Revealing Site Occupancy in a Complex Oxide: Terbium Iron Garnet

Ethan Rosenberg; Jackson Bauer; Eunsoo Cho; Abinash Kumar; Jonathan Pelliciari; Connor A. Occhialini; Shuai Ning; Allison Kaczmarek; Richard Rosenberg; John W. Freeland; Yu Chia Chen; Jian Ping Wang; James LeBeau; Riccardo Comin; F. M.F. de Groot; Caroline A. Ross

doi:10.1002/smll.202300824

Revealing Site Occupancy in a Complex Oxide: Terbium Iron Garnet

Ethan Rosenberg^*, Jackson Bauer, Eunsoo Cho, Abinash Kumar, Jonathan Pelliciari, Connor A. Occhialini, Shuai Ning, Allison Kaczmarek, Richard Rosenberg, John W. Freeland, Yu Chia Chen, Jian Ping Wang, James LeBeau, Riccardo Comin, F. M.F. de Groot, Caroline A. Ross^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

Complex oxide films stabilized by epitaxial growth can exhibit large populations of point defects which have important effects on their properties. The site occupancy of pulsed laser-deposited epitaxial terbium iron garnet (TbIG) films with excess terbium (Tb) is analyzed, in which the terbium:iron (Tb:Fe)ratio is 0.86 compared to the stoichiometric value of 0.6. The magnetic properties of the TbIG are sensitive to site occupancy, exhibiting a higher compensation temperature (by 90 K) and a lower Curie temperature (by 40 K) than the bulk Tb₃Fe₅O₁₂ garnet. Data derived from X-ray core-level spectroscopy, magnetometry, and molecular field coefficient modeling are consistent with occupancy of the dodecahedral sites by Tb³⁺, the octahedral sites by Fe³⁺, Tb³⁺ and vacancies, and the tetrahedral sites by Fe³⁺ and vacancies. Energy dispersive X-ray spectroscopy in a scanning transmission electron microscope provides direct evidence of Tb_Fe antisites. A small fraction of Fe²⁺ is present, and oxygen vacancies are inferred to be present to maintain charge neutrality. Variation of the site occupancies provides a path to considerable manipulation of the magnetic properties of epitaxial iron garnet films and other complex oxides, which readily accommodate stoichiometries not found in their bulk counterparts.

Original language	English
Article number	2300824
Journal	Small
Volume	19
Issue number	30
DOIs	https://doi.org/10.1002/smll.202300824
Publication status	Published - 26 Jul 2023

Bibliographical note

Publisher Copyright:
© 2023 Wiley-VCH GmbH.

Funding

The authors acknowledge support from the National Science Foundation awards 1419807, 1808190, and 2128199, and from SMART, an nCORE Center supported by SRC and NIST. Shared facilities of the MRSEC under award NSF 1419807 were used. Work at the Advanced Photon Source was supported by the U.S. Department of Energy, Basic Energy Sciences under Grant no. D‐EAC02‐06CH11357. The authors acknowledge support from the National Science Foundation awards 1419807, 1808190, and 2128199, and from SMART, an nCORE Center supported by SRC and NIST. Shared facilities of the MRSEC under award NSF 1419807 were used. Work at the Advanced Photon Source was supported by the U.S. Department of Energy, Basic Energy Sciences under Grant no. D-EAC02-06CH11357.

Funders	Funder number
National Science Foundation	2128199, 1808190, 1419807
U.S. Department of Energy
Semiconductor Research Corporation
National Institute of Standards and Technology	NSF 1419807
Basic Energy Sciences	D‐EAC02‐06CH11357
Office of Sex Offender Sentencing, Monitoring, Apprehending, Registering, and Tracking

Keywords

complex oxides
defect engineering
epitaxial stabilization
garnets
magnetic thin films

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10.1002/smll.202300824

Small - 2023 - Rosenberg - Revealing Site Occupancy in a Complex Oxide Terbium Iron GarnetFinal published version, 1.56 MBLicence: Taverne

