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Magnetism in Nanomaterials: Principles of Nanomagnetism
Magnetism in Nanomaterials: Principles of Nanomagnetism
Advanced Reading
Principles of Nanomagnetism
A.P. Guimarães
Springer-Verlag, Berlin, 2009.
Introduction to Magnetism
Magnetism is virtually universal.
Coherent magnetic fields have been found at the scale of the galaxies and cluster
of galaxies. (1-3 G)
Earth's magnetic field has a strength of about 1 G and reverses itself with an
average period of about 2105 years.
Magnetic nanoparticles are found in some rocks and can be used to determine the
earth's magnetic field (strength and direction) in the past.
Magnetotactic bacteria have nanometer-sized magnets, which they use for
alignment with the earth's magnetic field.
Many birds (e.g. the homing pigeon) and other living creatures have clusters of
nanoparticles (~2-4 nm in the pigeon) in their beak area, which helps them with
their homing ability.
Macroscopic Microscopic
(Charge currents) (Atomic scale)
If a loop of area A is carrying a current I, the intrinsic intensity of the magnetic field is
given by the magnetic moment vector (m or ) directed from the north pole to the south
pole; such that the magnitude of m is given by: m = IA (units: [Am2]).
The magnetic moment is the measure of the strength of the magnet and is the ability to
produce (and be affected by) a magnetic field.
Magnetic induction/Magnetic flux density (B) = Magnetic flux per unit area. Units:
[Tesla = Weber/m2 = Vs/m2 = Kg/s2/A]
B is the magnetic flux density inside the material.
B = 0 (H + M) (0 is the magnetic permeability of vacuum
= H/m = Wb/A/m = mKg/s2A2)
Permeability ().Units: [dimensionless]
B
H
Magnetic anisotropy
Anisotropy means that various directions in the crystals are non-equivalent with
respect magnetization (M) and this implies that M may not be in the same direction
of the applied field. There are many contributions to this anisotropy as we shall see
later, crystalline (magneto-crystalline) anisotropy being the prominent one.
Atomic origin of magnetic moments
Origin of Magnetism
This is classical way of looking
Due to Electrons
at a quantum effect !
Spin of the nucleus Orbital motion of electrons Spin of electrons
Small effect
i) Nuclear spin (which is slow and has a small contribution to the overall magnetic effect)
Note: at very low temperatures magnetism due to nuclear spin may become important
The magnetic moment due to spin is equal to the magnetic moment due to orbital
motion (in the first Bohr orbit) and is approximately expressed in terms of the Bohr magneton
(B):
eh
mB B 9.27 1024 Am 2
4 m
Understanding magnetism (and formulating theories) to understand the effects observed:
Direct coupling → Moments (spin, orbital motion, nuclear) localized to an atom and their
direct interaction with moments in neighbouring atoms
Mediated interaction →Moments (magnetism) arising from itinerant electrons in the bands
of metals (with the possibility of mediation of interaction via free electrons).
Superexchange → Local magnetic moments interacting with other local moments via the
mediation of non-magnetic elements (super-exchange) e.g. antiferromagnetism in MnO.
Effect of temperature
(Ferromagnets can become paramagnets. Alignment of magnetic moments in a paramagnet
due a field is thermally assisted)
MAGNETISM
All matter Arising out of band structure of metals
Diamagnetism Arising out of atomic magnetic moments
(permanent) (Spin + Oribital) Pauli spin paramagnetism
Variation of mass susceptibility with temperature (in Kelvin): the Curie law and the
Curie-Weiss law (with a positive value of ). The behaviour of a diamagnetic
material is shown for comparison. Diamagnets have small negative susceptibility
which essentially does not change with temperature.
Ferromagnetism (FM)
Ferromagnetism, Antiferromagnetism and Ferrimagnetism involve no new types of
magnetic moments; but involve the way the magnetic moments are coupled (arranged).
Two important ways of understanding ferromagnetism in metals are: (as listed in the
introduction to the magnetic properties):
(i) assuming that moments are localized to atoms,
(ii) using the band structure of metals (giving rise to itinerant electrons).
The former is conceptually easier and has been assumed in the 'molecular field theory' and
the Heisenberg's approach. It should be noted right at the outset that even in metals (e.g.
Fe), most of the electrons behave as if they are 'localized' and the number of itinerant
electrons could be a small number.
In Fe there are 8 valence electrons which occupy the (3d + 4s) bands. Out of these 8
electrons only ~0.95 in the 4s band are 'truly' free/itinerant and remaining ~7.05 are
occupy the 'localized' 3d band.
In Ni the corresponding quantities are: (3d + 4s) = 10, free 4s0.6, localized 3d9.4.
Band Theory to Understand Ferromagnetism
As mentioned before a correct theory of magnetism in metals has to involve bands as the
electrons are not localized to atoms. However, as noted before, most of the electrons
(especially in 3d metals which are elemental magnets) are rather localized and the 'free'
electrons (4s) do not contribute to the ferromagnetic behaviour. Truly speaking the 3d
electrons in transition metals are neither fully localized nor fully free.
Band theory is able to explain the non-integral values of magnetic moment per atom; though,
the values may often not match exactly.
