Antiferromagnetic defect structure in single crystals
Abstract
The origins of the metal-insulator and magnetic transitions exhibited by perovskite rare-earth nickelates, RNiO3 (where R is a rare-earth element), remain open issues, with charge disproportionation, magnetic interactions, and lattice response across multiple length scales being among the many possible origins. Recently, growth of single crystals of LaNiO3, which is the only member of these compounds that remains metallic in its ground state, has been reported, opening a new chapter in the investigation of the perovskite nickelates. Here, using a combination of magnetometry, heat capacity, and neutron scattering on as-grown and purposely reduced LaNiO3-delta crystals, we show that both antiferromagnetic and ferromagnetic phases with a Neel temperature of similar to 152 K and a Curie temperature of similar to 225 K can be induced by reduction of the oxygen content. Transmission electron microscopy shows that these phases are characterized by ordered oxygen vacancy defect structures that exist as dilute secondary phases in as-grown crystals despite growth in partial oxygen pressures up to at least 130 bar. The demonstration of antiferromagnetism resulting from oxygen vacancy ordered structures implies that stoichiometry must be explicitly considered when interpreting the bulk properties of LaNiO3-(delta) single crystals; accordingly, the implications of our results for putativemore »
- Authors:
-
[3];
[4];
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Univ. of Illinois at Chicago, Chicago, IL (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation (NSF); USDOE
- OSTI Identifier:
- 1454392
- Alternate Identifier(s):
- OSTI ID: 1441245; OSTI ID: 1461509
- Grant/Contract Number:
- AC05-00OR22725; AC02-06CH11357
- 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
Citation Formats
Wang, Bi -Xia, Rosenkranz, Stephan, Rui, X., Zhang, Junjie, Ye, Feng, Zheng, Hong, Klie, R. F., Mitchell, John F., and Phelan, Daniel. Antiferromagnetic defect structure in LaNiO3–δ single crystals. United States: N. p., 2018.
Web. doi:10.1103/PhysRevMaterials.2.064404.
Wang, Bi -Xia, Rosenkranz, Stephan, Rui, X., Zhang, Junjie, Ye, Feng, Zheng, Hong, Klie, R. F., Mitchell, John F., & Phelan, Daniel. Antiferromagnetic defect structure in LaNiO3–δ single crystals. United States. https://doi.org/10.1103/PhysRevMaterials.2.064404
Wang, Bi -Xia, Rosenkranz, Stephan, Rui, X., Zhang, Junjie, Ye, Feng, Zheng, Hong, Klie, R. F., Mitchell, John F., and Phelan, Daniel. Tue .
"Antiferromagnetic defect structure in LaNiO3–δ single crystals". United States. https://doi.org/10.1103/PhysRevMaterials.2.064404. https://www.osti.gov/servlets/purl/1454392.
@article{osti_1454392,
title = {Antiferromagnetic defect structure in LaNiO3–δ single crystals},
author = {Wang, Bi -Xia and Rosenkranz, Stephan and Rui, X. and Zhang, Junjie and Ye, Feng and Zheng, Hong and Klie, R. F. and Mitchell, John F. and Phelan, Daniel},
abstractNote = {The origins of the metal-insulator and magnetic transitions exhibited by perovskite rare-earth nickelates, RNiO3 (where R is a rare-earth element), remain open issues, with charge disproportionation, magnetic interactions, and lattice response across multiple length scales being among the many possible origins. Recently, growth of single crystals of LaNiO3, which is the only member of these compounds that remains metallic in its ground state, has been reported, opening a new chapter in the investigation of the perovskite nickelates. Here, using a combination of magnetometry, heat capacity, and neutron scattering on as-grown and purposely reduced LaNiO3-delta crystals, we show that both antiferromagnetic and ferromagnetic phases with a Neel temperature of similar to 152 K and a Curie temperature of similar to 225 K can be induced by reduction