Manipulating multiple order parameters via oxygen vacancies: The case of Eu0.5Ba0.5TiO3-δ

Li, Weiwei; He, Qian; Wang, Le; Zeng, Huizhong; Bowlan, John; Ling, Langsheng; Yarotski, Dmitry A.; Zhang, Wenrui; Zhao, Run; Dai, Jiahong; Gu, Junxing; Shen, Shipeng; Guo, Haizhong; Pi, Li; Wang, Haiyan; Wang, Yongqiang; Velasco-Davalos, Ivan A.; Wu, Yangjiang; Hu, Zhijun; Chen, Bin; Li, Run-Wei; Sun, Young; Jin, Kuijuan; Zhang, Yuheng; Chen, Hou-Tong; Ju, Sheng; Ruediger, Andreas; Shi, Daning; Borisevich, Albina Y.; Yang, Hao

doi:10.1103/PhysRevB.96.115105

Manipulating multiple order parameters via oxygen vacancies: The case of $E u_{0.5} B a_{0.5} Ti O_{3 - δ}$

Journal Article · Wed Sep 06 00:00:00 EDT 2017 · Physical Review B

DOI:https://doi.org/10.1103/PhysRevB.96.115105· OSTI ID:1457304

Li, Weiwei ^[1]; He, Qian ^[2]; Wang, Le ^[3]; Zeng, Huizhong ^[4]; Bowlan, John ^[5]; Ling, Langsheng ^[6]; Yarotski, Dmitry A. ^[5]; Zhang, Wenrui ^[7]; Zhao, Run ^[8]; Dai, Jiahong ^[9]; Gu, Junxing ^[3]; Shen, Shipeng ^[3]; Guo, Haizhong ^[3]; Pi, Li ^[6]; Wang, Haiyan ^[7]; Wang, Yongqiang ^[5]; Velasco-Davalos, Ivan A. ^[10]; Wu, Yangjiang ^[11]; Hu, Zhijun ^[11]; Chen, Bin ^[12] more »

Nanjing Univ. of Aeronautics and Astronautics (China). College of Science; Univ. of Cambridge (United Kingdom). Dept. of Materials Science and Metallurgy
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
Chinese Academy of Sciences (CAS), Beijing (China). Beijing National Lab. for Condensed Matter Physics. Inst. of Physics
Univ. of Electronic Science and Technology of China, Chengdu (China). State Key Lab. of Electronic Thin Films and Integrated Devices
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Chinese Academy of Sciences (CAS), Hefei (China). High Magnetic Field Lab.
Texas A & M Univ., College Station, TX (United States). Materials Science and Engineering Program. Dept. of Electrical and Computer Engineering
Nanjing Univ. of Aeronautics and Astronautics (China). College of Science
Soochow Univ., Suzhou (China). College of Physics, Optoelectronics and Energy
National Inst. of Scientific Research-Energy, Materials and Telecommunications (INRS-EMT), Varennes, QC (Canada)
Soochow Univ., Suzhou (China). Center for Soft Condensed Matter Physics and Interdisciplinary Research
Chinese Academy of Sciences (CAS), Ningbo (China). Key Lab. of Magnetic Materials and Devices. Ningbo Inst. of Materials Technology and Engineering

Controlling functionalities, such as magnetism or ferroelectricity, by means of oxygen vacancies ($${V}_{\mathrm{O}}$$) is a key issue for the future development of transition-metal oxides. Progress in this field is currently addressed through $${V}_{\mathrm{O}}$$ variations and their impact on mainly one order parameter. In this paper, we reveal a mechanism for tuning both magnetism and ferroelectricity simultaneously by using $${V}_{\mathrm{O}}$$. Combining experimental and density-functional theory studies of $$\mathrm{E}{\mathrm{u}}_{0.5}\mathrm{B}{\mathrm{a}}_{0.5}\mathrm{Ti}{\mathrm{O}}_{3{-}{\delta}}$$, we demonstrate that oxygen vacancies create $$\mathrm{T}{\mathrm{i}}^{3+}3{d}^{1}$$ defect states, mediating the ferromagnetic coupling between the localized Eu $$4{f}^{7}$$ spins, and increase an off-center displacement of Ti ions, enhancing the ferroelectric Curie temperature. Finally, the dual function of Ti sites also promises a magnetoelectric coupling in the $$\mathrm{E}{\mathrm{u}}_{0.5}\mathrm{B}{\mathrm{a}}_{0.5}\mathrm{Ti}{\mathrm{O}}_{3{-}{\delta}}$$.