The density of states varies in a complicated manner.
In Fe the 3d electrons are all not fully localized and about 5-8% have some itinerant
character and these electrons mediate the exchange coupling between the localized moments.
Using the observed magnetic moment per atom (H) of Fe to be 2.2B the up-spin and down-
spin occupancy can be calculated as: ,
Nd Nd 7.05 Nd Nd 2.2 Nd 4.62, Nd 2.42
(a) (b)
Simplified use of band theory to understand ferromagnetism: (a) Fe (inset shows the
alignment of up and down spin bands in the absence of exchange coupling), (b)
Ni. Two important points to be noted are: (i) the N(E) is actually more
complicated than the simplified curve shown, (ii) N(E) is different for Fe and Ni,
but has been shown/assumed to be same. 3d band has a high density of states
close to Fermi level (EF).
The above discussions can be summarized as a few thumb-rules for existence of
ferromagnetism in metals:
(i) the bands giving rise to magnetism must have vacant levels (e.g. 3d bands in Fe, Co, Ni)
for unpaired electrons to be promoted to;
(ii) close to the Fermi level the density of states should be high– this ensures that when
electrons are promoted to the unfilled higher energy levels the energy cost is small (high
density of states implies a smaller spacing in energy);
(iii) assuming direct exchange, the interatomic distance should be correct for exchange
forces to be operative (leading to parallel alignment).
Effect of External Magnetic Field
Spatially correlated collective quantized modes lead to demagnetization (called spin waves
(or magnons)).
Ferromagnet becomes paramagnet above Curie temperature (Tc). At Tc susceptibility
becomes infinite. Even beyond Tc there are local clusters ('spin clusters') of aligned magnetic
moments.
Maximum magnetization is obtained when all the moments have parallel orientation– let this
state correspond to a magnetization M0 (or 0).
It is expected that a plot of s/0 versus T/Tc will approximately lie on one another for
different materials.
Wherein, EExternal corresponds to the energy of total magnetic moment in the external magnetic
field.
Magnetoresistance
The resistance of a conductor changes when placed in an external magnetic field. This
effect is called magnetoresistance.
The resistance is higher if the field is parallel to the current and lower if the field is
perpendicular to the current. In general the resistance depends on the angle between the
current and magnetic field and this effect is called Anisotropic Magnetoresistance
(AMR).
The change is usually small (~ 5%; can be as large as 50% as in the case of some
ferromagnetic uranium compounds). Magnetoresistance arises from a larger probability
of s-d scattering of electrons in a direction parallel to the magnetic field. AMR effect is
used in magnetic field sensing devices.
Magnetism in Nanomaterials
Magnetic nanostructures in bulk materials
When we go from bulk to ‘nano’ only the structure sensitive magnetic properties (like
coercivity) is expected to change significantly.
0D 1D 2D Bulk
Fe can have a maximum possible moment of 6B/atom (3B orbital + 3B spin)
this implies that in 0D nanocrystals very little of the orbital magnetic moment is quenched
Superparamagnetism
As the size of a particle is reduced the whole particle becomes a single domain below a
critical size.
This aspect can be understood in two distinct ways:
i) a particle smaller than the domain wall thickness cannot sustain a domain wall (noting
that domain wall thickness may not be constant with size),
ii) the magnetostatic energy increases as r3 ('r' being the radius of the particle) and the
domain wall energy is a function of r2 there must be a critical radius (rc) below which
domain walls are not stable.
(in reality the calculation is complicated by other factors).
The general trend is:
= magnetic moment per unit mass = m/mass. Units: [Am2/kg]
rc ~ f 2
Ms Ms is saturation magnetization
2-3 orders of magnitude
Reduction in size
Performance
Magnetism of Clusters
Like other properties of clusters, magnetic properties of clusters can change with the
addition (or removal) of an atom. Clusters considered here have few to a thousand of
atoms typically (extending upto about 5 nm).
Important factors which determine the magnetic behaviour of clusters are:
(i) atomic structure,
(ii) nearest neighbours distance,
(iii) purity and defect structure of the cluster.
Ferromagnetic clusters
In small clusters (with less than 20 atoms) there are large oscillations in the magnetic
moment of the cluster (calculated as magnetic moment per atom).
For more than 600 atoms in the cluster 'bulk-like' behaviour emerges (i.e. with increasing
number of atoms the oscillations die down and bulk behaviour emerges).
Fe can have a maximum possible moment of 6B/atom (3B orbital + 3B spin).
Fe12 cluster has a moment of 5.4B/atom practically very little of the orbital moment
is quenched in the cluster.
Fe13 however has a moment of only 2.44B.
Ni13 cluster has an abnormally low moment as well and this is attributed to the
icosahedral structure of the cluster (which is densely packed).
With larger and larger cluster size the orbital contribution seems to be low; but, there is
still an enhancement of the magnetic moment over the bulk value. Thus structure and
packing seem to play an important role in the net magnetic moment obtained.
Variation of Magnetic moment per atom in Fe clusters with cluster size.
Enhancement over bulk value is to be noted.
Antiferromagnetic clusters
In antiferromagnetic materials we do not expect any net magnetic moment in the bulk.
