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Ferromagnetic materials
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1.1 Ferromagnets

TERM PAPERS In this material, there are domains in which the magnetic fields of the
individual atoms align, but the orientation of the magnetic fields of the
Add a new page domains is random, giving rise to no net magnetic field. This is illustrated
below.

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A useful property of ferromagnets is that when an external magnetic field is
satyesh vincent xue
yamalia yuan zengmin applied to them, the magnetic fields of the individual domains tend to line up
in the direction of this external field, due to the nature of the magnetic
forces, which causes the external magnetic field to be enhanced. This is
Info illustrated below.

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Historically, the term ferromagnet was used for any material that could
exhibit spontaneous magnetization: a net magnetic moment in the absence
of an external magnetic field. This general definition is still in common use.
More recently, however, different classes of spontaneous magnetization have
been identified when there is more than one magnetic ion per primitive cell
of the material, leading to a stricter definition of "ferromagnetism" that is
often used to distinguish it from ferrimagnetism. In particular, a material is
"ferromagnetic" in this narrower sense only if all of its magnetic ions add a

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positive contribution to the net magnetization. If some of the magnetic ions
subtract from the net magnetization (if they are partially anti-aligned), then
the material is "ferrimagnetic". If the ions anti-align completely so as to have
zero net magnetization, despite the magnetic ordering, then it is an
antiferromagnet. All of these alignment effects only occur at temperatures
below a certain critical temperature, called the Curie temperature (for
ferromagnets and ferrimagnets) or the Nel temperature (for
antiferromagnets).

1.2 Origin of magnetization

The spin of an electron, combined with its orbital angular momentum, results
in a magnetic dipole moment and creates a magnetic field. In many materials
(specifically, those with a filled electron shell), however, the total dipole
moment of all the electrons is zero (i.e., the spins are in up/down pairs).
Only atoms with partially filled shells can experience a net magnetic moment
in the absence of an external field. Ferromagnetic materials contain many
atoms with unpaired spins. When these tiny magnetic dipoles are aligned in
the same direction, they create a measurable macroscopic field.

These permanent dipoles (often called simply "spins" even though they also
generally include orbital angular momentum) tend to align in parallel to an
external magnetic field, an effect called paramagnetism. (A related but much
weaker effect is diamagnetism, due to the orbital motion induced by an
external field, resulting in a dipole moment opposite to the applied field.)
Ferromagnetism involves an additional phenomenon, however, the dipoles
tend to align spontaneously, without any applied field. This is a purely
quantum-mechanical effect.

In a ferromagnet, they tend to align in the same direction because of the

Pauli principle: two electrons with the same spin cannot also have the same
"position", which effectively reduces the energy of their electrostatic
interaction compared to electrons with opposite spin. Mathematically, this is
expressed more precisely in terms of the spin-statistics theorem: because
electrons are fermions with half-integer spin, their wave functions are
antisymmetric under interchange of particle positions. This can be seen in,
for example, the Hartree-Fock approximation to lead to a reduction in the
electrostatic potential energy. This difference in energy is called the
exchange energy.

The exchange interaction is primarily responsible for the ordering of atomic

moments occurring in magnetic solids. The aforementioned interaction
described by classical electromagnetism usually plays only a marginal role.
For instance, in iron (Fe) the exchange interaction between two atoms is
about 1000 times stronger than that classical interaction. There is a small
number "exotic" ferromagnets in which the exchange interactions are
exceptionally weak, and then the classical dipole-dipole interactions may
become the dominant ones. However, such system become ferromagnetic
only at very low temperatures, usually below 1 K. But if the Curie
temperature in a given material is higher than a few Kelvins, then its
ferromagnetism is surely produced by exchange interactions. In such
systems the classical dipole-dipole interactions may only give rise to
secondary effects, e.g., to weak magnetic anisotropy.

1.3 Curie temperature

As we mentioned above, in section 1.2, the very significant dipole alignment

site-name in ferromagnetic
.wikidot.com Share onmaterials is a magnetic ordering due to quantum effects.
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Spin ordering is disrupted by thermal energy:

Ethermal = kB T (1)

where, kB is Boltzmann constant, T is temperature in kelvin.

