Structure-property trends in a hollandite multiferroic by Fe doping: Structural, magnetic and dielectric characterization of nanocrystalline BaMn3-: XFexTi4O14+ δ

Frederick Pearsall; Frederick Pearsall; Frederick Pearsall; Nasim Farahmand; Nasim Farahmand; Nasim Farahmand; Julien Lombardi; Julien Lombardi; Julien Lombardi; Sunil Dehipawala; Zheng Gai; Stephen O'Brien; Stephen O'Brien; Stephen O'Brien

doi:10.1039/d0tc00703j

Structure-property trends in a hollandite multiferroic by Fe doping: Structural, magnetic and dielectric characterization of nanocrystalline BaMn_{3-: X}Fe_xTi₄O_{14+ δ}

Frederick Pearsall, Frederick Pearsall, Frederick Pearsall, Nasim Farahmand, Nasim Farahmand, Nasim Farahmand, Julien Lombardi, Julien Lombardi, Julien Lombardi, Sunil Dehipawala, Zheng Gai, Stephen O'Brien, Stephen O'Brien, Stephen O'Brien

Scanning Tunneling Microscopy Group

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3 Scopus citations

Abstract

BaMn3Ti4O14+δ (δ = 0.25, BMT-134), a recently discovered single-phase multiferroic complex oxide was doped with varying concentrations of Fe in order to assess the effect on magnetic and dielectric behavior. The novel compound BaMn3-xFexTi4O14+δ (BMFT) was prepared via a sol-gel chemical solution processing method. Four substituted variations were synthesized: BaMn3-xFexTi4O14+δ (BMFT) with x = 1, 1.5, 2, and 2.25. The approach afforded a nanocrystalline product, with control over structure and morphology, while successfully allowing increasing amounts of iron to be incorporated into the structure. All variants belong to the same hollandite I4/m crystal class as the parent compound, confirmed by powder XRD. Electron microscopy (TEM, EDS and SEM) provided characterization of the microstructure and elemental composition. Mössbauer spectroscopy was used to probe the local chemical environment of Fe present within the nanocrystals, to indicate oxidation state and bonding geometry. The BMFT material system was characterized as a function of temperature and applied magnetic field: M-T and M-H curves were obtained (by MPMS) and allowed the determination of Curie/Weiss constants through fitting and low temperature hysteresis respectively. The Weiss constant becomes increasingly positive as Fe is added until an observed inflection point, indicative of an antiferromagnetic to paramagnetic short-range interaction transition. The frequency dependent dielectric permittivity of the series of BMFT compounds with differing Fe concentration, was obtained on MIM structures prepared from pressed pellets with a nanostructured morphology. The results show how Fe concentration can strongly influence dielectric behavior. Dielectric constants ranging from 100-1600 (low frequencies) to 150-200 (high frequencies) were observed, together with a decrease in the AC conductivity with increasing Fe.

Original language	English
Pages (from-to)	7916-7927
Number of pages	12
Journal	Journal of Materials Chemistry C
Volume	8
Issue number	23
DOIs	https://doi.org/10.1039/d0tc00703j
State	Published - Jun 21 2020

Funding

This work was supported by the National Science Foundation, under NSF DMR award #1461499, and with an additional support from NSF CREST #1547830. SO and FP are grateful to AGEP award supplements NSF DMR #1719250 and #1831127, on behalf of FP. FP and SO are grateful to Dr Jun Ouyang and Dr Jackie Li for useful discussions regarding dielectric behavior, and to Dr Jon Owen for useful discussions in general. FP and JL are grateful to Jorge Morales for help with the EM. All magnetic characterization was conducted at the Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, which is a DOE Office of Science User Facility (supported under project number CNMS2017-211). SO and NF thank Ioannis Kymissis and Christine McGinn for assistance with the impedance data.

