Low-temperature terahertz spectroscopy of LaFeO3, PrFeO3, ErFeO3, and LuFeO3: Quasimagnon resonances and ground-state multiplet transitions

Néstor E. Massa, Leire del Campo, Vinh Ta Phuoc, Paula Kayser, and José Antonio Alonso
Phys. Rev. B 108, 115116 – Published 8 September 2023

Abstract

We report on zone center terahertz excitations of non-Jahn Teller LaFeO3, PrFeO3, ErFeO3, and LuFeO3 distorted perovskites under external magnetic fields up 7 T. Our measurements on low-temperature/low-energy absorptions of LaFeO3 show quasiantiferromagnetic (q-AFM) and quasiferromagnetic (q-FM) magnons at ωqAFM31.4cm1 and ωqFM26.7cm1 in the Γ4(Gx,Ay,Fz) representation with near degeneracy linearly lifted by the field. LuFeO3 is characterized by zero-field magnetic resonances at ωqAFM26.3cm1 and ωqFM22.4cm1 in addition to Fe3+ Zeeman-split crystal field (CF) 6A1 ground transitions at 10.4cm1 triggered by subtle structural deviations induced by the Lu4f14 smaller ionic radius at the A site. This local quasinoncentrosymmetric departure is also found in ErFeO3 (Kramers 4f11 Er3+(I15/24); Γ2(Fx,Cy,Gz)<TSR93K) but with the 4cm1 Fe3+ Zeeman branching strongly biased toward higher energies due to 3d4f exchange. Magnons at ωqAFM31.5cm1 and ωqFM21.5cm1 in ErFeO3 do not undergo field-induced band splits but a 13-fold increase in the q-AFM (ωqAMF)/q-FM (ωqAFM) intensity ratio. There is a remarkable field-dependent CF matching population balance between Fe3+ higher and Er3+ lower Zeeman branches. The Er3+(I15/24) multiplet, at the 49.5, 110.5, and 167.3cm1, coincides with external lattice mode frequencies, suggesting strong lattice-driven spin-phonon interactions. Far-infrared absorption ratios under mild external fields reveal magnetic dependence only for those zone-center phonons involving moving magnetic ions. Overall, our results support the viability of magnetic state manipulation by phonons. Quasiantiferroresonances and quasiferroresonances in PrFeO3 turn much broader as non-Kramers Pr3 introduces ligand changes at the A site, leading into near degeneracy the q-AFM mode and the lowest Pr3+ CF transition. They merge into a single broad mostly unresolved feature at 7 T. We conclude that low-energy excitations in RFeO3 (R=rareearth) strongly depend on the lanthanide ionic size, thus indivisibly tied to the mechanism associated with the origin of canted FM. In addition, minute lattice displacements also underlie considering noncentrosymmetric the most distorted RFeO3 (R=rareearth). In these perovskites, the changes triggered in the lattice by the smaller rare earth and the nonlinear intrinsic oxygen ion polarizability, known to drive lattice instabilities, provide grounds for interplay of ionic and electronic interactions yielding ferroelectric spontaneous polarization.

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  • Received 24 August 2022
  • Revised 3 May 2023
  • Accepted 4 August 2023

DOI:https://doi.org/10.1103/PhysRevB.108.115116

©2023 American Physical Society

Physics Subject Headings (PhySH)

Condensed Matter, Materials & Applied Physics

Authors & Affiliations

Néstor E. Massa1,*, Leire del Campo2, Vinh Ta Phuoc3, Paula Kayser4,†, and José Antonio Alonso5

  • 1Centro CEQUINOR, Consejo Nacional de Investigaciones Científicas y Técnicas, Universidad Nacional de La Plata, Bv. 120 1465, B1904 La Plata, Argentina
  • 2Centre National de la Recherche Scientifique, CEMHTI UPR3079, Université Orléans, F-45071 Orléans, France
  • 3Groupement de Recherche Matériaux Microélectronique Acoustique Nanotechnologies-UMR 7347 CNRS, Université de Tours, INSA CVL, Parc Grandmont F-37200, TOURS, France
  • 4Centre for Science at Extreme Conditions and School of Chemistry, University of Edinburgh, Kings Buildings, Mayfield Road, EH9 3FD Edinburgh, United Kingdom
  • 5Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (CSIC), Cantoblanco, E-28049 Madrid, Spain

  • *neemmassa@gmail.com
  • Present address: Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain.

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Issue

Vol. 108, Iss. 11 — 15 September 2023

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