Orbital Engineering in Nickelate Heterostructures Driven by Anisotropic Oxygen Hybridization rather than Orbital Energy Levels
Abstract
We used resonant inelastic x-ray scattering to investigate the electronic origin of orbital polarization in nickelate heterostructures taking LaTiO3-LaNiO3-3×(LaAlO3), a system with exceptionally large polarization, as a model system. Furthermore, we find that heterostructuring generates only minor changes in the Ni 3d orbital energy levels, contradicting the often-invoked picture in which changes in orbital energy levels generate orbital polarization. Instead, O K-edge x-ray absorption spectroscopy demonstrates that orbital polarization is caused by an anisotropic reconstruction of the oxygen ligand hole states. This also provides an explanation for the limited success of theoretical predictions based on tuning orbital energy levels and implies that future theories should focus on anisotropic hybridization as the most effective means to drive large changes in electronic structure and realize novel emergent phenomena.
- Authors:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Condensed Matter Physics and Materials Science
- National Synchrotron Radiation Research Center, Hsinchu (Taiwan)
- Paul Scherrer Inst. (PSI), Villigen (Switzerland). Research Dept.
- Yale Univ., New Haven, CT (United States). Dept. of Applied Physics
- Yale Univ., New Haven, CT (United States). Dept. of Applied Physics and Dept. of Mechanical Engineering and Materials Science
- National Synchrotron Radiation Research Center, Hsinchu (Taiwan); National Tsing Hua Univ., Hsinchu (Taiwan). Dept. of Physics
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1336148
- Alternate Identifier(s):
- OSTI ID: 1327546
- Report Number(s):
- BNL-112639-2016-JA
Journal ID: ISSN 0031-9007; PRLTAO; R&D Project: PO011; KC0201060
- Grant/Contract Number:
- SC00112704; 1047478
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review Letters
- Additional Journal Information:
- Journal Volume: 117; Journal Issue: 14; Journal ID: ISSN 0031-9007
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY
Citation Formats
Fabbris, G., Meyers, D., Okamoto, J., Pelliciari, J., Disa, A. S., Huang, Y., Chen, Z. -Y., Wu, W. B., Chen, C. T., Ismail-Beigi, S., Ahn, C. H., Walker, F. J., Huang, D. J., Schmitt, T., and Dean, M. P. M. Orbital Engineering in Nickelate Heterostructures Driven by Anisotropic Oxygen Hybridization rather than Orbital Energy Levels. United States: N. p., 2016.
Web. doi:10.1103/PhysRevLett.117.147401.
Fabbris, G., Meyers, D., Okamoto, J., Pelliciari, J., Disa, A. S., Huang, Y., Chen, Z. -Y., Wu, W. B., Chen, C. T., Ismail-Beigi, S., Ahn, C. H., Walker, F. J., Huang, D. J., Schmitt, T., & Dean, M. P. M. Orbital Engineering in Nickelate Heterostructures Driven by Anisotropic Oxygen Hybridization rather than Orbital Energy Levels. United States. https://doi.org/10.1103/PhysRevLett.117.147401
Fabbris, G., Meyers, D., Okamoto, J., Pelliciari, J., Disa, A. S., Huang, Y., Chen, Z. -Y., Wu, W. B., Chen, C. T., Ismail-Beigi, S., Ahn, C. H., Walker, F. J., Huang, D. J., Schmitt, T., and Dean, M. P. M. Fri .
"Orbital Engineering in Nickelate Heterostructures Driven by Anisotropic Oxygen Hybridization rather than Orbital Energy Levels". United States. https://doi.org/10.1103/PhysRevLett.117.147401. https://www.osti.gov/servlets/purl/1336148.
@article{osti_1336148,
title = {Orbital Engineering in Nickelate Heterostructures Driven by Anisotropic Oxygen Hybridization rather than Orbital Energy Levels},
author = {Fabbris, G. and Meyers, D. and Okamoto, J. and Pelliciari, J. and Disa, A. S. and Huang, Y. and Chen, Z. -Y. and Wu, W. B. and Chen, C. T. and Ismail-Beigi, S. and Ahn, C. H. and Walker, F. J. and Huang, D. J. and Schmitt, T. and Dean, M. P. M.},
abstractNote = {We used resonant inelastic x-ray scattering to investigate the electronic origin of orbital polarization in nickelate heterostructures taking LaTiO3-LaNiO3-3×(LaAlO3), a system with exceptionally large polarization, as a model system. Furthermore, we find that heterostructuring generates only minor changes in the Ni 3d orbital energy levels, contradicting the often-invoked picture in which changes in orbital energy levels generate orbital polarization. Instead, O K-edge x-ray absorption spectroscopy demonstrates that orbital polarization is caused by an anisotropic reconstruction of the oxygen ligand hole states. This also provides an explanation for the limited success of theoretical predictions based on tuning orbital energy levels and implies that future theories should focus on anisotropic hybridization as the most effective means to drive large changes in electronic structure and realize novel emergent phenomena.},
doi = {10.1103/PhysRevLett.117.147401},
journal = {Physical Review Letters},
number = 14,
volume = 117,
place = {United States},
year = {Fri Sep 30 00:00:00 EDT 2016},
month = {Fri Sep 30 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Electronic structure of possible nickelate analogs to the cuprates
journal, March 1999
- Anisimov, V. I.; Bukhvalov, D.; Rice, T. M.
