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Title: Oxygen vacancy formation energies in PbTiO 3 / SrTiO 3 superlattice

Abstract

The defect stability in a prototypical perovskite oxide superlattice consisting of $${\mathrm{SrTiO}}_{3}$$ and $${\mathrm{PbTiO}}_{3}$$ (STO/PTO) is determined by using first principles density functional theory calculations. Specifically, the oxygen vacancy formation energies $${E}_{\mathrm{v}}$$ in the paraelectric and ferroelectric phases of a superlattice with four atomic layers of STO and four layers of PTO (4STO/4PTO) are determined and compared. The effects of charge state, octahedral rotation, polarization, and interfaces on $${E}_{\mathrm{v}}$$ are examined in this paper. The formation energies vary layer by layer in the superlattices, with $${E}_{\mathrm{v}}$$ being higher in the ferroelectric phase than that in the paraelectric phase. The two interfaces constructed in these oxide superlattices, which are symmetrically equivalent in the paraelectric systems, exhibit very different formation energies in the ferroelectric superlattices and this can be seen to be driven by the coupling of ferroelectric and rotational modes. At equivalent lattice sites, $${E}_{\mathrm{v}}$$ of charged vacancies is generally lower than that of neutral vacancies. Octahedral rotations $$({\mathrm{a}}^{0}{\mathrm{a}}^{0}{\mathrm{c}}^{{-}})$$ in the superlattices have a significant effect on $${E}_{\mathrm{v}}$$, increasing the formation energy of vacancies located near the interface but decreasing the formation energy of the oxygen vacancies located in the bulk-like regions of the STO and PTO constituent parts. The formation-energy variations among different layers are found to be primarily caused by the difference in the local relaxation at each layer. Finally, these fundamental insights into the defect stability in perovskite superlattices can be used to tune defect properties by controlling the constituent materials of superlattices and interface engineering.

Authors:
 [1];  [1];  [2];  [3];  [2];  [4];  [5]
  1. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science. Computational Science and Engineering Division
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science
  5. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering. Joint Inst. for Advanced Materials
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); ORNL Laboratory Directed Research and Development (LDRD) Program; The Univ. of Tennessee (UT) Science Alliance Joint Directed Research and Development Program (United States)
OSTI Identifier:
1460196
Alternate Identifier(s):
OSTI ID: 1457079
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 6; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; crystal defects; ferroelectrics; superlattices

Citation Formats

Zhang, Lipeng, Bredeson, Isaac, Birenbaum, Axiel Y., Kent, P. R. C., Cooper, Valentino R., Ganesh, P., and Xu, Haixuan. Oxygen vacancy formation energies in PbTiO3/SrTiO3 superlattice. United States: N. p., 2018. Web. doi:10.1103/PhysRevMaterials.2.064409.
Zhang, Lipeng, Bredeson, Isaac, Birenbaum, Axiel Y., Kent, P. R. C., Cooper, Valentino R., Ganesh, P., & Xu, Haixuan. Oxygen vacancy formation energies in PbTiO3/SrTiO3 superlattice. United States. doi:10.1103/PhysRevMaterials.2.064409.
Zhang, Lipeng, Bredeson, Isaac, Birenbaum, Axiel Y., Kent, P. R. C., Cooper, Valentino R., Ganesh, P., and Xu, Haixuan. Mon . "Oxygen vacancy formation energies in PbTiO3/SrTiO3 superlattice". United States. doi:10.1103/PhysRevMaterials.2.064409. https://www.osti.gov/servlets/purl/1460196.
@article{osti_1460196,
title = {Oxygen vacancy formation energies in PbTiO3/SrTiO3 superlattice},
author = {Zhang, Lipeng and Bredeson, Isaac and Birenbaum, Axiel Y. and Kent, P. R. C. and Cooper, Valentino R. and Ganesh, P. and Xu, Haixuan},
abstractNote = {The defect stability in a prototypical perovskite oxide superlattice consisting of ${\mathrm{SrTiO}}_{3}$ and ${\mathrm{PbTiO}}_{3}$ (STO/PTO) is determined by using first principles density functional theory calculations. Specifically, the oxygen vacancy formation energies ${E}_{\mathrm{v}}$ in the paraelectric and ferroelectric phases of a superlattice with four atomic layers of STO and four layers of PTO (4STO/4PTO) are determined and compared. The effects of charge state, octahedral rotation, polarization, and interfaces on ${E}_{\mathrm{v}}$ are examined in this paper. The formation energies vary layer by layer in the superlattices, with ${E}_{\mathrm{v}}$ being higher in the ferroelectric phase than that in the paraelectric phase. The two interfaces constructed in these oxide superlattices, which are symmetrically equivalent in the paraelectric systems, exhibit very different formation energies in the ferroelectric superlattices and this can be seen to be driven by the coupling of ferroelectric and rotational modes. At equivalent lattice sites, ${E}_{\mathrm{v}}$ of charged vacancies is generally lower than that of neutral vacancies. Octahedral rotations $({\mathrm{a}}^{0}{\mathrm{a}}^{0}{\mathrm{c}}^{{-}})$ in the superlattices have a significant effect on ${E}_{\mathrm{v}}$, increasing the formation energy of vacancies located near the interface but decreasing the formation energy of the oxygen vacancies located in the bulk-like regions of the STO and PTO constituent parts. The formation-energy variations among different layers are found to be primarily caused by the difference in the local relaxation at each layer. Finally, these fundamental insights into the defect stability in perovskite superlattices can be used to tune defect properties by controlling the constituent materials of superlattices and interface engineering.},
doi = {10.1103/PhysRevMaterials.2.064409},
journal = {Physical Review Materials},
number = 6,
volume = 2,
place = {United States},
year = {2018},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Table 1 Table 1: The c/a ratio and energy per unit cell relative to the FE phase for the 4STO/4PTO superlattices studied.