of the oxygen content. Transmission electron microscopy shows that these phases are characterized by ordered oxygen vacancy defect structures that exist as dilute secondary phases in as-grown crystals despite growth in partial oxygen pressures up to at least 130 bar. The demonstration of antiferromagnetism resulting from oxygen vacancy ordered structures implies that stoichiometry must be explicitly considered when interpreting the bulk properties of LaNiO3-(delta) single crystals; accordingly, the implications of our results for putative oxygen-stoichiometric LaNiO3 are discussed.},
doi = {10.1103/PhysRevMaterials.2.064404},
journal = {Physical Review Materials},
number = 6,
volume = 2,
place = {United States},
year = {Tue Jun 12 00:00:00 EDT 2018},
month = {Tue Jun 12 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 28 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Landau Theory of Charge and Spin Ordering in the Nickelates
journal, January 2011
- Lee, SungBin; Chen, Ru; Balents, Leon
- Physical Review Letters, Vol. 106, Issue 1
Preparation and crystal structure of the deficient perovskite LaNiO 2.5 , solved from neutron powder diffraction data
journal, January 1995
- Alonso, José Antonio; Martínez-Lope, María Jesús
- J. Chem. Soc., Dalton Trans., Issue 17
Synthesis, Crystal Structure, and Properties of Oxygen-Deficient Lanthanum Nickelate LaNiO 3− x (0 ≤ x ≤ 0.5)
journal, March 1994
- Moriga, Toshihiro; Usaka, Osamu; Imamura, Tomomi
- Bulletin of the Chemical Society of Japan, Vol. 67, Issue 3
Charge Ordering as Alternative to Jahn-Teller Distortion
journal, April 2007
- Mazin, I. I.; Khomskii, D. I.; Lengsdorf, R.
- Physical Review Letters, Vol. 98, Issue 17
Implementation of cross correlation for energy discrimination on the time-of-flight spectrometer CORELLI
journal, March 2018
- Ye, Feng; Liu, Yaohua; Whitfield, Ross
- Journal of Applied Crystallography, Vol. 51, Issue 2
Electronic properties of the metallic perovskite : Correlated behavior of 3 d electrons
journal, September 1992
- Sreedhar, K.; Honig, J. M.; Darwin, M.
- Physical Review B, Vol. 46, Issue 10
Complete phase diagram of rare-earth nickelates from first-principles
journal, April 2017
- Varignon, Julien; Grisolia, Mathieu N.; Íñiguez, Jorge
- npj Quantum Materials, Vol. 2, Issue 1
Room-temperature monoclinic distortion due to charge disproportionation in perovskites with small rare-earth cations Y, Er, Tm, Yb, and Lu): A neutron diffraction study
journal, January 2000
- Alonso, J. A.; Martínez-Lope, M. J.; Casais, M. T.
- Physical Review B, Vol. 61, Issue 3
Gaps and pseudogaps in perovskite rare earth nickelates
journal, June 2015
- Allen, S. James; Hauser, Adam J.; Mikheev, Evgeny
- APL Materials, Vol. 3, Issue 6
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
Metal-insulator transition in a two-band model for the perovskite nickelates
journal, October 2011
- Lee, SungBin; Chen, Ru; Balents, Leon
- Physical Review B, Vol. 84, Issue 16
Valence states and magnetic properties of LaNi 1-x Mn x O 3 (for 0⩽x⩽0.2 and x=0.5)
journal, May 1984
- Vasanthacharya, N. Y.; Ganguly, P.; Goodenough, J. B.
- Journal of Physics C: Solid State Physics, Vol. 17, Issue 15
Characterization of oxygen-deficient phases appearing in reduction of the perovskite-type LaNiO3 to La2Ni2O5
journal, July 1995
- Moriga, T.
- Solid State Ionics, Vol. 79
Long-range charge order in the low-temperature insulating phase of
journal, December 2008
- Medarde, M.; Fernández-Díaz, M. T.; Lacorre, Ph.
- Physical Review B, Vol. 78, Issue 21
Novel metal oxides prepared by ingenious synthetic routes
journal, April 1986
- Rao, C. N. R.; Gopalakrishnan, J.; Vidyasagar, K.
- Journal of Materials Research, Vol. 1, Issue 2
Epitaxial growth and surface metallic nature of LaNiO3 thin films
journal, June 2008
- Tsubouchi, K.; Ohkubo, I.; Kumigashira, H.
