Unconventional crystal-field splitting in noncentrosymmetric BaTiO3 thin films

Song, Yang; Liu, Xiaoran; Wen, Fangdi; Kareev, M.; Zhang, Ruyi; Pei, Yujuan; Bi, Jiachang; Shafer, Padraic; N'Diaye, Alpha T.; Arenholz, Elke; Park, Se Young; Cao, Yanwei; Chakhalian, J.

doi:10.1103/physrevmaterials.4.024413

Unconventional crystal-field splitting in noncentrosymmetric BaTiO₃ thin films

Journal Article · Mon Feb 24 00:00:00 EST 2020 · Physical Review Materials

DOI:https://doi.org/10.1103/physrevmaterials.4.024413· OSTI ID:1634075

^[1]; Liu, Xiaoran ^[2]; ^[2]; Kareev, M. ^[2]; Zhang, Ruyi ^[1]; ^[1]; Bi, Jiachang ^[1]; Shafer, Padraic ^[3]; N'Diaye, Alpha T. ^[3]; Arenholz, Elke ^[3]; Park, Se Young ^[4]; Cao, Yanwei ^[1]; Chakhalian, J. ^[2]

Chinese Academy of Sciences (CAS), Zhejiang (China); Univ. of Chinese Academy of Sciences, Beijing (China)
Rutgers Univ., Piscataway, NJ (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Inst. for Basic Science, Seoul (Korea); Seoul National Univ. (Korea)

Understanding the crystal-field splitting and orbital polarization in noncentrosymmetric systems such as ferroelectric materials is fundamentally important. In this work, taking BaTiO₃ as a representative material, we investigate titanium crystal-field splitting and orbital polarization in noncentrosymmetric TiO₆ octahedra with resonant x-ray linear dichroism at the Ti L_2,3 edge. The high-quality BaTiO₃ thin films were deposited on DyScO₃ (110) single crystal substrates in a layer-by-layer way by pulsed laser deposition. The reflection high-energy electron diffraction and element specific x-ray absorption spectroscopy were performed to characterize the structural and electronic properties of the films. In sharp contrast to conventional crystal-field splitting and orbital configuration (d_xz/d_yz < d_xy < d_3z²-r² < d_x²-y² or d_xy < d_xz/d_yz < d_x²-y² < d_3z²-r²) expected from compressive or tensile epitaxial strain, respectively, it is revealed that d_xz, d_yz, and d_xy orbitals are nearly degenerate, whereas d_3z²-r² and d_x²-y² orbitals are split with an energy gap ~100 meV in the epitaxial BaTiO₃ films. We find that the unexpected degenerate orbitals d_xz/d_yz/d_xy result from the competition between the orbital splitting induced by epitaxial strain and that induced by polar distortions of BaTiO₃ films. Our results provide a route to manipulate orbital degree of freedom by switching electric polarization in ferroelectric materials.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: Gordon and Betty Moore Foundation; National Natural Science Foundation of China (NNSFC); Ningbo Science and Technology Bureau; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1634075

Alternate ID(s):: OSTI ID: 1601703

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 2 Vol. 4; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

References (59)

