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Title: Unconventional Continuous Structural Disorder at the Order-Disorder Phase Transition in the Hexagonal Manganites

Abstract

The improper ferroelectricity in YMnO3 and other related multiferroic hexagonal manganites are known to cause topologically protected ferroelectric domains that give rise to rich and diverse physical phenomena. The local structure and structural coherence across the ferroelectric transition,however, were previously not well understood. Here we reveal the evolution of the local structure with temperature in YMnO3 using neutron total scattering techniques, and interpret them with the help of first-principles calculations and with a first-principles-based effective Hamiltonian. The results show that, at room temperature, the local and average structures are consistent with the established ferroelectric P63cm symmetry. On heating, both local and average structural analyses show striking anomalies from ~800K up to the Curie temperature and signatures of a locally more preserved structure than on average, consistent with increasing fluctuations of the order parameter angle. These fluctuations result in an unusual local symmetry lowering into a continuum of structures on heating. This local symmetry breaking persists into the high-symmetry non-polar phase,constituting an unconventional type of order-disorder transition, and we pinpoint it as the reason for the anomalous behaviour near the phase transition. The hidden disorder revealed in YMnO3 by total scattering is expected to find analogies in other materials with structuralmore » frustration or characteristic energy barriers of different magnitudes.« less

Authors:
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Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1530478
Alternate Identifier(s):
OSTI ID: 1524558
Report Number(s):
BNL-211732-2019-JAAM
Journal ID: ISSN 2160-3308; PRXHAE; 031001
Grant/Contract Number:  
SC0012704
Resource Type:
Published Article
Journal Name:
Physical Review. X
Additional Journal Information:
Journal Name: Physical Review. X Journal Volume: 9 Journal Issue: 3; Journal ID: ISSN 2160-3308
Publisher:
American Physical Society
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Skjærvø, Sandra H., Meier, Quintin N., Feygenson, Mikhail, Spaldin, Nicola A., Billinge, Simon J. L., Bozin, Emil S., and Selbach, Sverre M. Unconventional Continuous Structural Disorder at the Order-Disorder Phase Transition in the Hexagonal Manganites. United States: N. p., 2019. Web. doi:10.1103/PhysRevX.9.031001.
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Skjærvø, Sandra H., Meier, Quintin N., Feygenson, Mikhail, Spaldin, Nicola A., Billinge, Simon J. L., Bozin, Emil S., & Selbach, Sverre M. Unconventional Continuous Structural Disorder at the Order-Disorder Phase Transition in the Hexagonal Manganites. United States. https://doi.org/10.1103/PhysRevX.9.031001
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Skjærvø, Sandra H., Meier, Quintin N., Feygenson, Mikhail, Spaldin, Nicola A., Billinge, Simon J. L., Bozin, Emil S., and Selbach, Sverre M. Mon . "Unconventional Continuous Structural Disorder at the Order-Disorder Phase Transition in the Hexagonal Manganites". United States. https://doi.org/10.1103/PhysRevX.9.031001.
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@article{osti_1530478,
title = {Unconventional Continuous Structural Disorder at the Order-Disorder Phase Transition in the Hexagonal Manganites},
author = {Skjærvø, Sandra H. and Meier, Quintin N. and Feygenson, Mikhail and Spaldin, Nicola A. and Billinge, Simon J. L. and Bozin, Emil S. and Selbach, Sverre M.},
abstractNote = {The improper ferroelectricity in YMnO3 and other related multiferroic hexagonal manganites are known to cause topologically protected ferroelectric domains that give rise to rich and diverse physical phenomena. The local structure and structural coherence across the ferroelectric transition,however, were previously not well understood. Here we reveal the evolution of the local structure with temperature in YMnO3 using neutron total scattering techniques, and interpret them with the help of first-principles calculations and with a first-principles-based effective Hamiltonian. The results show that, at room temperature, the local and average structures are consistent with the established ferroelectric P63cm symmetry. On heating, both local and average structural analyses show striking anomalies from ~800K up to the Curie temperature and signatures of a locally more preserved structure than on average, consistent with increasing fluctuations of the order parameter angle. These fluctuations result in an unusual local symmetry lowering into a continuum of structures on heating. This local symmetry breaking persists into the high-symmetry non-polar phase,constituting an unconventional type of order-disorder transition, and we pinpoint it as the reason for the anomalous behaviour near the phase transition. The hidden disorder revealed in YMnO3 by total scattering is expected to find analogies in other materials with structural frustration or characteristic energy barriers of different magnitudes.},
doi = {10.1103/PhysRevX.9.031001},
journal = {Physical Review. X},
number = 3,
volume = 9,
place = {United States},
year = {Mon Jul 01 00:00:00 EDT 2019},
month = {Mon Jul 01 00:00:00 EDT 2019}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1103/PhysRevX.9.031001
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Cited by: 31 works
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Figures / Tables:

