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  • Letter
  • Open Access

Magnetic structure of oxygen-deficient perovskite nickelates with ordered vacancies

Yongjin Shin and James M. Rondinelli*

  • Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, USA

  • *jrondinelli@northwestern.edu
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Phys. Rev. Research 4, L022069 – Published 30 June, 2022

DOI: https://doi.org/10.1103/PhysRevResearch.4.L022069

Abstract

The oxygen vacancy concentration in LaNiO3−δ nickelate perovskites affects magnetic interactions and long-range magnetic order through changes in local electronic configurations, crystal field splitting energies, and polyhedral arrangements. Here we use density functional theory calculations to examine the magnetic structure of LaNiO2.5 and LaNiO2.75 with structural ordered oxygen vacancies (OOV). These OOV phases exhibit columnar arrangements of NiO4 square planar units, which adopt low-spin Ni2+ (d8) configurations with nominally zero magnetic moment (S=0), interconnected by NiO6 octahedral units. The magnetic structure of the OOV phases are governed by the flexible charge state of the NiO6 octahedral units, whose density and connectivity depends on the oxygen vacancy concentration. LaNiO2.5 is stable in an insulating A-type antiferromagnetic (AFM) phase derived from octahedral units comprising Ni2+ in AFM chains. LaNiO2.75 is a narrow-gap insulator with zigzag-type AFM order originating from weakly localized electrons in columnar breathing distortions to the NiO6 units. Our results suggest that nanoscale OOV phases within single-phase LaNiO3−δ crystals can account for its reported complex magnetic ground-state structure.

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References (47)