Funders	Funder number
DOE Office of Science	CNMS2017-211
National Science Foundation	1547830, 1461499
Oak Ridge National Laboratory

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Pearsall, F., Pearsall, F., Pearsall, F., Farahmand, N., Farahmand, N., Farahmand, N., Lombardi, J., Lombardi, J., Lombardi, J., Dehipawala, S., Gai, Z., O'Brien, S., O'Brien, S., & O'Brien, S. (2020). Structure-property trends in a hollandite multiferroic by Fe doping: Structural, magnetic and dielectric characterization of nanocrystalline BaMn_{3-: X}Fe_xTi₄O_{14+ δ}. Journal of Materials Chemistry C, 8(23), 7916-7927. https://doi.org/10.1039/d0tc00703j

@article{bcc7522756e84e9fa827bf9753114fee,

title = "Structure-property trends in a hollandite multiferroic by Fe doping: Structural, magnetic and dielectric characterization of nanocrystalline BaMn3-: XFexTi4O14+ δ",

abstract = "BaMn3Ti4O14+δ (δ = 0.25, BMT-134), a recently discovered single-phase multiferroic complex oxide was doped with varying concentrations of Fe in order to assess the effect on magnetic and dielectric behavior. The novel compound BaMn3-xFexTi4O14+δ (BMFT) was prepared via a sol-gel chemical solution processing method. Four substituted variations were synthesized: BaMn3-xFexTi4O14+δ (BMFT) with x = 1, 1.5, 2, and 2.25. The approach afforded a nanocrystalline product, with control over structure and morphology, while successfully allowing increasing amounts of iron to be incorporated into the structure. All variants belong to the same hollandite I4/m crystal class as the parent compound, confirmed by powder XRD. Electron microscopy (TEM, EDS and SEM) provided characterization of the microstructure and elemental composition. M{\"o}ssbauer spectroscopy was used to probe the local chemical environment of Fe present within the nanocrystals, to indicate oxidation state and bonding geometry. The BMFT material system was characterized as a function of temperature and applied magnetic field: M-T and M-H curves were obtained (by MPMS) and allowed the determination of Curie/Weiss constants through fitting and low temperature hysteresis respectively. The Weiss constant becomes increasingly positive as Fe is added until an observed inflection point, indicative of an antiferromagnetic to paramagnetic short-range interaction transition. The frequency dependent dielectric permittivity of the series of BMFT compounds with differing Fe concentration, was obtained on MIM structures prepared from pressed pellets with a nanostructured morphology. The results show how Fe concentration can strongly influence dielectric behavior. Dielectric constants ranging from 100-1600 (low frequencies) to 150-200 (high frequencies) were observed, together with a decrease in the AC conductivity with increasing Fe.",

author = "Frederick Pearsall and Frederick Pearsall and Frederick Pearsall and Nasim Farahmand and Nasim Farahmand and Nasim Farahmand and Julien Lombardi and Julien Lombardi and Julien Lombardi and Sunil Dehipawala and Zheng Gai and Stephen O'Brien and Stephen O'Brien and Stephen O'Brien",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",

year = "2020",

month = jun,

day = "21",

doi = "10.1039/d0tc00703j",

language = "English",

volume = "8",

pages = "7916--7927",

journal = "Journal of Materials Chemistry C",

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publisher = "Royal Society of Chemistry",

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Pearsall, F, Pearsall, F, Pearsall, F, Farahmand, N, Farahmand, N, Farahmand, N, Lombardi, J, Lombardi, J, Lombardi, J, Dehipawala, S, Gai, Z, O'Brien, S, O'Brien, S & O'Brien, S 2020, 'Structure-property trends in a hollandite multiferroic by Fe doping: Structural, magnetic and dielectric characterization of nanocrystalline BaMn_{3-: X}Fe_xTi₄O_{14+ δ}', Journal of Materials Chemistry C, vol. 8, no. 23, pp. 7916-7927. https://doi.org/10.1039/d0tc00703j

Structure-property trends in a hollandite multiferroic by Fe doping: Structural, magnetic and dielectric characterization of nanocrystalline BaMn_{3-: X}Fe_xTi₄O_{14+ δ}. / Pearsall, Frederick; Pearsall, Frederick; Pearsall, Frederick et al.
In: Journal of Materials Chemistry C, Vol. 8, No. 23, 21.06.2020, p. 7916-7927.