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As the temperature increases, thermal motion, or entropy, competes with the
ferromagnetic tendency for dipoles to align. When the temperature rises
beyond a certain point, called the Curie temperature Tc, there is a second-
order phase transition and the system can no longer maintain a spontaneous
magnetization, although it still responds paramagnetically to an external
field, i.e. above Tc the spontaneous magnetization due to ferromagnetic
ordering is lost, ferromagnetic ordering is destroyed and the material
behaves paramagnetically. Below that temperature, there is a spontaneous
symmetry breaking and random domains form (in the absence of an external
field). The Curie temperature itself is a critical point, where the magnetic
susceptibility is theoretically infinite and, although there is no net
magnetization, domain-like spin correlations fluctuate at all length scales.

Curie temperatures of some ferromagnetic materials are as follows:

Fe: Tc=1043K
Ni: Tc=627K
Co: Tc=1388K
F eOF e 2 O3 : Tc=858K
N iOF e 2 O3 : Tc=858K
CuOF e 2 O3 : Tc=728K
M gOF e 2 O3 : Tc=713K
MnBi: Tc=630K
MnSb: Tc=587K
M nOF e 2 O3 : Tc=573K
Y3 F e 5 O12 : Tc=560K
CrO2 : Tc=386K
MnAs: Tc=318K
Gd: Tc=292K

1.4 Domain structure

In ferromagnetic materials, small regions with a particular overall spin

orientation are termed domains. This strong (large) spin alignment leads to
huge permeabilities:

Material Relative Permeability r

Nickel 250
Cobalt 600
Iron (pure) 4,000
compare to paramagnetic metal:
Aluminium 1

At long distances (after many thousands of ions), the exchange energy

advantage is overtaken by the classical tendency of dipoles to anti-align. This
is why, in an equilibriated (non-magnetized) ferromagnetic material, the
dipoles in the whole material are not aligned. Rather, they organize into
magnetic domains (also known as Weiss domains) that are aligned
(magnetized) at short range, but at long range adjacent domains are anti-
aligned.[3] The boundary between two domains, where the magnetization
flips, is called a domain wall (i.e., a Bloch/Nel wall, depending upon whether
the magnetization rotates parallel/perpendicular to the domain interface) and
is a gradual transition on the atomic scale (covering a distance of about 300
ions for iron).[2]

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1.5 Hysteresis

When a ferromagnetic material is magnetized in one direction, it will not

relax back to zero magnetization when the imposed magnetizing field is
removed. It must be driven back to zero by a field in the opposite direction.
If an alternating magnetic field is applied to the material, its magnetization
will trace out a loop called a hysteresis loop. The lack of retraceability of the
magnetization curve is the property called hysteresis and it is related to the
existence of magnetic domains in the material. Once the magnetic domains
are reoriented, it takes some energy to turn them back again. This property
of ferrromagnetic materials is useful as a magnetic "memory". Some
compositions of ferromagnetic materials will retain an imposed magnetization
indefinitely and are useful as "permanent magnets". The magnetic memory
aspects of iron and chromium oxides make them useful in audio tape
recording and for the magnetic storage of data on computer disks.

The magnetic field within an unmagnetized piece of steel is zero. As the

magnetizing force (H) is increased from zero, the flux density (B) within the
part will also increase from zero. The curve from points A to E in Figure
above illustrates this behavior. In the region of point E, the flux density
increases up to a point and then tends to level off; this condition is called
magnetic saturation and for a magnetically saturated ferromagnetic material,
the relative permeability (m) is approximately equal to 1. When the
magnetizing force is reduced to zero the flux density does not return to zero.
Instead, the flux density returns to a value shown at point F in Figure above.

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This is the amount of residual magnetism resulting from the applied
magnetizing force (H) that reached the point E in the hysteresis curve. As the
magnetizing force (H) is increased from zero in the opposite direction, the
flux density (B) will decrease to zero, as shown at point G in Figure above,
and then start to increase to point I. The magnetizing force (H) represented
by the distance OG on the H axis in Figure above is called the coercive force.
It represents the strength of the magnetizing force (H) required to reduce
the flux density (B) to zero in a saturated ferromagnetic material. A further
increase in the magnetizing force (H) to the point I results in saturation of
the material in a direction opposite to that represented by point E. Reduction
of the magnetizing force (H) to zero from point I will reduce the flux density
(B) to the value represented by point J. Application of a magnetizing force
(H) in the original direction will change the flux density (B) as shown in the
portion JK of the hysteresis curve. Increasing the magnetizing force (H)
sufficiently will return the material to saturation as illustrated at point E.