View Accepted Manuscript (DOE)

Research Organization:: Chinese Academy of Sciences (CAS), Beijing (China); Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Nanjing Univ. of Aeronautics and Astronautics (China); National Inst. of Scientific Research-Energy, Materials and Telecommunications (INRS-EMT), Varennes, QC (Canada); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Soochow Univ., Suzhou (China); Texas A & M Univ., College Station, TX (United States)

Sponsoring Organization:: Fonds de recherche du Québec - Nature et technologies (FRQNT) (Canada); National Basic Research Program of China; National Natural Science Foundation of China (NSFC); National Science Foundation (NSF) (United States); Natural Sciences and Engineering Research Council of Canada (NSERC); Program for Postgraduates Research Innovation in University of Jiangsu Province (China); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1457304

Alternate ID(s):: OSTI ID: 1378818

Report Number(s):: LA-UR--15-29487

Journal Information:: Physical Review B, Journal Name: Physical Review B Journal Issue: 11 Vol. 96; ISSN 2469-9950

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

References (34)

Atomically Resolved Mapping of Polarization and Electric Fields Across Ferroelectric/Oxide Interfaces by Z-contrast Imaging Chang, Hye Jung; Kalinin, Sergei V.; Morozovska, Anna N. Advanced Materials, Vol. 23, Issue 21 https://doi.org/10.1002/adma.201004641	journal	April 2011
Anti-ferrodistortive-Like Oxygen-Octahedron Rotation Induced by the Oxygen Vacancy in Cubic SrTiO ₃ Choi, Minseok; Oba, Fumiyasu; Kumagai, Yu Advanced Materials, Vol. 25, Issue 1 https://doi.org/10.1002/adma.201203580	journal	October 2012
Scanning Transmission Electron Microscopy Pennycook, Stephen J.; Nellist, Peter D. https://doi.org/10.1007/978-1-4419-7200-2	book	January 2011
Why Are There so Few Magnetic Ferroelectrics? Hill, Nicola A. The Journal of Physical Chemistry B, Vol. 104, Issue 29 https://doi.org/10.1021/jp000114x	journal	July 2000
Oxygen-Vacancy-Induced Polar Behavior in (LaFeO ₃ ) ₂ /(SrFeO ₃ ) Superlattices Mishra, Rohan; Kim, Young-Min; Salafranca, Juan Nano Letters, Vol. 14, Issue 5 https://doi.org/10.1021/nl500601d	journal	April 2014
Room-temperature magnetoresistance in an oxide material with an ordered double-perovskite structure Kobayashi, K. -I.; Kimura, T.; Sawada, H. Nature, Vol. 395, Issue 6703 https://doi.org/10.1038/27167	journal	October 1998
Origin of ferroelectricity in perovskite oxides Cohen, Ronald E. Nature, Vol. 358, Issue 6382 https://doi.org/10.1038/358136a0	journal	July 1992
A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface Ohtomo, A.; Hwang, H. Y. Nature, Vol. 427, Issue 6973 https://doi.org/10.1038/nature02308	journal	January 2004
Multiferroic and magnetoelectric materials Eerenstein, W.; Mathur, N. D.; Scott, J. F. Nature, Vol. 442, Issue 7104 https://doi.org/10.1038/nature05023	journal	August 2006
Multiferroics progress and prospects in thin films Ramesh, R.; Spaldin, Nicola A. Nature Materials, Vol. 6, Issue 1, p. 21-29 https://doi.org/10.1038/nmat1805	journal	January 2007
Multiferroic memories Scott, J. F. Nature Materials, Vol. 6, Issue 4 https://doi.org/10.1038/nmat1868	journal	March 2007
A multiferroic material to search for the permanent electric dipole moment of the electron Rushchanskii, K. Z.; Kamba, S.; Goian, V. Nature Materials, Vol. 9, Issue 8 https://doi.org/10.1038/nmat2799	journal	July 2010
Persistent optically induced magnetism in oxygen-deficient strontium titanate Rice, W. D.; Ambwani, P.; Bombeck, M. Nature Materials, Vol. 13, Issue 5 https://doi.org/10.1038/nmat3914	journal	March 2014
Direct imaging of the coexistence of ferromagnetism and superconductivity at the LaAlO₃/SrTiO₃ interface Bert, Julie A.; Kalisky, Beena; Bell, Christopher Nature Physics, Vol. 7, Issue 10, p. 767-771 https://doi.org/10.1038/nphys2079	journal	September 2011
Oxygen-Vacancy-Induced Antiferromagnetism to Ferromagnetism Transformation in Eu0.5Ba0.5TiO3−δ Multiferroic Thin Films Li, Weiwei; Zhao, Run; Wang, Le Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02618	journal	September 2013
Study of strain fields at a-Si/c-Si interface Yu, Zhiheng; Muller, David A.; Silcox, John Journal of Applied Physics, Vol. 95, Issue 7 https://doi.org/10.1063/1.1649463	journal	April 2004
Multiferroics: Past, present, and future Spaldin, Nicola A.; Cheong, Sang-Wook; Ramesh, Ramamoorthy Physics Today, Vol. 63, Issue 10 https://doi.org/10.1063/1.3502547	journal	October 2010