Manipulation of Electric Field Effect by Orbital Switch Cui, Bin; Song, Cheng; Mao, Haijun Advanced Functional Materials, Vol. 26, Issue 5 https://doi.org/10.1002/adfm.201504036	journal	December 2015
Structural and Electronic Reconstructions at the LaAlO ₃ /SrTiO ₃ Interface Salluzzo, M.; Gariglio, S.; Torrelles, X. Advanced Materials, Vol. 25, Issue 16 https://doi.org/10.1002/adma.201204555	journal	February 2013
On the origin of ferroelectricity in perovskite-type crystals Bersuker, I. B. Physics Letters, Vol. 20, Issue 6 https://doi.org/10.1016/0031-9163(66)91127-9	journal	April 1966
An updated version of wannier90: A tool for obtaining maximally-localised Wannier functions Mostofi, Arash A.; Yates, Jonathan R.; Pizzi, Giovanni Computer Physics Communications, Vol. 185, Issue 8 https://doi.org/10.1016/j.cpc.2014.05.003	journal	August 2014
The CTM4XAS program for EELS and XAS spectral shape analysis of transition metal L edges Stavitski, Eli; de Groot, Frank M. F. Micron, Vol. 41, Issue 7 https://doi.org/10.1016/j.micron.2010.06.005	journal	October 2010
Pseudo Jahn–Teller origin of ferroelectric instability in BaTiO3 type perovskites: The Green's function approach and beyond Polinger, V.; Garcia-Fernandez, P.; Bersuker, I. B. Physica B: Condensed Matter, Vol. 457 https://doi.org/10.1016/j.physb.2014.09.048	journal	January 2015
Pseudo-Jahn–Teller Effect—A Two-State Paradigm in Formation, Deformation, and Transformation of Molecular Systems and Solids Bersuker, Isaac B. Chemical Reviews, Vol. 113, Issue 3 https://doi.org/10.1021/cr300279n	journal	January 2013
Structures of the ferroelectric phases of barium titanate Kwei, G. H.; Lawson, A. C.; Billinge, S. J. L. The Journal of Physical Chemistry, Vol. 97, Issue 10 https://doi.org/10.1021/j100112a043	journal	March 1993
Crystal Structure and the Paraelectric-to-Ferroelectric Phase Transition of Nanoscale BaTiO ₃ Smith, Millicent B.; Page, Katharine; Siegrist, Theo Journal of the American Chemical Society, Vol. 130, Issue 22 https://doi.org/10.1021/ja0758436	journal	June 2008
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
Ferroelectric Properties of Individual Barium Titanate Nanowires Investigated by Scanned Probe Microscopy Yun, Wan Soo; Urban, Jeffrey J.; Gu, Qian Nano Letters, Vol. 2, Issue 5, p. 447-450 https://doi.org/10.1021/nl015702g	journal	May 2002
Origin of ferroelectricity in perovskite oxides Cohen, Ronald E. Nature, Vol. 358, Issue 6382 https://doi.org/10.1038/358136a0	journal	July 1992
Thin-film ferroelectric materials and their applications Martin, Lane W.; Rappe, Andrew M. Nature Reviews Materials, Vol. 2, Issue 2 https://doi.org/10.1038/natrevmats.2016.87	journal	November 2016
Strong polarization enhancement in asymmetric three-component ferroelectric superlattices Lee, Ho Nyung; Christen, Hans M.; Chisholm, Matthew F. Nature, Vol. 433, Issue 7024 https://doi.org/10.1038/nature03261	journal	January 2005
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
Electric in-plane polarization in multiferroic CoFe2O4/BaTiO3 nanocomposite tuned by magnetic fields Schmitz-Antoniak, Carolin; Schmitz, Detlef; Borisov, Pavel Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3051	journal	June 2013
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
Titanium dx y ferromagnetism at the LaAlO3/SrTiO3 interface Lee, J. -S.; Xie, Y. W.; Sato, H. K. Nature Materials, Vol. 12, Issue 8 https://doi.org/10.1038/nmat3674	journal	June 2013
A ferroelectric quantum phase transition inside the superconducting dome of Sr1−xCaxTiO3−δ Rischau, Carl Willem; Lin, Xiao; Grams, Christoph P. Nature Physics, Vol. 13, Issue 7 https://doi.org/10.1038/nphys4085	journal	April 2017
Ferroelectricity woos pairing Gabay, Marc; Triscone, Jean-Marc Nature Physics, Vol. 13, Issue 7 https://doi.org/10.1038/nphys4124	journal	April 2017
Anomalous orbital structure in a spinel–perovskite interface Cao, Yanwei; Liu, Xiaoran; Shafer, Padraic npj Quantum Materials, Vol. 1, Issue 1 https://doi.org/10.1038/npjquantmats.2016.9	journal	August 2016
Artificial two-dimensional polar metal at room temperature Cao, Yanwei; Wang, Zhen; Park, Se Young Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03964-9	journal	April 2018