FIG. 1 FIG. 1: Structures of YMnO3 phases. (a) The high-symmetry nonpolar (NP) structure with purple MnO5 bipyramids and turquoise Y cations. Oxygens are shown in red. (b) The Landau free energy of the hexagonal manganites as a function of the two-component order parameter ($\mathcal{Q}$, Φ) resembling a Mexican hat, with themore » NP structure at the top. In the brim of the hat, the polar (P), antipolar (AP), and intermediate (IM) subgroup structures occur at the minima, maxima, and intermediate regions, respectively. (c) Group-subgroup relationship between the high-symmetry nonpolar structure and the subgroup structures found in the brim of the Mexican-hat energy landscape. (d) The order-parameter observables for the polar subgroup are the bipyramidal tilt amplitude (angles αA and αP) and corrugation of Y cations (ΔY). Note that ΔY denotes the distance in the c direction between Y1 and Y2. Green arrows indicate the directions of the bipyramidal tilts. The angle between the O1-O2 line and the c axis defines the apical tilt αA and is a robust measure of the order-parameter amplitude Q irrespective of the value of Φ. The plane through the three in-plane oxygens (one O3 and two O4) relative to the ab plane defines the planar tilt angle αP and is related to both the order-parameter amplitude Q and angle Φ. (e)–(g), Structures of the subgroups at different order-parameter angles Φ: Y off-centering pattern (top) and bipyramidal tilting directions, indicated by green arrows (bottom). Atomic sites for the three subgroups are labeled and coded with colored circles to emphasize which positions are symmetry related in each phase. Atom positions with the same color markings are aligned along the c axis and have the same multiplicity. A detailed overview of the atomic positions for the space groups is given in Fig. S1 of the Supplemental Material [26].« less
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Works referenced in this record:

Dynamical Response of Ferroelectrics in Terms of a Classical Anharmonic-Oscillator Model
journal, May 2004

  • Onodera, Yositaka
  • Journal of the Physical Society of Japan, Vol. 73, Issue 5
  • DOI: 10.1143/JPSJ.73.1216

Goldstone-like phonon modes in a (111)-strained perovskite
journal, January 2018

Epitaxially grown YMnO 3 film: New candidate for nonvolatile memory devices
journal, August 1996

  • Fujimura, Norifumi; Ishida, Tadashi; Yoshimura, Takeshi
  • Applied Physics Letters, Vol. 69, Issue 7
  • DOI: 10.1063/1.117969

Emergence of Long-Range Order in BaTiO 3 from Local Symmetry-Breaking Distortions
journal, May 2016

Order-disorder-order phase transitions in the pyrochlore superconductor Cd 2 Re 2 O 7
journal, June 2005

Dynamic structural disorder in cristobalite: neutron total scattering measurement and reverse Monte Carlo modelling
journal, December 2000

  • Tucker, Matthew G.; Squires, Matthew P.; Dove, Martin T.
  • Journal of Physics: Condensed Matter, Vol. 13, Issue 3
  • DOI: 10.1088/0953-8984/13/3/304

Dielectric spectroscopy of paraelectric soft modes
journal, June 1987

The evolution of multiferroics
journal, July 2016

Collective Magnetism at Multiferroic Vortex Domain Walls
journal, February 2012

  • Geng, Yanan; Lee, N.; Choi, Y. J.
  • Nano Letters, Vol. 12, Issue 12
  • DOI: 10.1021/nl301432z

Coexistence of the Phonon and Relaxation Soft Modes in the Terahertz Dielectric Response of Tetragonal BaTiO 3
journal, October 2008

Partial glass isosymmetry transition in multiferroic hexagonal ErMn O 3
journal, February 2016

Nonlinear optical signatures of the tensor order in Cd2Re2O7 
journal, August 2006

  • Petersen, Jesse C.; Caswell, Michael D.; Dodge, J. Steven
  • Nature Physics, Vol. 2, Issue 9
  • DOI: 10.1038/nphys392

The origin of ferroelectricity in magnetoelectric YMnO3
journal, February 2004

  • Van Aken, Bas B.; Palstra, Thomas T. M.; Filippetti, Alessio
  • Nature Materials, Vol. 3, Issue 3
  • DOI: 10.1038/nmat1080