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Works referenced in this record:

Interfacial enhancement of ferroelectricity in CaTi O 3 /BaTi O 3 superlattices
journal, January 2011


Field-Dependent Domain Distortion and Interlayer Polarization Distribution in PbTiO 3 / SrTiO 3 Superlattices
journal, January 2013


Polarization enhancement in short period superlattices via interfacial intermixing
journal, July 2007


Composition dependent intrinsic defect structures in SrTiO 3
journal, January 2014

  • Liu, Bin; Cooper, Valentino R.; Xu, Haixuan
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 29
  • DOI: 10.1039/C4CP01510J

Interplay of Octahedral Rotations and Lone Pair Ferroelectricity in CsPbF 3
journal, August 2015


Atomic level observation of octahedral distortions at the perovskite oxide heterointerface
journal, July 2013

  • Aso, Ryotaro; Kan, Daisuke; Shimakawa, Yuichi
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep02214

Improper ferroelectricity in perovskite oxide artificial superlattices
journal, April 2008

  • Bousquet, Eric; Dawber, Matthew; Stucki, Nicolas
  • Nature, Vol. 452, Issue 7188
  • DOI: 10.1038/nature06817

Observation of polar vortices in oxide superlattices
journal, January 2016

  • Yadav, A. K.; Nelson, C. T.; Hsu, S. L.
  • Nature, Vol. 530, Issue 7589
  • DOI: 10.1038/nature16463

Dimensional control of defect dynamics in perovskite oxide superlattices
journal, March 2018


Perovskite Oxides: Preparation, Characterizations, and Applications in Heterogeneous Catalysis
journal, August 2014

  • Zhu, Junjiang; Li, Hailong; Zhong, Linyun
  • ACS Catalysis, Vol. 4, Issue 9
  • DOI: 10.1021/cs500606g

Control of oxygen octahedral rotations and physical properties in SrRuO 3 films
journal, December 2013


Mott Transition and Suppression of Orbital Fluctuations in Orthorhombic 3 d 1 Perovskites
journal, April 2004


Effects of strain and oxygen vacancies on the ferroelectric and antiferrodistortive distortions in PbTiO 3 / SrTiO 3 superlattice
journal, September 2015


Tunable Oxygen Vacancy Formation Energetics in the Complex Perovskite Oxide Sr x La 1– x Mn y Al 1– y O 3
journal, November 2014

  • Deml, Ann M.; Stevanović, Vladan; Holder, Aaron M.
  • Chemistry of Materials, Vol. 26, Issue 22
  • DOI: 10.1021/cm5033755

Understanding the interactions between oxygen vacancies at SrTiO 3 (001) surfaces
journal, August 2014


Tailoring the Properties of Artificially Layered Ferroelectric Superlattices
journal, December 2007

  • Dawber, M.; Stucki, N.; Lichtensteiger, C.
  • Advanced Materials, Vol. 19, Issue 23
  • DOI: 10.1002/adma.200700965

Intrinsic Material Properties Dictating Oxygen Vacancy Formation Energetics in Metal Oxides
journal, May 2015