Ferroelectrically tunable magnetic skyrmions in ultrathin oxide heterostructures Wang, Lingfei; Feng, Qiyuan; Kim, Yoonkoo Nature Materials, Vol. 17, Issue 12 https://doi.org/10.1038/s41563-018-0204-4	journal	November 2018
Polar metal phase stabilized in strained La-doped BaTiO3films Takahashi, K. S.; Matsubara, Y.; Bahramy, M. S. Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-04635-3	journal	July 2017
Fatigue of piezoelectric properties in Pb(Zr,Ti)O ₃ films Kholkin, A. L.; Colla, E. L.; Tagantsev, A. K. Applied Physics Letters, Vol. 68, Issue 18 https://doi.org/10.1063/1.116189	journal	April 1996
Strain modification of epitaxial perovskite oxide thin films using structural transitions of ferroelectric BaTiO3 substrate Lee, M. K.; Nath, T. K.; Eom, C. B. Applied Physics Letters, Vol. 77, Issue 22 https://doi.org/10.1063/1.1328762	journal	November 2000
Ferroelectric thin films: Review of materials, properties, and applications Setter, N.; Damjanovic, D.; Eng, L. Journal of Applied Physics, Vol. 100, Issue 5 https://doi.org/10.1063/1.2336999	journal	September 2006
Electric field control of magnetic anisotropies and magnetic coercivity in Fe/BaTiO3(001) heterostructures Brivio, S.; Petti, D.; Bertacco, R. Applied Physics Letters, Vol. 98, Issue 9 https://doi.org/10.1063/1.3554432	journal	February 2011
Magnetism and electronic structure of YTiO3 thin films Cao, Yanwei; Shafer, P.; Liu, Xiaoran Applied Physics Letters, Vol. 107, Issue 11 https://doi.org/10.1063/1.4931039	journal	September 2015
Orbital configuration in CaTiO3 films on NdGaO3 Cao, Yanwei; Park, Se Young; Liu, Xiaoran Applied Physics Letters, Vol. 109, Issue 15 https://doi.org/10.1063/1.4964828	journal	October 2016
Evolution of element-specific electronic structures in alkaline titanates Fan, Wei; Song, Yang; Bi, Jiachang AIP Advances, Vol. 9, Issue 6 https://doi.org/10.1063/1.5109588	journal	June 2019
Interface-induced multiferroism by design in complex oxide superlattices Guo, Hangwen; Wang, Zhen; Dong, Shuai Proceedings of the National Academy of Sciences https://doi.org/10.1073/pnas.1706814114	journal	June 2017
The pressure temperature phase diagram of BaTiO ₃ : a macroscopic description of the low-temperature behaviour Hayward, S. A.; Salje, E. K. H. Journal of Physics: Condensed Matter, Vol. 14, Issue 36 https://doi.org/10.1088/0953-8984/14/36/101	journal	August 2002
Self-interaction correction to density-functional approximations for many-electron systems Perdew, J. P.; Zunger, Alex Physical Review B, Vol. 23, Issue 10, p. 5048-5079 https://doi.org/10.1103/PhysRevB.23.5048	journal	May 1981
L 2 , 3 x-ray-absorption edges of d 0 compounds: K + , Ca 2 + , Sc 3 + , and Ti 4 + in O h (octahedral) symmetry de Groot, F. M. F.; Fuggle, J. C.; Thole, B. T. Physical Review B, Vol. 41, Issue 2 https://doi.org/10.1103/PhysRevB.41.928	journal	January 1990
Theory of polarization of crystalline solids King-Smith, R. D.; Vanderbilt, David Physical Review B, Vol. 47, Issue 3 https://doi.org/10.1103/PhysRevB.47.1651	journal	January 1993
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Local Jahn-Teller distortion in La 1 − x Sr x MnO 3 observed by pulsed neutron diffraction Louca, Despina; Egami, T.; Brosha, E. L. Physical Review B, Vol. 56, Issue 14 https://doi.org/10.1103/PhysRevB.56.R8475	journal	October 1997
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Ab initio study of the phase diagram of epitaxial BaTiO 3 Diéguez, Oswaldo; Tinte, Silvia; Antons, A. Physical Review B, Vol. 69, Issue 21 https://doi.org/10.1103/PhysRevB.69.212101	journal	June 2004
Probing ferroelectricity in PbZr 0.2 Ti 0.8 O 3 with polarized soft x rays Arenholz, E.; van der Laan, G.; Fraile-Rodríguez, A. Physical Review B, Vol. 82, Issue 14 https://doi.org/10.1103/PhysRevB.82.140103	journal	October 2010
Ferroelectric substrate effects on the magnetism, magnetotransport, and electroresistance of La 0.7 Ca 0.3 MnO 3 thin films on BaTiO 3 Alberca, A.; Munuera, C.; Tornos, J. Physical Review B, Vol. 86, Issue 14 https://doi.org/10.1103/PhysRevB.86.144416	journal	October 2012
Polar instability under electrostatic doping in tetragonal SnTi O 3 Ma, Chao; He, Xu; Jin, Kui-juan Physical Review B, Vol. 96, Issue 3 https://doi.org/10.1103/PhysRevB.96.035140	journal	July 2017
