Separation of K+ and Bi3+ displacements in a Pb-free, monoclinic piezoelectric at the morphotropic phase boundary

T. Wesley Surta; Lynette Keeney; Alicia M. Manjón-Sanz; Catriona Crawford; Alexandra Morscher; Luke M. Daniels; John B. Claridge; Andrew J. Bell; Jonathan Alaria; Matthew J. Rosseinsky

doi:10.1016/j.actamat.2023.119594

Separation of K⁺ and Bi³⁺ displacements in a Pb-free, monoclinic piezoelectric at the morphotropic phase boundary

T. Wesley Surta, Lynette Keeney, Alicia M. Manjón-Sanz, Catriona Crawford, Alexandra Morscher, Luke M. Daniels, John B. Claridge, Andrew J. Bell, Jonathan Alaria, Matthew J. Rosseinsky

Powder Diffraction

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

Abstract

The best piezoelectric properties of any perovskite oxide known are found in the solid solution of the relaxor Pb(Mg_1/3Nb_2/3)O₃ and ferroelectric PbTiO₃. Despite its impressive properties, this system has limited analogy. We present the compositional exploration of the Pb-free analogue (1-x)(K_1/2Bi_1/2)(Mg_1/3Nb_2/3)O₃-x(K_1/2Bi_1/2)TiO₃ (KBMN-KBT). We locate the morphotropic phase boundary between x = 0.86 and 0.88 changing from Cm to Pm symmetry and the optimally performing composition at x = 0.88. We report a piezoelectric figure of merit (d₃₃*) of 192 pm V⁻¹ from strain measurements. Diffraction methods reveal disordered displacements of K⁺ and Bi³⁺ which persist from the KBMN endmember through multiple changes in symmetry. Rearrangement of the Bi³⁺ displacements along the uncommon [011]_c direction drives the physical response. Ferroelectric, dielectric, and piezoresponse force microscopy are used to study the progression of physical properties through the MPB and attribute the mechanism to a polarization rotation. Taking account for local, short-range, and average structural features yield a balanced perspective on the structure and properties of this system, isolating the driving force within this system to the Bi³⁺ bonding configuration. This work yields a strong analogy to the Pb-based analogue, and provides strategies for further optimization.

Original language	English
Article number	119594
Journal	Acta Materialia
Volume	265
DOIs	https://doi.org/10.1016/j.actamat.2023.119594
State	Published - Feb 15 2024

Bibliographical note

Publisher Copyright:
© 2023

Funding

We thank the EPSRC ( EP/R011753 , EP/R010293 , and EP/N004884 ) for funding this research. We would like to thank Alba Synchrotron Light Source (MSPD) for supporting this research. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (IPTS-25965.1 for POWGEN experiment) for supporting this research through their user programmes. This research was partially funded by ASCENT+ Access to European Infrastructure for Nanoelectronics (EU Horizon 2020 Programme Grant No 871130) and the Royal Irish Academy / Royal Society International Exchange Cost-Share Programme 2019. We acknowledge the ICSF Faraday Challenge Project “All-Solid-State Lithium Anode Battery” [Grant No. FIRG026] for funding the studentship of A.M. L.K. would like to thank her support from the Royal Society and Science Foundation Ireland University Fellowship URF\R\201008 . We thank the Leverhulme Trust through the Leverhulme Research Centre for Functional Materials Design ( RC-2015-036 ). We thank the EPSRC (EP/R011753, EP/R010293, and EP/N004884) for funding this research. We would like to thank Alba Synchrotron Light Source (MSPD) for supporting this research. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (IPTS-25965.1 for POWGEN experiment) for supporting this research through their user programmes. This research was partially funded by ASCENT+ Access to European Infrastructure for Nanoelectronics (EU Horizon 2020 Programme Grant No 871130) and the Royal Irish Academy / Royal Society International Exchange Cost-Share Programme 2019. We acknowledge the ICSF Faraday Challenge Project “All-Solid-State Lithium Anode Battery” [Grant No. FIRG026] for funding the studentship of A.M. L.K. would like to thank her support from the Royal Society and Science Foundation Ireland University Fellowship URF\R\201008. We thank the Leverhulme Trust through the Leverhulme Research Centre for Functional Materials Design (RC-2015-036).

