Pb(Ti 1 − x Ni x )O 3 − x solid solutions: Effects of cation arrangement on band gap journal, May 2011

Designed nonlocal pseudopotentials for enhanced transferability journal, May 1999

Structure and energetics of antiferroelectric PbZrO 3 journal, November 1995

Trapping of oxygen vacancies in the twin walls of perovskite journal, January 2010

Momentum-space formalism for the total energy of solids journal, November 1979

Ultrahigh strain and piezoelectric behavior in relaxor based ferroelectric single crystals journal, August 1997

Oxygen-vacancy ordering as a fatigue mechanism in perovskite ferroelectrics journal, June 2000

Nonmonotonic T C Trends in Bi-Based Ferroelectric Perovskite Solid Solutions journal, January 2007

Cation ordering in complex oxides journal, October 1999

Local structure and macroscopic properties in Pb Mg 1 ∕ 3 Nb 2 ∕ 3 O 3 − Pb Ti O 3 and Pb Zn 1 ∕ 3 Nb 2 ∕ 3 O 3 − Pb Ti O 3 solid solutions journal, December 2004

Pb-free semiconductor ferroelectrics: A theoretical study of Pd-substituted Ba ( Ti 1 − x Ce x ) O 3 solid solutions journal, November 2010

New Highly Polar Semiconductor Ferroelectrics through d 8 Cation-O Vacancy Substitution into PbTiO 3 : A Theoretical Study journal, December 2008

Zr-Modified Pb(Mg 1/3 Nb 2/3 )O 3 with a Long-Range Cation Order journal, September 2008

Optimized pseudopotentials journal, January 1990

Band-gap engineering via local environment in complex oxides journal, June 2011

On the Non‐Orthogonality Problem Connected with the Use of Atomic Wave Functions in the Theory of Molecules and Crystals journal, March 1950

Projection of plane-wave calculations into atomic orbitals journal, September 1995

Structural and dynamic properties of oxygen vacancies in perovskite oxides—analysis of defect chemistry by modern multi-frequency and pulsed EPR techniques
journal, January 2011

Influence of long-range cation order on relaxor properties of doped $Pb ({Mg}_{1 / 3} {Nb}_{2 / 3}) O_{3}$ ceramics
journal, April 2009

Generalized Gradient Approximation Made Simple
journal, October 1996

Applications of Modern Ferroelectrics
journal, February 2007

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976

Special points for Brillouin-zone integrations
journal, June 1976

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

Predicting morphotropic phase boundary locations and transition temperatures in Pb- and Bi-based perovskite solid solutions from crystal chemical data and first-principles calculations
journal, November 2005

Fatigue and switching in ferroelectric memories: Theory and experiment
journal, December 1990

A model for fatigue in ferroelectric perovskite thin films
journal, February 2000

Post density functional theoretical studies of highly polar semiconductive Pb(Ti $_{1 - x}$ Ni $_{x}$ )O $_{3 - x}$ solid solutions: Effects of cation arrangement on band gap
journal, May 2011

Designed nonlocal pseudopotentials for enhanced transferability
journal, May 1999

Structure and energetics of antiferroelectric ${PbZrO}_{3}$
journal, November 1995

Trapping of oxygen vacancies in the twin walls of perovskite
journal, January 2010

Momentum-space formalism for the total energy of solids
journal, November 1979

Ultrahigh strain and piezoelectric behavior in relaxor based ferroelectric single crystals
journal, August 1997

Oxygen-vacancy ordering as a fatigue mechanism in perovskite ferroelectrics
journal, June 2000

Nonmonotonic $T_{C}$ Trends in Bi-Based Ferroelectric Perovskite Solid Solutions
journal, January 2007

Cation ordering in complex oxides
journal, October 1999

Local structure and macroscopic properties in $Pb {Mg}_{1 ∕ 3} {Nb}_{2 ∕ 3} O_{3} - Pb Ti O_{3}$ and $Pb {Zn}_{1 ∕ 3} {Nb}_{2 ∕ 3} O_{3} - Pb Ti O_{3}$ solid solutions
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On the Non‐Orthogonality Problem Connected with the Use of Atomic Wave Functions in the Theory of Molecules and Crystals
journal, March 1950

Projection of plane-wave calculations into atomic orbitals
journal, September 1995