Two-dimensional electron systems in A TiO 3 perovskites ( A = Ca , Ba, Sr): Control of orbital hybridization and energy order Rödel, T. C.; Vivek, M.; Fortuna, F. Physical Review B, Vol. 96, Issue 4 https://doi.org/10.1103/PhysRevB.96.041121	journal	July 2017
Strain-engineering stabilization of BaTi O 3 -based polar metals Ma, Chao; Jin, Kui-juan; Ge, Chen Physical Review B, Vol. 97, Issue 11 https://doi.org/10.1103/PhysRevB.97.115103	journal	March 2018
Probing ferroelectricity in highly conducting materials through their elastic response: Persistence of ferroelectricity in metallic BaTiO 3 − δ Cordero, F.; Trequattrini, F.; Craciun, F. Physical Review B, Vol. 99, Issue 6 https://doi.org/10.1103/PhysRevB.99.064106	journal	February 2019
Orbital Reconstruction and the Two-Dimensional Electron Gas at the LaAlO3/SrTiO3 Interface Salluzzo, M.; Cezar, J. C.; Brookes, N. B. Physical Review Letters, Vol. 102, Issue 16, Article No. 166804 https://doi.org/10.1103/PhysRevLett.102.166804	journal	April 2009
Origin of Interface Magnetism in BiMnO 3 / SrTiO 3 and LaAlO 3 / SrTiO 3 Heterostructures Salluzzo, M.; Gariglio, S.; Stornaiuolo, D. Physical Review Letters, Vol. 111, Issue 8 https://doi.org/10.1103/PhysRevLett.111.087204	journal	August 2013
Two-Dimensional Electron Gases at LaAlO 3 / SrTiO 3 Interfaces: Orbital Symmetry and Hierarchy Engineered by Crystal Orientation Pesquera, D.; Scigaj, M.; Gargiani, P. Physical Review Letters, Vol. 113, Issue 15 https://doi.org/10.1103/PhysRevLett.113.156802	journal	October 2014
Magnetic Interactions at the Nanoscale in Trilayer Titanates Cao, Yanwei; Yang, Zhenzhong; Kareev, M. Physical Review Letters, Vol. 116, Issue 7 https://doi.org/10.1103/PhysRevLett.116.076802	journal	February 2016
Ground State of the Electron Gas by a Stochastic Method Ceperley, D. M.; Alder, B. J. Physical Review Letters, Vol. 45, Issue 7, p. 566-569 https://doi.org/10.1103/PhysRevLett.45.566	journal	August 1980
Ferroelectric Schottky Diode Blom, P. W. M.; Wolf, R. M.; Cillessen, J. F. M. Physical Review Letters, Vol. 73, Issue 15 https://doi.org/10.1103/PhysRevLett.73.2107	journal	October 1994
Phase Diagram of BaTi O 3 Ishidate, T.; Abe, S.; Takahashi, H. Physical Review Letters, Vol. 78, Issue 12 https://doi.org/10.1103/PhysRevLett.78.2397	journal	March 1997
Macroscopic polarization in crystalline dielectrics: the geometric phase approach Resta, Raffaele Reviews of Modern Physics, Vol. 66, Issue 3 https://doi.org/10.1103/RevModPhys.66.899	journal	July 1994
Physics of thin-film ferroelectric oxides Dawber, M.; Rabe, K. M.; Scott, J. F. Reviews of Modern Physics, Vol. 77, Issue 4 https://doi.org/10.1103/RevModPhys.77.1083	journal	October 2005
Enhancement of Ferroelectricity in Strained BaTiO₃ Thin Films Choi, K. J.; Biegalski, M.; Li, Y. L. Science, Vol. 306, Issue 5698, p. 1005-1009 https://doi.org/10.1126/science.1103218	journal	November 2004
MATERIALS SCIENCE: The Renaissance of Magnetoelectric Multiferroics Spaldin, N. A. Science, Vol. 309, Issue 5733 https://doi.org/10.1126/science.1113357	journal	July 2005
Strain Tuning of Ferroelectric Thin Films Schlom, Darrell G.; Chen, Long-Qing; Eom, Chang-Beom Annual Review of Materials Research, Vol. 37, Issue 1 https://doi.org/10.1146/annurev.matsci.37.061206.113016	journal	August 2007

Similar Records

Orbital configuration in CaTiO₃ films on NdGaO₃

Journal Article · Wed Oct 12 20:00:00 EDT 2016 · Applied Physics Letters · OSTI ID:1347292

Fourfold symmetric planar Hall effect in epitaxial La{sub 1−x}Sr{sub x}CoO{sub 3} thin films

Journal Article · Tue Apr 07 00:00:00 EDT 2015 · Journal of Applied Physics · OSTI ID:22399383

Related Subjects

36 MATERIALS SCIENCE
LDA
complex oxides
crystal summetry
density functional theory
electric polarization
ferroelectricity
ferroelectrics
noncentrosymmetric materials
orbital order
perovskite
x-ray absorption spectroscopy

Unconventional crystal-field splitting in noncentrosymmetric BaTiO3 thin films

Citation Formats

References (59)

Similar Records

Related Subjects

Unconventional crystal-field splitting in noncentrosymmetric BaTiO₃ thin films