- Applied Physics Letters, Vol. 92, Issue 26
An electron diffraction study of new phases in the LaNiO3−x system
journal, February 1989
- Gonzalezcalbet, J.; Sayagues, M.; Valletregi, M.
- Solid State Ionics, Vol. 32-33
Systematic study of insulator-metal transitions in perovskites RNiO3 (R=Pr,Nd,Sm,Eu) due to closing of charge-transfer gap
journal, April 1992
- Torrance, J.; Lacorre, P.; Nazzal, A.
- Physical Review B, Vol. 45, Issue 14
Charge Disproportionation in Perovskites: Simultaneous Metal-Insulator and Structural Transition in
journal, May 1999
- Alonso, J. A.; García-Muñoz, J. L.; Fernández-Díaz, M. T.
- Physical Review Letters, Vol. 82, Issue 19
Experimental evidence for bipolaron condensation as a mechanism for the metal-insulator transition in rare-earth nickelates
journal, January 2018
- Shamblin, Jacob; Heres, Maximilian; Zhou, Haidong
- Nature Communications, Vol. 9, Issue 1
Reduction of the perovskite-type LnNiO3 (Ln=Pr, Nd) to Ln3Ni3O7 with monovalent nickel ions
journal, December 1994
- Moriga, T.; Usaka, O.; Nakabayashi, I.
- Solid State Ionics, Vol. 74, Issue 3-4
Complex vs Band Formation in Perovskite Oxides
journal, March 1965
- Goodenough, J. B.; Raccah, P. M.
- Journal of Applied Physics, Vol. 36, Issue 3
Ni 3d – O 2p hybridization dependent magnetic properties of LaNiO3 thin films
journal, November 2016
- Kumar, Yogesh; Singh, Abhinav Pratap; Sharma, S. K.
- Thin Solid Films, Vol. 619
Neutron-diffraction study of the magnetic properties of perovskite-like compounds LaBO3
journal, April 1957
- Koehler, W. C.; Wollan, E. O.
- Journal of Physics and Chemistry of Solids, Vol. 2, Issue 2
Direct Observation of Charge Order in an Epitaxial Film
journal, March 2002
- Staub, U.; Meijer, G. I.; Fauth, F.
- Physical Review Letters, Vol. 88, Issue 12
Antiferromagnetic correlations in the metallic strongly correlated transition metal oxide LaNiO3
journal, January 2018
- Guo, H.; Li, Z. W.; Zhao, L.
- Nature Communications, Vol. 9, Issue 1
Crystal structure and magnetism in the defect perovskite LaNiO2.5
journal, June 1997
- Alonso, J. A.; Martínez-Lope, M. J.; García-Muñoz, J. L.
- Physica B: Condensed Matter, Vol. 234-236
Metal-insulator transition in oxygen-deficient perovskites
journal, December 1996
- Sánchez, R. D.; Causa, M. T.; Caneiro, A.
- Physical Review B, Vol. 54, Issue 23
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
Low-dimensional Mott material: Transport in ultrathin epitaxial LaNiO3 films
journal, February 2010
- Son, Junwoo; Moetakef, Pouya; LeBeau, James M.
- Applied Physics Letters, Vol. 96, Issue 6
Reduced forms of LaNiO 3 perovskite. Part 1.—Evidence for new phases: La 2 Ni 2 O 5 and LaNiO 2
journal, January 1983
- Crespin, Michel; Levitz, Pierre; Gatineau, Lucien
- J. Chem. Soc., Faraday Trans. 2, Vol. 79, Issue 8
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
Interfacial Control of Magnetic Properties at LaMnO 3 /LaNiO 3 Interfaces
journal, October 2015
- Gibert, M.; Viret, M.; Torres-Pardo, A.
- Nano Letters, Vol. 15, Issue 11
Insulating Pockets in Metallic LaNiO 3
journal, November 2015
- Li, Bing; Louca, Despina; Yano, Shinichiro
- Advanced Electronic Materials, Vol. 2, Issue 2
Neutron-diffraction study of R ( R =La,Pr,Nd,Sm): Electronically induced structural changes across the metal-insulator transition
journal, August 1992
- García-Muñoz, J. L.; Rodríguez-Carvajal, J.; Lacorre, P.
