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Multiferroics

HEMANTH J, (34421017)
M.SC. II-YEAR,
DEPARTMENT OF NUCLEAR PHYSICS,
UNIVERSITY OF MADRAS.
Multiferroic - 2
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Some single phase and composite Multiferroics 4
Outline: 5
 History
 Magnetoelectric effect
 Ferroics
 Multiferroics
 Recipes for multiferroicity
 Case study of BiFeO3
 Applications
 References
History:
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 1888 -Rontgen discovered that moving dielectric became magnetized when
placed in electric field.

 1894 -P. Curie: discussed correlation of magnetic and electric properties in low
symmetry crystals.

 1926 -P. Debye coined the term ‘magneto-electric coupling’.

 1959 -I. E. Dzyaloshinskii: predicted the magnetoelectric effect in

Antiferromagnetic Cr2O3

 1994 -H. Schmid, coined the term ‘multiferroics’

 Magneto-electric effect
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 The magnetoelectric (ME) effect, the appearance of an
electric polarization on applying a magnetic field or by
appearance of magnetization on applying an electric field.

 Materials in which ferromagnetism and ferroelectricity

occur simultaneously in the same phase and allow coupling
between the ferromagnetic and ferroelectric phase.
Ferroic Materials : 8
 Materials which have a spontaneous, switchable internal alignment.

Types of Ferroic Materials :

 Ferro-magnetic Materials

 Ferro-electric Materials

 Ferro-elastic Materials
Types of ferroics based on the properties :
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 Ferro-magnetic Materials - Materials
with a spontaneous magnetization that
can be switched by a applied magnetic
field.

 Ferro-electric Materials - Materials with

a spontaneous electric polarization that
can be switched by an applied electric
field.

 Ferro-elastic materials - Materials with

spontaneous deformation that can be
switched by an applied stress
Primary Ferroics 10
What are Multiferroics ?
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 Multiferroic materials are a special class of solid-state compounds.
 At least two order states such as magnetic, electric or piezo-elastic phases coexist.
 Ferromagnets displaying strong piezo-magnetic, piezo ferroelectrics and special class of
magneto-elastic or electro-elastic coupled multiferroics.
Relation: Magnetoelectric Multiferroic
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 Not all Magnetoelectric are Multiferroics.
 Example : Cr2O3 is a Magnetoelectric antiferromagnet without electric ordering.

 Not all Multiferroics are Magnetoelectric.

 Example : Hexagonal YMnO3 a ferroelectric antiferromagnet in which the
Magnetoelectric effect is forbidden by symmetry.

 All ferroelectric ferromagnets can be Magnetoelectric.

 Example : Ni3B7O13I
Two traditional foes: Ferroelectricity and Magnetism
Ferroelectricity
 Material should be Insulator.
 Noncentrosymmetricity
between cation & anion.
 Transition metal ions with an
empty d shell (like 3d0).
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Magnetism
 Most magnetic materials are
conducting metals.
 Centro-symmetricity
between cation & anion so
that no dipole moment forms.
 For magnetism one needs
partially filled d shells of
Transition metals.
Recipes of Multiferroicity
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 Incorporation of two different cation
 Noncentrosymmetric magnetic ordering
 Geometric ferroelectrics
Incorporation of two different cation:
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 One of which provides the magnetism, the other the ferroelectricity into a single
compound

 For Bismuth ferrite:

Fe3+ Ferromagnetism

Bi3+ Ferroelectricity
Noncentrosymmetric magnetic ordering :
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 This idea was first introduced in the 1970 by Robert Newnham and Coworkers, who
recognized that the noncentrosymmetric, spiral-antiferromagnetic ground state of
Chromium Chrysoberyl (Cr2BeO4) results in a small ferroelectric polarization, even
if the atomic structure itself is centrosymmetric
 A Case Study : Bismuth Ferrite 17

Long known to be both antiferromagnetic – its magnetic moments align in opposing

directions, So that the net magnetization is zero – and ferroelectric, Bismuth ferrite is
multiferroic in the popular use of the term.Since it is readily synthesized in bulk and thin
film forms and both its antiferromagnetic Neel temperature and ferroelectric curie
temperature are well above room temperature, it is undoubtably the most studied
multiferroic today.
 BiFeO3 (BFO) as a Multiferroic Material 18

 Among all the known multiferroics, it is the only one

exhibiting both of its ferroic properties at room temperature.

 Due to High ferroelectric Curie point(TC ~1103K) and Anti

ferromagnetic (AFM) Neel point(TN ~ 647 K ).
 Recently, BFO single crystals are reported to have highest
electric polarization among all the known ferroelectrics.

 Epitaxial BFO thin films are reported to have very high remanent
magnetization (175 emu/cc for films of thickness ~ 70 nm).
 These epitaxial thin films are also found to have
electromagnetic coupling constant as high as 3 V/cm/Oe.
 Crystal structure of BiFeO3
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 In bulk form, it has rhombohedrally distorted perovskite structure
with R3c space group symmetry.
 G type antiferromagnetic structure

 Lattice parameters
Theoretically calculated
a = b = c = 5.63 Å
α = β = γ = 59.35°
Experimentally observed
a = b = c = 5.63 Å
α = β = γ = 60.36°
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Schematic diagram of (001)-oriented BiFeO3 crystal structure and the ferroelectric

polarization (bold arrows) and antiferromagnetic plane (shaded planes)
 Applications
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Spintronic devices

Memories (FeRAMs & MRAMs )

Transducers

Actuators

Detectors

Sensors

Microwave devices
 References
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 J.F.Scott, Nature Materials,6,(256-257),2007
 N.A. Spaldin,Sang-Wook Cheong and R.Ramesh,Review article,Physics Today, October2010
 N. Hill and N.A. Spaldin,Magnetic Materials (Cambridge University Press,
 Cambridge,2003)
 T.Kimura et al.,Nature,426,55 (2003)
 D.I. Khomskii,bull.Am. Phys. Soc. C,21.002 (2001)
 B.Yu et al.,J.Phys. D : Appl. Phys.41(2008)
 Pradhan et al., J.Appl. Phys. 97(2005)
 Zhoo T. et al. ,Nature Materials,5,823(2006)
 M.Fiebig, J.Phys,D:Appl. Phys.38,R123-R152(2005)
 N.A.Hill, J. Phys.chem. B 104 ,6694(2000)
 Mathur N. D.,Nature,442,759-765 (2006)
 I.E. Dzyaloshinskii, JETP 10628(1959)
 D.N. Astrov, JETP 11 708(1960)
 B.D. Cullity, Introduction to Magnetic Materials, Addison-Wesley, Reading
 Massachusetts,(1972)
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