  1. J. B. Torrance, P. Lacorre, A. I. Nazzal, E. J. Ansaldo, and C. Niedermayer, Systematic study of insulator-metal transitions in perovskites RNiO3 (R = Pr, Nd, Sm, Eu) due to closing of charge-transfer gap, Phys. Rev. B 45, 8209 (1992).
  2. J. A. Alonso, J. L. García-Muñoz, M. T. Fernández-Díaz, M. A. G. Aranda, M. J. Martínez-Lope, and M. T. Casais, Charge disproportionation in RNiO3 perovskites: Simultaneous Metal-Insulator and Structural Transition in YNiO3, Phys. Rev. Lett. 82, 3871 (1999).
  3. M. L. Medarde, Structural, magnetic, and electronic properties of R NiO3 perovskites (R = rare earth), J. Phys.: Condens. Matter 9, 1679 (1997).
  4. A. Mercy, J. Bieder, J. Íñiguez, and P. Ghosez, Structurally triggered metal-insulator transition in rare-earth nickelates, Nat. Commun. 8, 1677 (2017).
  5. J. Varignon, M. N. Grisolia, J. Íñiguez, A. Barthélémy, and M. Bibes, Complete phase diagram of rare-earth nickelates from first principles, npj Quantum Mater. 2, 21 (2017).
  6. N. Wagner, D. Puggioni, and J. M. Rondinelli, Learning from correlations based on local structure: Rare-earth nickelates revisited, J. Chem. Inf. Model. 58, 2491 (2018).
  7. S. B. Lee, R. Chen, and L. Balents, Landau Theory of Charge and Spin Ordering in the Nickelates, Phys. Rev. Lett. 106, 016405 (2011).
  8. S. B. Lee, R. Chen, and L. Balents, Metal-insulator transition in a two-band model for the perovskite nickelates, Phys. Rev. B 84, 165119 (2011).
  9. J. Zhang, H. Zheng, Y. Ren, and J. F. Mitchell, High-pressure floating-zone growth of perovskite nickelate LaNiO3 single crystals, Cryst. Growth Des. 17, 2730 (2017).
  10. B.-X. Wang, S. Rosenkranz, X. Rui, J. Zhang, F. Ye, H. Zheng, R. F. Klie, J. F. Mitchell, and D. Phelan, Antiferromagnetic defect structure in LaNiO3−δ single crystals, Phys. Rev. Materials 2, 064404 (2018).
  11. K. Dey, W. Hergett, P. Telang, M. M. Abdel-Hafiez, and R. Klingeler, Magnetic properties of high-pressure optical floating-zone grown LaNiO3 single crystals, J. Cryst. Growth 524, 125157 (2019).
  12. H. Guo, Z. W. Li, L. Zhao, Z. Hu, C. F. Chang, C.-Y. Kuo, W. Schmidt, A. Piovano, T. W. Pi, O. Sobolev, D. I. Khomskii, L. H. Tjeng, and A. C. Komarek, Antiferromagnetic correlations in the metallic strongly correlated transition metal oxide LaNiO3, Nat. Commun. 9, 43 (2018).
  13. T. Moriga, O. Usaka, I. Nakabayashi, T. Kinouchi, S. Kikkawa, and F. Kanamaru, Characterization of oxygen-deficient phases appearing in reduction of the perovskite-type LaNiO3 to La2 Ni2 O5, Solid State Ionics 79, 252 (1995).
  14. R. D. Sánchez, M. T. Causa, A. Caneiro, A. Butera, M. Vallet-Regí, M. J. Sayagués, J. González-Calbet, F. García-Sanz, and J. Rivas, Metal-insulator transition in oxygen-deficient LaNiO3−x perovskites, Phys. Rev. B 54, 16574 (1996).
  15. A. S. Botana and M. R. Norman, Similarities and Differences between LaNiO2 and CaCuO2 and Implications for Superconductivity, Phys. Rev. X 10, 011024 (2020).
  16. D. Li, K. Lee, B. Y. Wang, M. Osada, S. Crossley, H. R. Lee, Y. Cui, Y. Hikita, and H. Y. Hwang, Superconductivity in an infinite-layer nickelate, Nature (London) 572, 624 (2019).
  17. M. Kotiuga, Z. Zhang, J. Li, F. Rodolakis, H. Zhou, R. Sutarto, F. He, Q. Wang, Y. Sun, Y. Wang, N. A. Aghamiri, S. B. Hancock, L. P. Rokhinson, D. P. Landau, Y. Abate, J. W. Freeland, R. Comin, S. Ramanathan, and K. M. Rabe, Carrier localization in perovskite nickelates from oxygen vacancies, Proc. Natl. Acad. Sci. USA 116, 21992 (2019).
  18. D. Misra and T. K. Kundu, Oxygen vacancy induced metal-insulator transition in LaNiO3, Eur. Phys. J. B 89, 4 (2016).
  19. X. Liao, V. Singh, and H. Park, Oxygen vacancy induced site-selective Mott transition in LaNiO3, Phys. Rev. B 103, 085110 (2021).
  20. J. M. González-Calbet, M. J. Sayagués, and M. Vallet-Regí, An electron diffraction study of new phases in the LaNiO3−x system, Solid State Ionics 32-33, 721 (1989).
  21. G. Kresse and J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54, 11169 (1996).
  22. G. Kresse and D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method, Phys. Rev. B 59, 1758 (1999).
  23. J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized Gradient Approximation Made Simple, Phys. Rev. Lett. 77, 3865 (1996).
  24. P. E. Blöchl, Projector augmented-wave method, Phys. Rev. B 50, 17953 (1994).
