Sillen-Aurivillius intergrowth phases as templates for naturally layered multiferroics

S. Liu; W. Miiller; Y. Liu; M. Avdeev; C. D. Ling

doi:10.1021/cm302342v

Sillen-Aurivillius intergrowth phases as templates for naturally layered multiferroics

S. Liu^*, W. Miiller, Y. Liu, M. Avdeev, C. D. Ling

^*Corresponding author for this work

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

31 Citations (Scopus)

Abstract

The ferroelectric Sillen-Aurivillius phase Bi ₅PbTi ₃O ₁₄Cl, a layered structure containing three-layer perovskite-type blocks, has been modified by substituting magnetic transition metal cations M ³⁺ = Cr ³⁺, Mn ³⁺, or Fe ³⁺ for ¹/ ₃ of the Ti ⁴⁺ cations, accompanied by co-doping of Bi ³⁺ for Pb ²⁺. The aim of the modification was to produce naturally layered ferroelectromagnetic compounds. Rietveld refinements against high-temperature synchrotron X-ray powder diffraction data show that the resulting new compounds Bi ₆Ti ₂MO ₁₄Cl undergo non-centrosymmetric (P2an) to centrosymmetric (P4/mmm) ferroelectric phase transitions for Bi ₆Ti ₂CrO ₁₄Cl at 974.6(2) K, Bi ₆Ti ₂MnO ₁₄Cl at 913.5(6) K, and Bi ₆Ti ₂FeO ₁₄Cl at 1044.8(1) K. Ferroelectric properties were measured on Bi ₆Ti ₂FeO ₁₄Cl using piezoresponse force microscopy which showed typical ferroelectric hysteresis behavior in the polarization with varying field strength as well as a piezoelectric strain. Combined Rietveld refinements against X-ray and neutron powder diffraction data indicate a statistical 1:2 distribution of M ³⁺ and Ti ⁴⁺ across all three perovskite layers, resulting in highly strained structures (enhancing the ferroelectricity compared to Bi ₅PbTi ₃O ₁₄Cl) and pronounced spin-glass (cluster glass-type) behavior below T _irr(0) = 4.46 K that we have characterized by detailed magnetic susceptibility and heat capacity measurements.

Original language	English
Pages (from-to)	3932-3942
Number of pages	11
Journal	Chemistry of Materials
Volume	24
Issue number	20
DOIs	https://doi.org/10.1021/cm302342v
Publication status	Published - 23 Oct 2012

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@article{6f0bb2ce3b0347f9a97b5cb65ad05834,

title = "Sillen-Aurivillius intergrowth phases as templates for naturally layered multiferroics",

abstract = "The ferroelectric Sillen-Aurivillius phase Bi 5PbTi 3O 14Cl, a layered structure containing three-layer perovskite-type blocks, has been modified by substituting magnetic transition metal cations M 3+ = Cr 3+, Mn 3+, or Fe 3+ for 1/ 3 of the Ti 4+ cations, accompanied by co-doping of Bi 3+ for Pb 2+. The aim of the modification was to produce naturally layered ferroelectromagnetic compounds. Rietveld refinements against high-temperature synchrotron X-ray powder diffraction data show that the resulting new compounds Bi 6Ti 2MO 14Cl undergo non-centrosymmetric (P2an) to centrosymmetric (P4/mmm) ferroelectric phase transitions for Bi 6Ti 2CrO 14Cl at 974.6(2) K, Bi 6Ti 2MnO 14Cl at 913.5(6) K, and Bi 6Ti 2FeO 14Cl at 1044.8(1) K. Ferroelectric properties were measured on Bi 6Ti 2FeO 14Cl using piezoresponse force microscopy which showed typical ferroelectric hysteresis behavior in the polarization with varying field strength as well as a piezoelectric strain. Combined Rietveld refinements against X-ray and neutron powder diffraction data indicate a statistical 1:2 distribution of M 3+ and Ti 4+ across all three perovskite layers, resulting in highly strained structures (enhancing the ferroelectricity compared to Bi 5PbTi 3O 14Cl) and pronounced spin-glass (cluster glass-type) behavior below T irr(0) = 4.46 K that we have characterized by detailed magnetic susceptibility and heat capacity measurements.",

keywords = "Sillen-Aurivillius, cluster-glass, multiferroic, neutron diffraction",

author = "S. Liu and W. Miiller and Y. Liu and M. Avdeev and Ling, {C. D.}",

year = "2012",

month = oct,

day = "23",

doi = "10.1021/cm302342v",

language = "English",

volume = "24",

pages = "3932--3942",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Sillen-Aurivillius intergrowth phases as templates for naturally layered multiferroics

AU - Liu, S.