Cite this

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title = "Revealing Site Occupancy in a Complex Oxide: Terbium Iron Garnet",

abstract = "Complex oxide films stabilized by epitaxial growth can exhibit large populations of point defects which have important effects on their properties. The site occupancy of pulsed laser-deposited epitaxial terbium iron garnet (TbIG) films with excess terbium (Tb) is analyzed, in which the terbium:iron (Tb:Fe)ratio is 0.86 compared to the stoichiometric value of 0.6. The magnetic properties of the TbIG are sensitive to site occupancy, exhibiting a higher compensation temperature (by 90 K) and a lower Curie temperature (by 40 K) than the bulk Tb3Fe5O12 garnet. Data derived from X-ray core-level spectroscopy, magnetometry, and molecular field coefficient modeling are consistent with occupancy of the dodecahedral sites by Tb3+, the octahedral sites by Fe3+, Tb3+ and vacancies, and the tetrahedral sites by Fe3+ and vacancies. Energy dispersive X-ray spectroscopy in a scanning transmission electron microscope provides direct evidence of TbFe antisites. A small fraction of Fe2+ is present, and oxygen vacancies are inferred to be present to maintain charge neutrality. Variation of the site occupancies provides a path to considerable manipulation of the magnetic properties of epitaxial iron garnet films and other complex oxides, which readily accommodate stoichiometries not found in their bulk counterparts.",

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author = "Ethan Rosenberg and Jackson Bauer and Eunsoo Cho and Abinash Kumar and Jonathan Pelliciari and Occhialini, {Connor A.} and Shuai Ning and Allison Kaczmarek and Richard Rosenberg and Freeland, {John W.} and Chen, {Yu Chia} and Wang, {Jian Ping} and James LeBeau and Riccardo Comin and {de Groot}, {F. M.F.} and Ross, {Caroline A.}",

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T2 - Terbium Iron Garnet

AU - Rosenberg, Ethan

AU - Bauer, Jackson

AU - Cho, Eunsoo

AU - Kumar, Abinash

AU - Pelliciari, Jonathan

AU - Occhialini, Connor A.

AU - Ning, Shuai

AU - Kaczmarek, Allison

AU - Rosenberg, Richard

AU - Freeland, John W.

AU - Chen, Yu Chia

AU - Wang, Jian Ping

AU - LeBeau, James

AU - Comin, Riccardo

AU - de Groot, F. M.F.

AU - Ross, Caroline A.

PY - 2023/7/26

Y1 - 2023/7/26

N2 - Complex oxide films stabilized by epitaxial growth can exhibit large populations of point defects which have important effects on their properties. The site occupancy of pulsed laser-deposited epitaxial terbium iron garnet (TbIG) films with excess terbium (Tb) is analyzed, in which the terbium:iron (Tb:Fe)ratio is 0.86 compared to the stoichiometric value of 0.6. The magnetic properties of the TbIG are sensitive to site occupancy, exhibiting a higher compensation temperature (by 90 K) and a lower Curie temperature (by 40 K) than the bulk Tb3Fe5O12 garnet. Data derived from X-ray core-level spectroscopy, magnetometry, and molecular field coefficient modeling are consistent with occupancy of the dodecahedral sites by Tb3+, the octahedral sites by Fe3+, Tb3+ and vacancies, and the tetrahedral sites by Fe3+ and vacancies. Energy dispersive X-ray spectroscopy in a scanning transmission electron microscope provides direct evidence of TbFe antisites. A small fraction of Fe2+ is present, and oxygen vacancies are inferred to be present to maintain charge neutrality. Variation of the site occupancies provides a path to considerable manipulation of the magnetic properties of epitaxial iron garnet films and other complex oxides, which readily accommodate stoichiometries not found in their bulk counterparts.

AB - Complex oxide films stabilized by epitaxial growth can exhibit large populations of point defects which have important effects on their properties. The site occupancy of pulsed laser-deposited epitaxial terbium iron garnet (TbIG) films with excess terbium (Tb) is analyzed, in which the terbium:iron (Tb:Fe)ratio is 0.86 compared to the stoichiometric value of 0.6. The magnetic properties of the TbIG are sensitive to site occupancy, exhibiting a higher compensation temperature (by 90 K) and a lower Curie temperature (by 40 K) than the bulk Tb3Fe5O12 garnet. Data derived from X-ray core-level spectroscopy, magnetometry, and molecular field coefficient modeling are consistent with occupancy of the dodecahedral sites by Tb3+, the octahedral sites by Fe3+, Tb3+ and vacancies, and the tetrahedral sites by Fe3+ and vacancies. Energy dispersive X-ray spectroscopy in a scanning transmission electron microscope provides direct evidence of TbFe antisites. A small fraction of Fe2+ is present, and oxygen vacancies are inferred to be present to maintain charge neutrality. Variation of the site occupancies provides a path to considerable manipulation of the magnetic properties of epitaxial iron garnet films and other complex oxides, which readily accommodate stoichiometries not found in their bulk counterparts.

KW - complex oxides

KW - defect engineering

KW - epitaxial stabilization

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ER -

Revealing Site Occupancy in a Complex Oxide: Terbium Iron Garnet

Abstract

Bibliographical note

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Keywords

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