  25. P. E. Blöchl, O. Jepsen, and O. K. Andersen, Improved tetrahedron method for Brillouin-zone integrations, Phys. Rev. B 49, 16223 (1994).
  26. H. J. Monkhorst and J. D. Pack, Special points for Brillouin-zone integrations, Phys. Rev. B 13, 5188 (1976).
  27. P. Wisesa, K. A. McGill, and T. Mueller, Efficient generation of generalized Monkhorst-Pack grids through the use of informatics, Phys. Rev. B 93, 155109 (2016).
  28. S. L. Dudarev, G. A. Botton, S. Y. Savrasov, C. J. Humphreys, and A. P. Sutton, Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study, Phys. Rev. B 57, 1505 (1998).
  29. A. Hampel and C. Ederer, Interplay between breathing mode distortion and magnetic order in rare-earth nickelates RNiO3 within DFT+U, Phys. Rev. B 96, 165130 (2017).
  30. A. Hampel, P. Liu, C. Franchini, and C. Ederer, Energetics of the coupled electronic-structural transition in the rare-earth nickelates, npj Quantum Mater. 4, 5 (2019).
  31. See Supplemental Material at http://link.aps.org/supplemental/10.1103/PhysRevResearch.4.L022069 for additional computational details including crystal structure information, phonon band structure, and density of states of other derivative structures.
  32. S. Estradé, F. Sánchez, G. Herranz, D. Pesquera, J. M. Rebled, N. Dix, M. J. Casanove, L. López-Conesa, C. Magén, J. Fontcuberta, and F. Peiró, Evidence of a minority monoclinic LaNiO2.5 phase in lanthanum nickelate thin films, Phys. Chem. Chem. Phys. 19, 9137 (2017).
  33. A. Subedi, Breathing distortions in the metallic, antiferromagnetic phase of LaNiO3, SciPost Phys. 5, 020 (2018).
  34. A. Togo, F. Oba, and I. Tanaka, First-principles calculations of the ferroelastic transition between rutile-type and CaCl2-type SiO2 at high pressures, Phys. Rev. B 78, 134106 (2008).
  35. H. T. Stokes, D. M. Hatch, and B. J. Campbell, ISODISTORT, ISOTROPY Software Suite, iso.byu.edu.
  36. B. J. Campbell, H. T. Stokes, D. E. Tanner, and D. M. Hatch, ISODISPLACE: A web-based tool for exploring structural distortions, J. Appl. Crystallogr. 39, 607 (2006).
  37. J. A. Alonso, M. J. MartinezLope, J. L. GarciaMunoz, and M. T. FernandezDiaz, A structural and magnetic study of the defect perovskite LaNiO2.5 from high-resolution neutron diffraction data, J. Phys.: Condens. Matter 9, 6417 (1997).
  38. J. A. J. A. Alonso, M. J. Martinez-lope, and M. J. Martínez-Lope, Preparation and crystal structure of the deficient perovskite LaNiO2.5, solved from neutron powder diffraction data, J. Chem. Soc., Dalton Trans.,2819 (1995).
  39. T. Moriga, O. Usaka, T. Imamura, I. Nakabayashi, I. Matsubara, T. Kinouchi, S. Kikkawa, and F. Kanamaru, Synthesis, crystal structure, and properties of oxygen-deficient lanthanum nickelate LaNiO3−x (0 ≤x≤ 0.5), Bull. Chem. Soc. Jpn. 67, 687 (1994).
  40. A. Malashevich and S. Ismail-Beigi, First-principles study of oxygen-deficient LaNiO3 structures, Phys. Rev. B 92, 144102 (2015).
  41. A. M. Glazer, The classification of tilted octahedra in perovskites, Acta Crystall. Sec. B 28, 3384 (1972).
  42. Y. Matsumoto, T. Yamamoto, K. Nakano, H. Takatsu, T. Murakami, K. Hongo, R. Maezono, H. Ogino, D. Song, C. M. Brown, C. Tassel, and H. Kageyama, High-pressure synthesis of A2 NiO2 Ag2 Se2 (A = Sr, Ba) with a high-spin Ni2+ in square-planar coordination, Angew. Chem., Int. Ed. 58, 756 (2019).
  43. J. B. Goodenough, Magnetism and the Chemical Bond (Interscience Publishers, John Wiley & Sons, 1963).
  44. J. Kanamori, Superexchange interaction and symmetry properties of electron orbitals, J. Phys. Chem. Solids 10, 87 (1959).
  45. I. I. Mazin, D. I. Khomskii, R. Lengsdorf, J. A. Alonso, W. G. Marshall, R. M. Ibberson, A. Podlesnyak, M. J. Martínez-Lope, and M. M. Abd-Elmeguid, Charge Ordering as Alternative to Jahn-Teller Distortion, Phys. Rev. Lett. 98, 176406 (2007).
  46. G. Giovannetti, S. Kumar, D. Khomskii, S. Picozzi, and J. van den Brink, Multiferroicity in Rare-Earth Nickelates R NiO3, Phys. Rev. Lett. 103, 156401 (2009).
  47. B. Li, D. Louca, S. Yano, L. G. Marshall, J. Zhou, and J. B. Goodenough, Insulating pockets in metallic LaNiO3, Adv. Elect. Mat. 2, 1500261 (2016).

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Phys. Rev. Research 4, L022069– Published 30 June, 2022
  • Received 21 April 2022
  • Accepted 3 June 2022
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Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.

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