AU - Miiller, W.

AU - Liu, Y.

AU - Avdeev, M.

AU - Ling, C. D.

PY - 2012/10/23

Y1 - 2012/10/23

N2 - The ferroelectric Sillen-Aurivillius phase Bi 5PbTi 3O 14Cl, a layered structure containing three-layer perovskite-type blocks, has been modified by substituting magnetic transition metal cations M 3+ = Cr 3+, Mn 3+, or Fe 3+ for 1/ 3 of the Ti 4+ cations, accompanied by co-doping of Bi 3+ for Pb 2+. The aim of the modification was to produce naturally layered ferroelectromagnetic compounds. Rietveld refinements against high-temperature synchrotron X-ray powder diffraction data show that the resulting new compounds Bi 6Ti 2MO 14Cl undergo non-centrosymmetric (P2an) to centrosymmetric (P4/mmm) ferroelectric phase transitions for Bi 6Ti 2CrO 14Cl at 974.6(2) K, Bi 6Ti 2MnO 14Cl at 913.5(6) K, and Bi 6Ti 2FeO 14Cl at 1044.8(1) K. Ferroelectric properties were measured on Bi 6Ti 2FeO 14Cl using piezoresponse force microscopy which showed typical ferroelectric hysteresis behavior in the polarization with varying field strength as well as a piezoelectric strain. Combined Rietveld refinements against X-ray and neutron powder diffraction data indicate a statistical 1:2 distribution of M 3+ and Ti 4+ across all three perovskite layers, resulting in highly strained structures (enhancing the ferroelectricity compared to Bi 5PbTi 3O 14Cl) and pronounced spin-glass (cluster glass-type) behavior below T irr(0) = 4.46 K that we have characterized by detailed magnetic susceptibility and heat capacity measurements.

AB - The ferroelectric Sillen-Aurivillius phase Bi 5PbTi 3O 14Cl, a layered structure containing three-layer perovskite-type blocks, has been modified by substituting magnetic transition metal cations M 3+ = Cr 3+, Mn 3+, or Fe 3+ for 1/ 3 of the Ti 4+ cations, accompanied by co-doping of Bi 3+ for Pb 2+. The aim of the modification was to produce naturally layered ferroelectromagnetic compounds. Rietveld refinements against high-temperature synchrotron X-ray powder diffraction data show that the resulting new compounds Bi 6Ti 2MO 14Cl undergo non-centrosymmetric (P2an) to centrosymmetric (P4/mmm) ferroelectric phase transitions for Bi 6Ti 2CrO 14Cl at 974.6(2) K, Bi 6Ti 2MnO 14Cl at 913.5(6) K, and Bi 6Ti 2FeO 14Cl at 1044.8(1) K. Ferroelectric properties were measured on Bi 6Ti 2FeO 14Cl using piezoresponse force microscopy which showed typical ferroelectric hysteresis behavior in the polarization with varying field strength as well as a piezoelectric strain. Combined Rietveld refinements against X-ray and neutron powder diffraction data indicate a statistical 1:2 distribution of M 3+ and Ti 4+ across all three perovskite layers, resulting in highly strained structures (enhancing the ferroelectricity compared to Bi 5PbTi 3O 14Cl) and pronounced spin-glass (cluster glass-type) behavior below T irr(0) = 4.46 K that we have characterized by detailed magnetic susceptibility and heat capacity measurements.

KW - Sillen-Aurivillius

KW - cluster-glass

KW - multiferroic

KW - neutron diffraction

UR - http://www.scopus.com/inward/record.url?scp=84867809578&partnerID=8YFLogxK

U2 - 10.1021/cm302342v

DO - 10.1021/cm302342v

M3 - Article

SN - 0897-4756

VL - 24

SP - 3932

EP - 3942

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 20

ER -

Sillen-Aurivillius intergrowth phases as templates for naturally layered multiferroics

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