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

TY - JOUR

T1 - Structure-property trends in a hollandite multiferroic by Fe doping

T2 - Structural, magnetic and dielectric characterization of nanocrystalline BaMn3-: XFexTi4O14+ δ

AU - Pearsall, Frederick

AU - Farahmand, Nasim

AU - Lombardi, Julien

AU - Dehipawala, Sunil

AU - Gai, Zheng

AU - O'Brien, Stephen

PY - 2020/6/21

Y1 - 2020/6/21

N2 - BaMn3Ti4O14+δ (δ = 0.25, BMT-134), a recently discovered single-phase multiferroic complex oxide was doped with varying concentrations of Fe in order to assess the effect on magnetic and dielectric behavior. The novel compound BaMn3-xFexTi4O14+δ (BMFT) was prepared via a sol-gel chemical solution processing method. Four substituted variations were synthesized: BaMn3-xFexTi4O14+δ (BMFT) with x = 1, 1.5, 2, and 2.25. The approach afforded a nanocrystalline product, with control over structure and morphology, while successfully allowing increasing amounts of iron to be incorporated into the structure. All variants belong to the same hollandite I4/m crystal class as the parent compound, confirmed by powder XRD. Electron microscopy (TEM, EDS and SEM) provided characterization of the microstructure and elemental composition. Mössbauer spectroscopy was used to probe the local chemical environment of Fe present within the nanocrystals, to indicate oxidation state and bonding geometry. The BMFT material system was characterized as a function of temperature and applied magnetic field: M-T and M-H curves were obtained (by MPMS) and allowed the determination of Curie/Weiss constants through fitting and low temperature hysteresis respectively. The Weiss constant becomes increasingly positive as Fe is added until an observed inflection point, indicative of an antiferromagnetic to paramagnetic short-range interaction transition. The frequency dependent dielectric permittivity of the series of BMFT compounds with differing Fe concentration, was obtained on MIM structures prepared from pressed pellets with a nanostructured morphology. The results show how Fe concentration can strongly influence dielectric behavior. Dielectric constants ranging from 100-1600 (low frequencies) to 150-200 (high frequencies) were observed, together with a decrease in the AC conductivity with increasing Fe.

AB - BaMn3Ti4O14+δ (δ = 0.25, BMT-134), a recently discovered single-phase multiferroic complex oxide was doped with varying concentrations of Fe in order to assess the effect on magnetic and dielectric behavior. The novel compound BaMn3-xFexTi4O14+δ (BMFT) was prepared via a sol-gel chemical solution processing method. Four substituted variations were synthesized: BaMn3-xFexTi4O14+δ (BMFT) with x = 1, 1.5, 2, and 2.25. The approach afforded a nanocrystalline product, with control over structure and morphology, while successfully allowing increasing amounts of iron to be incorporated into the structure. All variants belong to the same hollandite I4/m crystal class as the parent compound, confirmed by powder XRD. Electron microscopy (TEM, EDS and SEM) provided characterization of the microstructure and elemental composition. Mössbauer spectroscopy was used to probe the local chemical environment of Fe present within the nanocrystals, to indicate oxidation state and bonding geometry. The BMFT material system was characterized as a function of temperature and applied magnetic field: M-T and M-H curves were obtained (by MPMS) and allowed the determination of Curie/Weiss constants through fitting and low temperature hysteresis respectively. The Weiss constant becomes increasingly positive as Fe is added until an observed inflection point, indicative of an antiferromagnetic to paramagnetic short-range interaction transition. The frequency dependent dielectric permittivity of the series of BMFT compounds with differing Fe concentration, was obtained on MIM structures prepared from pressed pellets with a nanostructured morphology. The results show how Fe concentration can strongly influence dielectric behavior. Dielectric constants ranging from 100-1600 (low frequencies) to 150-200 (high frequencies) were observed, together with a decrease in the AC conductivity with increasing Fe.

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U2 - 10.1039/d0tc00703j

DO - 10.1039/d0tc00703j

M3 - Article

AN - SCOPUS:85086887607

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JO - Journal of Materials Chemistry C

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ER -

Structure-property trends in a hollandite multiferroic by Fe doping: Structural, magnetic and dielectric characterization of nanocrystalline BaMn_{3-: X}Fe_xTi₄O_{14+ δ}

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