- Physical Review B, Vol. 59, Issue 12
Turning a Nickelate Fermi Surface into a Cupratelike One through Heterostructuring
journal, June 2009
- Hansmann, P.; Yang, Xiaoping; Toschi, A.
- Physical Review Letters, Vol. 103, Issue 1
Multiplet effects in X-ray spectroscopy
journal, January 2005
- Groot, Frank de
- Coordination Chemistry Reviews, Vol. 249, Issue 1-2
Estimating Hybridization of Transition Metal and Oxygen States in Perovskites from O K -edge X-ray Absorption Spectroscopy
journal, January 2014
- Suntivich, Jin; Hong, Wesley T.; Lee, Yueh-Lin
- The Journal of Physical Chemistry C, Vol. 118, Issue 4
Band gaps and electronic structure of transition-metal compounds
journal, July 1985
- Zaanen, J.; Sawatzky, G. A.; Allen, J. W.
- Physical Review Letters, Vol. 55, Issue 4
Multiplet resonance lifetimes in resonant inelastic x-ray scattering involving shallow core levels
journal, November 2012
- Wray, L. Andrew; Yang, Wanli; Eisaki, Hiroshi
- Physical Review B, Vol. 86, Issue 19
Physics of Ultrathin Films and Heterostructures of Rare-Earth Nickelates
journal, July 2016
- Middey, S.; Chakhalian, J.; Mahadevan, P.
- Annual Review of Materials Research, Vol. 46, Issue 1
Orbital Order and Possible Superconductivity in Superlattices
journal, January 2008
- Chaloupka, Jiří; Khaliullin, Giniyat
- Physical Review Letters, Vol. 100, Issue 1
Structural, magnetic and electronic properties of perovskites (R = rare earth)
journal, February 1997
- Medarde, María Luisa
- Journal of Physics: Condensed Matter, Vol. 9, Issue 8
Spin and charge ordering in self-doped Mott insulators
journal, May 2000
- Mizokawa, T.; Khomskii, D. I.; Sawatzky, G. A.
- Physical Review B, Vol. 61, Issue 17
Strain-modulated Mott transition in EuNiO ultrathin films
journal, August 2013
- Meyers, D.; Middey, S.; Kareev, M.
- Physical Review B, Vol. 88, Issue 7
Electronic structure of studied by photoemission and x-ray-absorption spectroscopy: Band gap and orbital ordering
journal, November 1995
- Mizokawa, T.; Fujimori, A.; Arima, T.
- Physical Review B, Vol. 52, Issue 19
Dynamical behavior of x-ray absorption and scattering at the L edge of titanium compounds: Experiment and theory
journal, January 1999
- Jiménez-Mier, J.; van Ek, J.; Ederer, D. L.
- Physical Review B, Vol. 59, Issue 4
Resonant inelastic x-ray scattering studies of elementary excitations
journal, June 2011
- Ament, Luuk J. P.; van Veenendaal, Michel; Devereaux, Thomas P.
- Reviews of Modern Physics, Vol. 83, Issue 2
Ab Initio determination of Cu 3d orbital energies in layered copper oxides
journal, August 2011
- Hozoi, Liviu; Siurakshina, Liudmila; Fulde, Peter
- Scientific Reports, Vol. 1, Issue 1
Engineered Mott ground state in a LaTiO3+δ/LaNiO3 heterostructure
journal, January 2016
- Cao, Yanwei; Liu, Xiaoran; Kareev, M.
- Nature Communications, Vol. 7, Issue 1
Bands, resonances, edge singularities and excitons in core level spectroscopy investigated within the dynamical mean-field theory
journal, December 2014
- Haverkort, M. W.; Sangiovanni, G.; Hansmann, P.