High-temperature phase transitions of hexagonal YMnO 3
journal, March 2011

Ferroelectric phase transitions in perovskites with off-center ion displacements
journal, August 1997

Insulating interlocked ferroelectric and structural antiphase domain walls in multiferroic YMnO3
journal, February 2010

  • Choi, T.; Horibe, Y.; Yi, H. T.
  • Nature Materials, Vol. 9, Issue 3
  • DOI: 10.1038/nmat2632

Observation of persistent centrosymmetricity in the hexagonal manganite family
journal, May 2012

Anisotropic conductance at improper ferroelectric domain walls
journal, February 2012

  • Meier, D.; Seidel, J.; Cano, A.
  • Nature Materials, Vol. 11, Issue 4
  • DOI: 10.1038/nmat3249

Elastic anomalies associated with structural and magnetic phase transitions in single crystal hexagonal YMnO 3
journal, January 2014

Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
journal, August 1995

γ and β cerium: LDA + U calculations of ground-state parameters
journal, April 2008

Orbital Correlations in the Pseudocubic O and Rhombohedral R Phases of LaMnO 3
journal, May 2005

A brief introduction to the ABINIT software package
journal, January 2005

Hidden order in hexagonal R Mn O 3 multiferroics ( R = Dy –Lu, In, Y, and Sc)
journal, June 2014

Critical Neutron Scattering in SrTi O 3 and KMn F 3
journal, December 1972

Equation of State Calculations by Fast Computing Machines
journal, June 1953

  • Metropolis, Nicholas; Rosenbluth, Arianna W.; Rosenbluth, Marshall N.
  • The Journal of Chemical Physics, Vol. 21, Issue 6
  • DOI: 10.1063/1.1699114

Reconciliation of local and long-range tilt correlations in underdoped La 2 − x Ba x CuO 4 ( 0 ≤ x ≤ 0.155 )
journal, February 2015

Scaling Behavior and Beyond Equilibrium in the Hexagonal Manganites
journal, December 2012

Ferroelectric transition in Y Mn O 3 from first principles
journal, September 2005

Ferroelectricity in the multiferroic hexagonal manganites
journal, September 2015

  • Lilienblum, Martin; Lottermoser, Thomas; Manz, Sebastian
  • Nature Physics, Vol. 11, Issue 12
  • DOI: 10.1038/nphys3468

High-temperature structural evolution of hexagonal multiferroic YMnO 3 and YbMnO 3
journal, July 2007

  • Jeong, Il-Kyoung; Hur, N.; Proffen, Th.
  • Journal of Applied Crystallography, Vol. 40, Issue 4
  • DOI: 10.1107/S0021889807025101

Hexagonal YMnO 3
journal, March 2001

  • Aken, Bas B. van; Meetsma, Auke; Palstra, Thomas T. M.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 57, Issue 3
  • DOI: 10.1107/S0108270100015663

Topological defects as relics of emergent continuous symmetry and Higgs condensation of disorder in ferroelectrics
journal, November 2014

  • Lin, Shi-Zeng; Wang, Xueyun; Kamiya, Yoshitomo
  • Nature Physics, Vol. 10, Issue 12
  • DOI: 10.1038/nphys3142

Pair-distribution functions of ferroelectric perovskites: Direct observation of structural ground states
journal, February 1995

Origin of morphotropic phase boundaries in ferroelectrics
journal, January 2008

  • Ahart, Muhtar; Somayazulu, Maddury; Cohen, R. E.
  • Nature, Vol. 451, Issue 7178
  • DOI: 10.1038/nature06459

Probing Local and Long-Range Structure Simultaneously:  An In Situ Study of the High-Temperature Phase Transition of α-AlF 3
journal, April 2004

  • Chupas, Peter J.; Chaudhuri, Santanu; Hanson, Jonathan C.
  • Journal of the American Chemical Society, Vol. 126, Issue 15
  • DOI: 10.1021/ja031553n

Polarization Rotation via a Monoclinic Phase in the Piezoelectric 92% PbZn 1 / 3 Nb 2 / 3 O 3 -8% PbTiO 3
journal, April 2001

Global Formation of Topological Defects in the Multiferroic Hexagonal Manganites
journal, October 2017

Crystallography and structural phase transitions, an introduction
journal, September 1991

  • Salje, E. K. H.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 47, Issue 5
  • DOI: 10.1107/S0108767391004300

Crystal structure, chemical expansion and phase stability of HoMnO3 at high temperature
journal, December 2012