1.6 Application

An area where ferromagnetic materials are employed is in magnetic

recording devices, such as for cassette tapes, floppy discs for computers, and
the magnetic stripe on the back of credit cards. These devices essentially
take information in the form of electrical signals and permanently encode it
into a magnetic material. The way this is done is illustrated below.

As an (AC) electrical signal passes through the wire loop, a magnetic field is
produced which passes through the ferromagnetic core, which in turn
produces a magnetic field in the vicinity of a moving magnetic tape. This
magnetic field aligns the magnets of atoms on the tape that happen to be
passing by it at that instant. A short time later the direction of the current
reverses, which reverses the direction of the magnetic field, which
subsequently reverses the orientation of the next atom on the tape which
passes by. In this way information stored in the electrical signal is encoded in
a particular orientation of the magnetic fields of individual atoms.[4]

There are also many applications, like Magnetic Response Of Ferromagnetic

Semiconductor[3] etc.

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Under certain conditions, two-dimensional electron systems in strong

magnetic field behave as quantum Hall ferromagnets. These unusual
ferromagnets have the novel property that the local magnetic vorticity (or
Skyrmion density) is directly related to the physical charge density. In view
of this vorticity/charge equivalence, electrical potentials couple directly to the
magnetic vorticity.

Within the present context, a Skyrmion is a configuration of a two-

dimensional ferromagnet which has a non-trivial global topological structure
(this Skyrmion configuration cannot be deformed into the magnetic
groundstate, in which all spins are aligned, by a smooth or continuous
process). The importance of Skyrmions for quantum Hall systems arises from
the discovery (based on both theoretical and experimental evidence) that
they describe the lowest-energy charged excitations of quantum Hall
ferromagnets, and therefore dominate many of the low-temperature
properties of these systems.[5]

1.7 Coupling of Ferromagnetics and FerroelectricsMultiferroics

The term multiferroic was first used by H. Schmid in 1994. His definition
referred to multiferroics as single phase materials which simultaneously
possess two or more primary ferroic properties. [7]

Multiferroic materials simultaneously show ferromagnetism and

ferroelectricity. They hold great potential for applications as the multiferroic
coupling allows switching of the ferroelectric state with a magnetic field and
vice versa. They could lead to a new generation of memory devices that can
be electrically written and magnetically read.

The multiferroics offer the possibility of combining the best qualities of

ferroelectric random access memories (FeRAMs) and magnetic random
access memories (MRAMs): fast low-power electrical write operation, and
non-destructive magnetic read operation. At the 256 Mbit level, such

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memory devices, would be a disruptive technology [15]and could eliminate

competition such as EEPROMs (electrically erasable programmable read-only
memories) for applications including megapixel photo memories for digital
cameras or audio memories in devices such as mp3 players.[16]

Typical multiferroics belong to the group of the perovskite transition metal

oxides, and include rare-earth manganites and -ferrites (e.g. TbMnO3,
HoMn2O5, LuFe2O4). Other examples are the bismuth alloys BiFeO3 and
BiMnO3, and non-oxides such as BaNiF4 and spinel chalcogenides, e.g.
ZnCr2Se4. These alloys show rich phase diagrams combining different ferroic
orders in separate phases. Apart from single phase multiferroics, composites
and heterostructures exhibiting more than one ferroic order parameter are
studied extensively. Some examples include magnetic thin films on
piezoelectric PMN-PT substrates and Metglass/PVDF/Metglass trilayer
structures. Besides scientific interest in their physical properties, multiferroics
have potential for applications as actuators, switches, magnetic field sensors
or new types of electronic memory devices.

For thin-film multiferroics, there are three types of thin-film architectures:

single-phase thin films, in which heteroepitaxial strain and crystal chemistry
are the key variables in controlling and improving magnetoelectric coupling;
horizontal heterostructures, in which the principles of heteroepitaxy at the
interfaces can be used to control and initiate magnetoelectric coupling at the
atomic scale; and nanoscale vertical heterostructures, in which coupling
occurs through vertical heteroepitaxy.[8]

(a) Single-component thin-film multiferroics

Perovskite-structure bismuth ferrite is currently the most studied single-

component multiferroic, in part because its large
polarization and high Curie temperature (~820 C) make it appealing for
applications in ferroelectric non-volatile memories and hightemperature
electronics. Measured polarizations for thin films grown by a variety of
techniques[9-12] initially showed a large spread of values. However, the
measured values are now converging to ~90 C cm2 along the [111]
direction of the pseudo-cubic perovskite unit cell, consistent with first-
principles calculations[14]. The large difference between the thin-film and
bulk values, initially attributed to epitaxial strain, could also result from
leakage effects in crystals caused by defect chemistry or the existence of
second phases, or mechanical constraints in granular bulk ceramics.