- EPL (Europhysics Letters), Vol. 108, Issue 5
Band approach to the excitation-energy dependence of x-ray fluorescence of
journal, July 1999
- Finkelstein, L. D.; Kurmaev, E. Z.; Korotin, M. A.
- Physical Review B, Vol. 60, Issue 4
Colloquium : Emergent properties in plane view: Strong correlations at oxide interfaces
journal, October 2014
- Chakhalian, Jak; Freeland, John W.; Millis, Andrew J.
- Reviews of Modern Physics, Vol. 86, Issue 4
NiO as a test case for high resolution resonant inelastic soft x-ray scattering
journal, August 2005
- Ghiringhelli, G.; Matsubara, M.; Dallera, C.
- Journal of Physics: Condensed Matter, Vol. 17, Issue 35
Effective Hamiltonian for the superconducting Cu oxides
journal, March 1988
- Zhang, F. C.; Rice, T. M.
- Physical Review B, Vol. 37, Issue 7
Cu -edge resonant inelastic x-ray scattering in edge-sharing cuprates
journal, March 2008
- Vernay, F.; Moritz, B.; Elfimov, I. S.
- Physical Review B, Vol. 77, Issue 10
Orbital reflectometry of oxide heterostructures
journal, February 2011
- Benckiser, Eva; Haverkort, Maurits W.; Brück, Sebastian
- Nature Materials, Vol. 10, Issue 3
Evolution of electronic structure across the rare-earth RNiO3 series
journal, April 2016
- Freeland, John W.; van Veenendaal, Michel; Chakhalian, Jak
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 208
Hybridization-controlled charge transfer and induced magnetism at correlated oxide interfaces
journal, January 2016
- Grisolia, M. N.; Varignon, J.; Sanchez-Santolino, G.
- Nature Physics, Vol. 12, Issue 5
Orbital character of states at the Fermi level in and ( R =Nd,Sm)
journal, February 1993
- Pellegrin, E.; Nücker, N.; Fink, J.
- Physical Review B, Vol. 47, Issue 6
Asymmetric Orbital-Lattice Interactions in Ultrathin Correlated Oxide Films
journal, September 2011
- Chakhalian, J.; Rondinelli, J. M.; Liu, Jian
- Physical Review Letters, Vol. 107, Issue 11
Resonant soft x-ray Raman scattering of NiO
journal, March 2002
- Magnuson, M.; Butorin, S. M.; Agui, A.
- Journal of Physics: Condensed Matter, Vol. 14, Issue 13
Polarization-dependent nickel x-ray-absorption spectra of
journal, January 1998
- Kuiper, Pieter; van Elp, J.; Rice, D. E.
- Physical Review B, Vol. 57, Issue 3
: A Self-Doped Double Exchange Ferromagnet
journal, May 1998
- Korotin, M. A.; Anisimov, V. I.; Khomskii, D. I.
- Physical Review Letters, Vol. 80, Issue 19
Origin of the band gap in the negative charge-transfer-energy compound
journal, September 1991
- Mizokawa, T.; Namatame, H.; Fujimori, A.
- Physical Review Letters, Vol. 67, Issue 12
Quantifying electronic correlation strength in a complex oxide: A combined DMFT and ARPES study of
journal, December 2015
- Nowadnick, E. A.; Ruf, J. P.; Park, H.
- Physical Review B, Vol. 92, Issue 24
Magnetic Oxide Heterostructures
journal, July 2014
- Bhattacharya, Anand; May, Steven J.
- Annual Review of Materials Research, Vol. 44, Issue 1
Possible interaction-driven topological phases in (111) bilayers of LaNiO
journal, November 2011
- Yang, Kai-Yu; Zhu, Wenguang; Xiao, Di
- Physical Review B, Vol. 84, Issue 20
Topological insulators from complex orbital order in transition-metal oxides heterostructures
journal, November 2011
- Rüegg, Andreas; Fiete, Gregory A.
- Physical Review B, Vol. 84, Issue 20
Effective crystal field and Fermi surface topology: A comparison of - and -orbital models
journal, November 2013
- Parragh, N.; Sangiovanni, G.; Hansmann, P.
- Physical Review B, Vol. 88, Issue 19
Charge Disproportionation without Charge Transfer in the Rare-Earth-Element Nickelates as a Possible Mechanism for the Metal-Insulator Transition
journal, March 2014
- Johnston, Steve; Mukherjee, Anamitra; Elfimov, Ilya
- Physical Review Letters, Vol. 112, Issue 10
Research Update: Orbital polarization in LaNiO 3 -based heterostructures
journal, June 2015
- Disa, Ankit S.; Walker, F. J.; Ismail-Beigi, Sohrab
- APL Materials, Vol. 3, Issue 6
A Thin Film Approach to Engineering Functionality into Oxides
journal, August 2008
- Schlom, Darrell G.; Chen, Long-Qing; Pan, Xiaoqing
- Journal of the American Ceramic Society, Vol. 91, Issue 8
Orbital control in strained ultra-thin LaNiO 3 /LaAlO 3 superlattices
journal, November 2011
- Freeland, J. W.; Liu, Jian; Kareev, M.