- Physical Review B, Vol. 46, Issue 8
Mass enhancement versus Stoner enhancement in strongly correlated metallic perovskites: and
journal, June 2014
- Zhou, J. -S.; Marshall, L. G.; Goodenough, J. B.
- Physical Review B, Vol. 89, Issue 24
Corelli: Efficient single crystal diffraction with elastic discrimination
journal, October 2008
- Rosenkranz, Stephan; Osborn, Raymond
- Pramana, Vol. 71, Issue 4
Bond disproportionation and dynamical charge fluctuations in the perovskite rare-earth nickelates
journal, November 2016
- Green, R. J.; Haverkort, M. W.; Sawatzky, G. A.
- Physical Review B, Vol. 94, Issue 19
Electronic structure and metal-insulator transition in
journal, March 2002
- Abbate, M.; Zampieri, G.; Prado, F.
- Physical Review B, Vol. 65, Issue 15
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
Exchange bias in LaNiO3–LaMnO3 superlattices
journal, January 2012
- Gibert, Marta; Zubko, Pavlo; Scherwitzl, Raoul
- Nature Materials, Vol. 11, Issue 3
A structural and magnetic study of the defect perovskite from high-resolution neutron diffraction data
journal, July 1997
- Alonso, J. A.; Martínez-Lope, M. J.; García-Muñoz, J. L.
- Journal of Physics: Condensed Matter, Vol. 9, Issue 30
XAFS Study on Reduction Process of Pauli-Paramagnetic LaNiO 3 to Antiferromagnetic La 2 Ni 2 O 5
journal, January 1993
- Moriga, Toshihiro; Kikkawa, Shinichi; Takahashi, Masao
- Japanese Journal of Applied Physics, Vol. 32, Issue S2
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
Conductivity enhancement of ultrathin LaNiO3 films in superlattices
journal, November 2010
- Son, Junwoo; LeBeau, James M.; Allen, S. James
- Applied Physics Letters, Vol. 97, Issue 20
Oxygen vacancy ordering in superlatives of the two novel oxides, La2Ni2O5 and La2Co2O5, prepared by low temperature reduction of the parent perovskites
journal, January 1985
- Vidyasagar, Kanamaluru; Reller, Armin; Gopalakrishnan, Jagannatha
- Journal of the Chemical Society, Chemical Communications, Issue 1
High-Pressure Floating-Zone Growth of Perovskite Nickelate LaNiO 3 Single Crystals
journal, April 2017
- Zhang, Junjie; Zheng, Hong; Ren, Yang
- Crystal Growth & Design, Vol. 17, Issue 5
Bond disproportionation and dynamical charge fluctuations in the perovskite rare earth nickelates
text, January 2016
- Green, Robert J.; Haverkort, Maurits W.; Sawatzky, George A.
- arXiv
Spin and charge ordering in self-doped Mott insulators
text, January 1999
- Mizokawa, T.; Khomskii, D. I.; Sawatzky, G. A.
- arXiv
Works referencing / citing this record:
Distortion mode anomalies in bulk : Illustrating the potential of symmetry-adapted distortion mode analysis for the study of phase transitions
journal, November 2019
- Gawryluk, D. J.; Klein, Y. M.; Shang, T.
- Physical Review B, Vol. 100, Issue 20
High pO2 Floating Zone Crystal Growth of the Perovskite Nickelate PrNiO3
journal, June 2019
- Zheng, Hong; Zhang, Junjie; Wang, Bixia
- Crystals, Vol. 9, Issue 7
High pO2 Floating Zone Crystal Growth of the Perovskite Nickelate PrNiO3
text, January 2019
- Zheng, Hong; Zhang, Junjie; Wang, Bixia
- arXiv
Late transition-metal oxides with infinite-layer structure: Nickelates versus cuprates
text, January 2019
- Lechermann, Frank
- arXiv