Funders	Funder number
ASCENT	871130
Alba Synchrotron Light Source
ICSF Faraday Challenge Project	FIRG026
MSPD
Royal Society and Science Foundation Ireland University	URF\R\201008
Office of Science
Oak Ridge National Laboratory	IPTS-25965.1
Engineering and Physical Sciences Research Council	EP/R011753, EP/N004884, EP/R010293
Leverhulme Trust	RC-2015-036
Royal Irish Academy

Keywords

Ferroelectric
Perovskite oxide
Piezoelectric
Relaxor
Structural analysis

Access to Document

10.1016/j.actamat.2023.119594

Cite this

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title = "Separation of K+ and Bi3+ displacements in a Pb-free, monoclinic piezoelectric at the morphotropic phase boundary",

abstract = "The best piezoelectric properties of any perovskite oxide known are found in the solid solution of the relaxor Pb(Mg1/3Nb2/3)O3 and ferroelectric PbTiO3. Despite its impressive properties, this system has limited analogy. We present the compositional exploration of the Pb-free analogue (1-x)(K1/2Bi1/2)(Mg1/3Nb2/3)O3-x(K1/2Bi1/2)TiO3 (KBMN-KBT). We locate the morphotropic phase boundary between x = 0.86 and 0.88 changing from Cm to Pm symmetry and the optimally performing composition at x = 0.88. We report a piezoelectric figure of merit (d33*) of 192 pm V−1 from strain measurements. Diffraction methods reveal disordered displacements of K+ and Bi3+ which persist from the KBMN endmember through multiple changes in symmetry. Rearrangement of the Bi3+ displacements along the uncommon [011]c direction drives the physical response. Ferroelectric, dielectric, and piezoresponse force microscopy are used to study the progression of physical properties through the MPB and attribute the mechanism to a polarization rotation. Taking account for local, short-range, and average structural features yield a balanced perspective on the structure and properties of this system, isolating the driving force within this system to the Bi3+ bonding configuration. This work yields a strong analogy to the Pb-based analogue, and provides strategies for further optimization.",

keywords = "Ferroelectric, Perovskite oxide, Piezoelectric, Relaxor, Structural analysis",

author = "Surta, {T. Wesley} and Lynette Keeney and Manj{\'o}n-Sanz, {Alicia M.} and Catriona Crawford and Alexandra Morscher and Daniels, {Luke M.} and Claridge, {John B.} and Bell, {Andrew J.} and Jonathan Alaria and Rosseinsky, {Matthew J.}",

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year = "2024",

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doi = "10.1016/j.actamat.2023.119594",

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T1 - Separation of K+ and Bi3+ displacements in a Pb-free, monoclinic piezoelectric at the morphotropic phase boundary

AU - Surta, T. Wesley

AU - Keeney, Lynette

AU - Manjón-Sanz, Alicia M.

AU - Crawford, Catriona

AU - Morscher, Alexandra

AU - Daniels, Luke M.

AU - Claridge, John B.

AU - Bell, Andrew J.

AU - Alaria, Jonathan

AU - Rosseinsky, Matthew J.

PY - 2024/2/15

Y1 - 2024/2/15

N2 - The best piezoelectric properties of any perovskite oxide known are found in the solid solution of the relaxor Pb(Mg1/3Nb2/3)O3 and ferroelectric PbTiO3. Despite its impressive properties, this system has limited analogy. We present the compositional exploration of the Pb-free analogue (1-x)(K1/2Bi1/2)(Mg1/3Nb2/3)O3-x(K1/2Bi1/2)TiO3 (KBMN-KBT). We locate the morphotropic phase boundary between x = 0.86 and 0.88 changing from Cm to Pm symmetry and the optimally performing composition at x = 0.88. We report a piezoelectric figure of merit (d33*) of 192 pm V−1 from strain measurements. Diffraction methods reveal disordered displacements of K+ and Bi3+ which persist from the KBMN endmember through multiple changes in symmetry. Rearrangement of the Bi3+ displacements along the uncommon [011]c direction drives the physical response. Ferroelectric, dielectric, and piezoresponse force microscopy are used to study the progression of physical properties through the MPB and attribute the mechanism to a polarization rotation. Taking account for local, short-range, and average structural features yield a balanced perspective on the structure and properties of this system, isolating the driving force within this system to the Bi3+ bonding configuration. This work yields a strong analogy to the Pb-based analogue, and provides strategies for further optimization.

AB - The best piezoelectric properties of any perovskite oxide known are found in the solid solution of the relaxor Pb(Mg1/3Nb2/3)O3 and ferroelectric PbTiO3. Despite its impressive properties, this system has limited analogy. We present the compositional exploration of the Pb-free analogue (1-x)(K1/2Bi1/2)(Mg1/3Nb2/3)O3-x(K1/2Bi1/2)TiO3 (KBMN-KBT). We locate the morphotropic phase boundary between x = 0.86 and 0.88 changing from Cm to Pm symmetry and the optimally performing composition at x = 0.88. We report a piezoelectric figure of merit (d33*) of 192 pm V−1 from strain measurements. Diffraction methods reveal disordered displacements of K+ and Bi3+ which persist from the KBMN endmember through multiple changes in symmetry. Rearrangement of the Bi3+ displacements along the uncommon [011]c direction drives the physical response. Ferroelectric, dielectric, and piezoresponse force microscopy are used to study the progression of physical properties through the MPB and attribute the mechanism to a polarization rotation. Taking account for local, short-range, and average structural features yield a balanced perspective on the structure and properties of this system, isolating the driving force within this system to the Bi3+ bonding configuration. This work yields a strong analogy to the Pb-based analogue, and provides strategies for further optimization.

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KW - Piezoelectric

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