Room-temperature ferroelectricity in SrTiO ₃ nanodots array formed by an ac -bias field Yeog Son, Jong; Lee, Jung-Hoon; Myung Jang, Hyun Applied Physics Letters, Vol. 103, Issue 10 https://doi.org/10.1063/1.4820407	journal	September 2013
Ferroelectromagnets Smolenskiĭ, G. A.; Chupis, I. E. Soviet Physics Uspekhi, Vol. 25, Issue 7 https://doi.org/10.1070/PU1982v025n07ABEH004570	journal	July 1982
Dielectric, magnetic and structural properties of novel multiferroic Eu _0.5 Ba _0.5 TiO ₃ ceramics Goian, V.; Kamba, S.; Nuzhnyy, D. Journal of Physics: Condensed Matter, Vol. 23, Issue 2 https://doi.org/10.1088/0953-8984/23/2/025904	journal	December 2010
Coupling between magnetism and dielectric properties in quantum paraelectric EuTiO 3 Katsufuji, T.; Takagi, H. Physical Review B, Vol. 64, Issue 5 https://doi.org/10.1103/PhysRevB.64.054415	journal	July 2001
Coupling between the magnetism and dielectric properties in Eu 1 − x Ba x TiO 3 Wu, Hua; Jiang, Qing; Shen, Wen Zhong Physical Review B, Vol. 69, Issue 1 https://doi.org/10.1103/PhysRevB.69.014104	journal	January 2004
Influence of strain and oxygen vacancies on the magnetoelectric properties of multiferroic bismuth ferrite Ederer, Claude; Spaldin, Nicola A. Physical Review B, Vol. 71, Issue 22 https://doi.org/10.1103/PhysRevB.71.224103	journal	June 2005
Electronic structure of the spin- 1 2 quantum magnet TiOCl Hoinkis, M.; Sing, M.; Schäfer, J. Physical Review B, Vol. 72, Issue 12 https://doi.org/10.1103/PhysRevB.72.125127	journal	September 2005
Antiferromagnetic superexchange via 3 d states of titanium in EuTiO 3 as seen from hybrid Hartree-Fock density functional calculations Akamatsu, Hirofumi; Kumagai, Yu; Oba, Fumiyasu Physical Review B, Vol. 83, Issue 21 https://doi.org/10.1103/PhysRevB.83.214421	journal	June 2011
Magnetic and superconducting phases at the LaAlO 3 /SrTiO 3 interface: The role of interfacial Ti 3 d electrons Pavlenko, N.; Kopp, T.; Tsymbal, E. Y. Physical Review B, Vol. 85, Issue 2 https://doi.org/10.1103/PhysRevB.85.020407	journal	January 2012
Role of Ti Antisitelike Defects in SrTiO 3 Choi, Minseok; Oba, Fumiyasu; Tanaka, Isao Physical Review Letters, Vol. 103, Issue 18 https://doi.org/10.1103/PhysRevLett.103.185502	journal	October 2009
Insulating Ferromagnetic LaCoO 3 − δ Films: A Phase Induced by Ordering of Oxygen Vacancies Biškup, Neven; Salafranca, Juan; Mehta, Virat Physical Review Letters, Vol. 112, Issue 8 https://doi.org/10.1103/PhysRevLett.112.087202	journal	February 2014
Multiferroic Vacancies at Ferroelectric PbTiO 3 Surfaces Shimada, Takahiro; Wang, Jie; Araki, Yasumitsu Physical Review Letters, Vol. 115, Issue 10 https://doi.org/10.1103/PhysRevLett.115.107202	journal	September 2015
Magnetic and Electric Phase Control in Epitaxial EuTiO 3 from First Principles Fennie, Craig J.; Rabe, Karin M. Physical Review Letters, Vol. 97, Issue 26 https://doi.org/10.1103/PhysRevLett.97.267602	journal	December 2006
Simple ways of determining perovskite structures Glazer, A. M. Acta Crystallographica Section A, Vol. 31, Issue 6 https://doi.org/10.1107/S0567739475001635	journal	November 1975
The classification of tilted octahedra in perovskites Glazer, A. M. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 28, Issue 11 https://doi.org/10.1107/S0567740872007976	journal	November 1972
Epitaxial BiFeO₃ Multiferroic Thin Film Heterostructures Wang, J.; Neaton, J. B.; Zheng, H. Science, Vol. 299, Issue 5613, p. 1719-1722 https://doi.org/10.1126/science.1080615	journal	March 2003
Functional Ion Defects in Transition Metal Oxides Kalinin, S. V.; Spaldin, N. A. Science, Vol. 341, Issue 6148 https://doi.org/10.1126/science.1243098	journal	August 2013

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A DFT investigation of the role of oxygen vacancies on the structural, electronic and magnetic properties of ATiO ₃ (A = Mn, Fe, Ni) multiferroic materials Ribeiro, R. A. P.; Longo, E.; Andrés, J. Physical Chemistry Chemical Physics, Vol. 20, Issue 45 https://doi.org/10.1039/c8cp04443k	journal	January 2018
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Manipulating multiple order parameters via oxygen vacancies: The case of E u0.5 B a0.5 Ti O3-δ

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Manipulating multiple order parameters via oxygen vacancies: The case of $E u_{0.5} B a_{0.5} Ti O_{3 - δ}$