(b) Horizontal multilayer heterostructures

Several interesting interfacial magnetoelectric effects have been proposed

theoretically and are particularly exciting areas for future experimental study.
First-principles density functional theory is used to demonstrate a
magnetoelectric effect in a ferromagnetic/ferroelectric heterostructure that
arises from a purely electronic mechanism, not mediated by strain. It is
shown that the displacement of atoms at the interface due to the ferroelectric
instability changes the overlap between atomic orbitals at the interface,
which in turn influences the magnetization of the magnetic layer resulting in
a magnetoelectric effect. In addition, first-principles calculations of metal
insulator heterostructures in the presence of a finite electric field show that a
polarized dielectric induces an electric polarization in the adjacent metal; if

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the metal is ferromagnetic, a region of coexisting electrical polarization and

magnetization will be produced at the interface.

(c) Vertical heterostructures

Vertical heterostructures have a larger interfacial surface area and are

intrinsically heteroepitaxial in three dimensions; this allow for stronger
coupling between ferroelectric and magnetic components. In addition, the 2D
clamping of the thin film on the substrate, suppress both the piezoelectric
response and the magnetoelectric coupling. Recent work has demonstrated
very strong magnetoelectric coupling in such nanostructures, through
switching of the magnetization on reversal of the ferroelectric
polarization[13].

The figure above is magnetic force microscopy image of thin-film multiferroic

nanostructures. The coupling of magnetic and ferroelectric materials make
them have many potential applications, such as filters and oscillators, and
electrically tuneable microwave. Coupling in the case of magnetic field
sensorsis results from the macroscopic mechanical coupling of the two
materials at the bonded interface. The crystallographic orientation control
play an important role in optimizing the magnetoelectric response.

1.8 References
[1] Richard M. Bozorth, Ferromagnetism, first published 1951, reprinted
1993 by IEEE Press, New York as a "Classic Reissue." ISBN 0-7803-1032-2.
[2] http://en.wikipedia.org/wiki/Ferromagnetism
[3] ScienceDaily (Mar. 11, 2009)
[4] http://theory.uwinnipeg.ca
[5] Information from Theory of Condensed Matter group, University of
Cambridge.
[6] http://www.phys.unsw.edu.au
[7] http://en.wikipedia.org/wiki/Multiferroics
[8] R. Ramesh and Nicola A. Spaldin, Nature Materials 6, 21 (2007)
[9] Wang, J. et al. Epitaxial BiFeO3 multiferroic thin fi lm heterostructures.
Science 299, 1719 (2003).
[10] Li, J. et al. Dramatically enhanced polarization in (001), (101), and
(111) BiFeO3 thin fi lms due to
epitaxial-induced transitions. Appl. Phys. Lett. 84, 52615263 (2004).
[11] Qi, X. et al. Epitaxial growth of BiFeO3 thin fi lms by LPE and sol-gel
methods. J. Magn. Magn. Mater. 283, 415421 (2004).
[12] Qi, X., Dho, J., Tomov, R., Blamire, M. G. & MacManus-Dricoll, J. L.
Greatly reduced leakage current and conduction mechanism in aliovalent-ion-
doped BiFeO3. Appl. Phys. Lett. 86, 062903 (2005).
[13] Zavaliche, F. et al. Electric fi eld-induced magnetization switching in
epitaxial columnar nanostructures. Nano Lett. 5, 17931796 (2005).
[14] Neaton, J. B., Ederer, C., Waghmare, U. V., Spaldin, N. A. & Rabe, K. M.
First-principles study of spontaneous polarization in multiferroic BiFeO3.

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Phys. Rev. B 71, 014113 (2005).
[15] Christensen, C. M. Th e Innovators Dilemma (Harvard Business School
Press, Boston, 1997).
[16] J. F. Scott, Nature Materials 6, 256 (2007)

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