- EPL (Europhysics Letters), Vol. 96, Issue 5
Strain and composition dependence of orbital polarization in nickel oxide superlattices
journal, September 2013
- Wu, M.; Benckiser, E.; Haverkort, M. W.
- Physical Review B, Vol. 88, Issue 12
Fermi level density of states modulation without charge transfer in nickelate superlattices
journal, March 2014
- Han, Myung Joon; van Veenendaal, Michel
- Journal of Physics: Condensed Matter, Vol. 26, Issue 14
GenX : an extensible X-ray reflectivity refinement program utilizing differential evolution
journal, November 2007
- Björck, Matts; Andersson, Gabriella
- Journal of Applied Crystallography, Vol. 40, Issue 6
Spin State of Negative Charge-Transfer Material
journal, September 2012
- Kuneš, J.; Křápek, V.; Parragh, N.
- Physical Review Letters, Vol. 109, Issue 11
Engineering Correlation Effects via Artificially Designed Oxide Superlattices
journal, September 2013
- Chen, Hanghui; Millis, Andrew J.; Marianetti, Chris A.
- Physical Review Letters, Vol. 111, Issue 11
Orbital Engineering in Symmetry-Breaking Polar Heterostructures
journal, January 2015
- Disa, Ankit S.; Kumah, Divine P.; Malashevich, Andrei
- Physical Review Letters, Vol. 114, Issue 2
Site-Selective Mott Transition in Rare-Earth-Element Nickelates
journal, October 2012
- Park, Hyowon; Millis, Andrew J.; Marianetti, Chris A.
- Physical Review Letters, Vol. 109, Issue 15
Reconstructed Fermi Surface of Underdoped Cuprate Superconductors
journal, July 2011
- Yang, H. -B.; Rameau, J. D.; Pan, Z. -H.
- Physical Review Letters, Vol. 107, Issue 4
O 1 s near-edge x-ray absorption of : Holes, polarons, and excitons
journal, April 1996
- Pellegrin, E.; Zaanen, J.; Lin, H. -J.
- Physical Review B, Vol. 53, Issue 16
Out-of-plane orbital characters of intrinsic and doped holes in
journal, April 1992
- Chen, C. T.; Tjeng, L. H.; Kwo, J.
- Physical Review Letters, Vol. 68, Issue 16
SAXES, a high resolution spectrometer for resonant x-ray emission in the 400–1600eV energy range
journal, November 2006
- Ghiringhelli, G.; Piazzalunga, A.; Dallera, C.
- Review of Scientific Instruments, Vol. 77, Issue 11
Spin-orbit-induced mixed-spin ground state in perovskites probed by x-ray absorption spectroscopy: Insight into the metal-to-insulator transition
journal, January 2005
- Piamonteze, C.; de Groot, F. M. F.; Tolentino, H. C. N.
- Physical Review B, Vol. 71, Issue 2
Interface Physics in Complex Oxide Heterostructures
journal, March 2011
- Zubko, Pavlo; Gariglio, Stefano; Gabay, Marc
- Annual Review of Condensed Matter Physics, Vol. 2, Issue 1
Modifying the Electronic Orbitals of Nickelate Heterostructures via Structural Distortions
journal, May 2013
- Chen, Hanghui; Kumah, Divine P.; Disa, Ankit S.
- Physical Review Letters, Vol. 110, Issue 18
Progress in perovskite nickelate research
journal, July 2008
- Catalan, G.
- Phase Transitions, Vol. 81, Issue 7-8
The CTM4XAS program for EELS and XAS spectral shape analysis of transition metal L edges
journal, October 2010
- Stavitski, Eli; de Groot, Frank M. F.
- Micron, Vol. 41, Issue 7
Tuning the Structure of Nickelates to Achieve Two-Dimensional Electron Conduction
journal, February 2014
- Kumah, Divine P.; Disa, Ankit S.; Ngai, Joseph H.
- Advanced Materials, Vol. 26, Issue 12
Sum Rules and Fundamental Spectra of Magnetic X-Ray Dichroism in Crystal Field Symmetry
journal, June 1994
- van der Laan, G.