  • Deml, Ann M.; Holder, Aaron M.; O’Hayre, Ryan P.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 10
  • DOI: 10.1021/acs.jpclett.5b00710

Electrostatic Coupling and Local Structural Distortions at Interfaces in Ferroelectric/Paraelectric Superlattices
journal, May 2012

  • Zubko, P.; Jecklin, N.; Torres-Pardo, A.
  • Nano Letters, Vol. 12, Issue 6
  • DOI: 10.1021/nl3003717

AMPLIMODES : symmetry-mode analysis on the Bilbao Crystallographic Server
journal, September 2009

  • Orobengoa, Danel; Capillas, Cesar; Aroyo, Mois I.
  • Journal of Applied Crystallography, Vol. 42, Issue 5
  • DOI: 10.1107/S0021889809028064

Magnetism and metal-insulator transition in oxygen-deficient SrTiO 3
journal, September 2015

  • Lopez-Bezanilla, Alejandro; Ganesh, P.; Littlewood, Peter B.
  • Physical Review B, Vol. 92, Issue 11
  • DOI: 10.1103/PhysRevB.92.115112

Interplay of Couplings between Antiferrodistortive, Ferroelectric, and Strain Degrees of Freedom in Monodomain PbTiO 3 / SrTiO 3 Superlattices
journal, November 2011


Phase transitions via selective elemental vacancy engineering in complex oxide thin films
journal, April 2016

  • Lee, Sang A.; Jeong, Hoidong; Woo, Sungmin
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep23649

The classification of tilted octahedra in perovskites
journal, November 1972

  • Glazer, A. M.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 28, Issue 11
  • DOI: 10.1107/S0567740872007976

PbTiO 3 /SrTiO 3 interface: Energy band alignment and its relation to the limits of Fermi level variation
journal, July 2011


Oxygen diffusion in solid oxide fuel cell cathode and electrolyte materials: mechanistic insights from atomistic simulations
journal, January 2011

  • Chroneos, Alexander; Yildiz, Bilge; Tarancón, Albert
  • Energy & Environmental Science, Vol. 4, Issue 8
  • DOI: 10.1039/c0ee00717j

Ferroelectric properties of BaZrO 3 /PbZrO 3 and SrZrO 3 /PbZrO 3 superlattices: An ab-initio study
journal, August 2014

  • Al-Aqtash, Nabil; Alsaad, Ahmad; Sabirianov, Renat
  • Journal of Applied Physics, Vol. 116, Issue 7
  • DOI: 10.1063/1.4893300

Octahedral Rotation-Induced Ferroelectricity in Cation Ordered Perovskites
journal, April 2012


First-principle study of ferroelectricity in PbTiO3/SrTiO3 superlattices
journal, November 2006


Interplay between intrinsic defects, doping, and free carrier concentration in SrTiO 3 thin films
journal, May 2012

  • Ertekin, Elif; Srinivasan, Varadharajan; Ravichandran, Jayakanth
  • Physical Review B, Vol. 85, Issue 19
  • DOI: 10.1103/PhysRevB.85.195460

Unusual Behavior of the Ferroelectric Polarization in PbTiO 3 / SrTiO 3 Superlattices
journal, October 2005


A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Determination of ground-state and low-energy structures of perovskite superlattices from first principles
journal, June 2014


Interfacial Octahedral Rotation Mismatch Control of the Symmetry and Properties of SrRuO 3
journal, June 2016

  • Gao, Ran; Dong, Yongqi; Xu, Han
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 23
  • DOI: 10.1021/acsami.6b02864

Polarity-induced oxygen vacancies at LaAlO 3 SrTiO 3 interfaces
journal, October 2010


Electronic structure of oxygen vacancies in SrTiO 3 and LaAlO 3
journal, October 2012


Materials for Intermediate-Temperature Solid-Oxide Fuel Cells
journal, July 2014


Structural and electronic properties of oxygen vacancies in cubic and antiferrodistortive phases of SrTiO 3
journal, May 2004


Oxygen vacancy diffusion in bulk SrTiO3 from density functional theory calculations
journal, June 2016


Optical identification of oxygen vacancy formation at SrTiO 3 –(Ba,Sr)TiO 3 heterostructures
journal, May 2014


Anti-ferrodistortive-Like Oxygen-Octahedron Rotation Induced by the Oxygen Vacancy in Cubic SrTiO 3
journal, October 2012


    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.