However, there is a possibility that in small clusters 'up' spins do not cancel out the 'down'
spins (leading to a net magnetic moment) these are anti-ferromagnets behaving as
ferromagnets!
Magnetic 'frustration' is also a possibility. (frustration the spin on a given atom does not
'know' which way to point).
Small clusters of Cr (one of the few metals which are antiferromagnetic- spin density
wave AFM) have an interesting rich set of possibilities (along with allied complications!).
A plot of magnetic moment per atom oscillates with size (as in the case of ferromagnetic
clusters). A given cluster size (e.g. Cr9) is expected to exist in multiple magnetization
states (in the case of Cr9 magnetization can be small (~0.65 B/atom) or as high as ~1.8
B/atom [1]). In addition to the 'multiple magnetization states' there is a possibility of co-
existence structural isomers.
Mn clusters show some similarities with ferromagnetic Fe clusters with regard to cluster
size dependence (with more than 10 atoms) [2]. Compact Mn13 (icosahedral) and Mn19
(double-icosahedral) clusters have very low magnetic moment as compared to
neighbouring clusters. Mn15 has the highest moment of 1.5 B/atom [2].
[1] L. A. Bloomfield, J. Deng, H. Zhang, and J. W. Emmert, in “Clusters and Nanostructure Interfaces” (P. Jena, S. N. Khanna, and B. K. Rao, Eds.), p. 213. World Scientific, Singapore, 2000.
[2] M. B. Knickelbein, Phys. Rev. Lett. 86, 5255 (2001).
Mn
A gas phase supersaturated metal vapour is ejected into flowing inert gas (which is
cooled).
The metal vapour is produced by: (i) thermal evaporation, (ii) laser ablation, (iii)
sputtering, etc.
Most mass separators require the clusters to be charged (the clusters need to be ionized if
they are not charged). Examples of mass filters include: Radio Frequency Quadrupole
filter, Wien filter, Time-of-flight mass spectrometer, Pulsed field mass selector, etc.
At the end of separation we can get a narrow distribution of masses of particles (in small
clusters we can even get a precise number of atoms in a cluster).
The experimental results presented for free clusters [Fe (ferromagnetic clusters) and Cr
and Mn (antiferromagnetic clusters)] are typically measured using a setup, which is based
on the Stern-Gerlach experiment (that detected electron spin) which is typically coupled
with pulsed laser vaporization technique (details in next slide).
A collimated cluster beam is guided into a magnetic field gradient (dB/dz). The field
gradient will deflect a cluster with magnetic moment by a distance ‘d’ given by the
equation as below (L length of the magnet, D distance from the end of the magnet to
the detector, M cluster mass, vx entrance velocity).
For clusters deposited on surfaces other techniques of measurement exist such as: X-Ray
Magnetic Circular Dichroism, Dichroism in Photoelectron Spectroscopy, Surface
Magneto-Optical Kerr Effect, UHV Vibrating Sample Magnetometry, etc.
For embedded clusters techniques like: Micro-SQUID Measurements, Micro-Hall Probes,
etc. can be used to measure the magnetic moments.
dB 2 (1 2 D / L)
d L
dz 2 Mvx2
Experimental setup for the measurement of magnetic moments
[1] F. Huang, M. T. Kief, G. J.Mankey, and R. F.Willis, Phys. Rev. B 49 (1994) 3962
[2] Z.Q. Qin, J. Pearson, and S. D. Bader, Phys. Rev. Lett. 67,1646 (1991).
Magnetism of Hybrids: Giant Magnetoresistance (GMR)
Due to exchange coupling of spins across an interface between a ferromagnetic phase and
an antiferromagnetic phase, there is a preferred direction (anisotropy) for the field, which
leads to a shift in the hysteresis (M-H) loop. [E.g. Co particles (ferromagnetic) covered
with CoO (antiferromagnetic with large crystal anisotropy)].
Steps involved in creating exchange anisotropy:
• Have a single domain FM particle (say Co) in contact with a AFM layer (CoO)
• Apply a field above the Néel temperature of the AFM phase to saturate the FM phase
• Cool the system below the Néel temperature of the AFM phase to introduce a
preferential alignment of spins across the interface (in the AFM phase). The spins in the
FM phase will maintain their orientation even after the field is removed.
• Construct the usual M-H loop
If the field is removed the spins in the FM phase will flip to the field-cooled orientation,
due to the influence of the AFM phase. As the field direction is reversed, the spins across
the interface in the AFM (with large crystal anisotropy) oppose the reversal of spins in the
FM phase. Hence, the exchange coupling leads to large coercivity value.
(a) Preferential ordering of spins in the antiferromagnetic phase across the interface.
(b) Application of a field in opposition to the magnetization of the ferromagnetic phase
leading to a disturbance of spins across the interface in the AF phase.
Nanodiscs Special spin arrangements with no bulk counterparts
Vortex spin structure of nanodiscs. In the core regions the spins have an out of plane
component (the magnitude of which has been shown with an out of plane
displacement of vectors).
Nanorings
Spin structures (states) in nanorings: (a) votex, (b) onion, (c) twisted