- Journal of the Physical Society of Japan, Vol. 63, Issue 6
Insights into the high temperature superconducting cuprates from resonant inelastic X-ray scattering
journal, February 2015
- Dean, M. P. M.
- Journal of Magnetism and Magnetic Materials, Vol. 376
High-resolution soft X-ray beamline ADRESS at the Swiss Light Source for resonant inelastic X-ray scattering and angle-resolved photoelectron spectroscopies
journal, July 2010
- Strocov, V. N.; Schmitt, T.; Flechsig, U.
- Journal of Synchrotron Radiation, Vol. 17, Issue 5
Emergent phenomena at oxide interfaces
journal, January 2012
- Hwang, H. Y.; Iwasa, Y.; Kawasaki, M.
- Nature Materials, Vol. 11, Issue 2
Exchange bias in LaNiO3–LaMnO3 superlattices
journal, January 2012
- Gibert, Marta; Zubko, Pavlo; Scherwitzl, Raoul
- Nature Materials, Vol. 11, Issue 3
Dynamical Mean-Field Theory of Nickelate Superlattices
journal, November 2011
- Han, M. J.; Wang, Xin; Marianetti, C. A.
- Physical Review Letters, Vol. 107, Issue 20
Influence of quantum confinement and strain on orbital polarization of four-layer superlattices: A DFT+DMFT study
journal, June 2016
- Park, Hyowon; Millis, Andrew J.; Marianetti, Chris A.
- Physical Review B, Vol. 93, Issue 23
Xclaim: A graphical interface for the calculation of core-hole spectroscopies
journal, July 2015
- Fernández-Rodríguez, Javier; Toby, Brian; van Veenendaal, Michel
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 202
Isotropic O 1s prepeak as evidence for polarons in La2NiO4 + δ
journal, March 1995
- Kuiper, P.; Rice, D. E.; Buttrey, D. J.
- Physica B: Condensed Matter, Vol. 208-209
X-ray spectroscopic study of thin films: An ferromagnetic insulator
journal, March 2015
- Tsuyama, T.; Matsuda, T.; Chakraverty, S.
- Physical Review B, Vol. 91, Issue 11
Quantum confinement of Mott electrons in ultrathin LaNiO /LaAlO superlattices
journal, April 2011
- Liu, Jian; Okamoto, S.; van Veenendaal, M.
- Physical Review B, Vol. 83, Issue 16
Observation of Two Nondispersive Magnetic Excitations in NiO by Resonant Inelastic Soft-X-Ray Scattering
journal, January 2009
- Ghiringhelli, G.; Piazzalunga, A.; Dallera, C.
- Physical Review Letters, Vol. 102, Issue 2
Chemical control of orbital polarization in artificially structured transition-metal oxides: from first principles
journal, October 2010
- Han, M. J.; Marianetti, C. A.; Millis, A. J.
- Physical Review B, Vol. 82, Issue 13
The Theory of Atomic Structure and Spectra
book, December 1981
- Cowan, Robert D.
- Los Alamos Series in Basic and Applied Sciences, Vol. 3
Works referencing / citing this record:
Ground-state oxygen holes and the metal–insulator transition in the negative charge-transfer rare-earth nickelates
journal, October 2016
- Bisogni, Valentina; Catalano, Sara; Green, Robert J.
- Nature Communications, Vol. 7, Issue 1
Large orbital polarization in nickelate-cuprate heterostructures by dimensional control of oxygen coordination
journal, February 2019
- Liao, Zhaoliang; Skoropata, Elizabeth; Freeland, J. W.
- Nature Communications, Vol. 10, Issue 1
Low-energy orbital excitations in strained films
journal, October 2019
- Wang, Ru-Pan; Geessinck, Jaap; Elnaggar, Hebatalla
- Physical Review B, Vol. 100, Issue 16
Hybridization-Switching Induced Mott Transition in Perovskites
journal, January 2019
- Paul, Atanu; Mukherjee, Anamitra; Dasgupta, Indra
- Physical Review Letters, Vol. 122, Issue 1
Digital modulation of the nickel valence state in a cuprate-nickelate heterostructure
text, January 2017
- Wrobel, F.; Geisler, B.; Wang, Y.
- arXiv
Emergent c-axis magnetic helix in manganite-nickelate superlattices
text, January 2018
- Fabbris, G.; Jaouen, N.; Meyers, D.
- arXiv
Epitaxial strain modulated electronic properties of interface controlled nickelate superlattice
text, January 2018
- Middey, S.; Meyers, D.; Ojha, Shashank Kumar
- arXiv