  • Selbach, Sverre M.; Nordli Løvik, Amund; Bergum, Kristin
  • Journal of Solid State Chemistry, Vol. 196
  • DOI: 10.1016/j.jssc.2012.07.024

Molecular-dynamics study of structural-phase transitions. I. One-component displacement models
journal, February 1976

Improper ferroelectricity and multiferroism in 2 H -BaMnO 3
journal, April 2013

Crystal structure and magnetic properties of hexagonal R MnO 3 ( R = Y , Lu, and Sc) and the effect of doping
journal, October 2002

First-principles computation of material properties: the ABINIT software project
journal, November 2002

Goldstone-Mode Phonon Dynamics in the Pyrochlore Cd 2 Re 2 O 7
journal, September 2005

Experimental evidence for an intermediate phase in the multiferroic YMnO 3
journal, October 2007

The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
journal, September 2012

  • Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287
  • DOI: 10.1016/j.nimb.2012.05.037

Symmetry and coupling of magnetic and electric order parameters in YMnO[sub 3]
journal, January 2002

  • Lottermoser, Th.; Fiebig, M.; Fröhlich, D.
  • Journal of Applied Physics, Vol. 91, Issue 10
  • DOI: 10.1063/1.1448790

Theory of displacive phase transitions in minerals
journal, April 1997

Structural phase transitions. II. Static critical behaviour
journal, February 1980

Momentum-resolved observations of the phonon instability driving geometric improper ferroelectricity in yttrium manganite
journal, January 2018

PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals
journal, July 2007

Functional electronic inversion layers at ferroelectric domain walls
journal, March 2017

  • Mundy, J. A.; Schaab, J.; Kumagai, Y.
  • Nature Materials, Vol. 16, Issue 6
  • DOI: 10.1038/nmat4878

Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992

Measurements and ab initio molecular dynamics simulations of the high temperature ferroelectric transition in hexagonal RMnO 3
journal, October 2011

  • Tyson, T. A.; Wu, T.; Chen, H. Y.
  • Journal of Applied Physics, Vol. 110, Issue 8
  • DOI: 10.1063/1.3656698

Lattice instabilities, isotope effect, and high- T c superconductivity in La 2 − x Ba x CuO 4
journal, July 1991

Landau theory of topological defects in multiferroic hexagonal manganites
journal, October 2013

  • Artyukhin, Sergey; Delaney, Kris T.; Spaldin, Nicola A.
  • Nature Materials, Vol. 13, Issue 1
  • DOI: 10.1038/nmat3786

Domains in ferroelectric YMnO3
journal, June 1967

  • šafránková, M.; Fousek, J.; KiŽaev, S. A.
  • Czechoslovak Journal of Physics, Vol. 17, Issue 6
  • DOI: 10.1007/BF01695179

Crossover between displacive and order/disorder behaviour in the Phi 4 model
journal, May 1992

Electrostatic topology of ferroelectric domains in YMnO3
journal, July 2010

  • Jungk, Tobias; Hoffmann, Ákos; Fiebig, Manfred
  • Applied Physics Letters, Vol. 97, Issue 1
  • DOI: 10.1063/1.3460286

Emergence of central mode in the paraelectric phase of ferroelectric perovskites
journal, February 2013

  • Weerasinghe, Jeevaka; Bellaiche, L.; Ostapchuk, T.
  • MRS Communications, Vol. 3, Issue 1
  • DOI: 10.1557/mrc.2013.5

The crystallography of correlated disorder
journal, May 2015

High-temperature lattice-dynamics evolution of YMn O 3 and YbMn O 3
journal, June 2015

Spin-phonon coupling and high-temperature phase transition in multiferroic material YMnO 3
journal, January 2015

  • Gupta, Mayanak Kumar; Mittal, Ranjan; Zbiri, Mohamed
  • Journal of Materials Chemistry C, Vol. 3, Issue 44
  • DOI: 10.1039/C5TC02096D

Effect of Ga doping on the multiferroic properties of R Mn 1 − x Ga x O 3 ( R = Ho , Y )
journal, December 2005

Implementation of the projector augmented-wave method in the ABINIT code: Application to the study of iron under pressure
journal, April 2008

Unusual ferroelectric and magnetic phases in multiferroic 2 H − BaMnO 3 ceramics
journal, May 2017

Y–O hybridization in the ferroelectric transition of YMnO3
journal, September 2009

  • Kim, Jinyoung; Cho, Kyung Chul; Koo, Yang Mo
  • Applied Physics Letters, Vol. 95, Issue 13
  • DOI: 10.1063/1.3233943
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