... U!-.

~--··

!Solid State -Physics

n;ttism is also 'a weak effect but, -unlike diamagnetism, the magnetic mome.nt
J:s aligned in the direction of the field. Ferromagnetism is a very s~ong effect
'and arises when the adjacent magnetic moments align themselves m the same
direction. In antiferronuJgnetism, the adjacent moments .are. equal an~ op-
posite to each other and hence complete cancellation of moments takes
is
place. FerrinuJgnetism similar to antiferromagnetism except that adjacent
moments are unequal in magnitude and hence complete cancellation of
moments does not take place. The magnetic materials. are classified accord-
i~g to the nature of the magnetism present. It may, however, be noted that
above a certain critical temperature, the distinction ·between various types
of magnetic materials disappears and all the materials bec0me paramagnetic.
The various types of magnetisms have been described m detail in the
following sections.
8.3 DIAMAGNETISM . .
. . \ . . .
As indicated above, di3!Dag~etism in a material arises due to changes
. in the atomic orbital states induced by the ·applied · magnetic· field. An
electron revolving in an orbit -constitutes an el~tric curie.nt. When a mag-
netic flux linked with such an electric circuit is changed, an induced current
is set up in such a direction as to oppose the change in flux in accordance
with the Lenz's law. The m~gnetic field of the induced current is opposite
to the applied field and produ~e.s the diamagnetic effect~ The 9CCtJrrence of
diamagnetism is manifested by the very · small _and negative value of. the
.magnetic susceptibility. Diamagnetism exists in all materials but is usually
suppressed due to the presence of ·stronger.effects such as P¥amagnetism,
ferromagnetism, etc. The diamagnetism has been described' quantitatively
by applying the .classical and quantum theriries. · -
8.3.1 Langevin's Classical Theory
Consider an electron revolving around the nucleus in a circular· orbit
with frequency C.0 0 • Since a moving electron is equivalent to a current, some
magnetic flux is linked with such a cu~ent loop. When an ex~mal magnetic
field is applied, the magn~tic flux linked with this current loop tends to change
which alters the current in the loop in such a way a8 to oppose the change
in flux. This change in current is manifested by the change in the frequency
of revolution of the eleCtron. If c.o 0 is. the frequency of r~olutiQil of the
electron in the absence of an applied field and p is the radius of the orbit,'
then we have ·

(8.9)
 Magnetism in Solids 231
where Ze represents the nuclear charge and m is the mass of the electron. It
gives the value of Ol 0 as ' ·.

(I) 0 . = (8.10)

. .
In the presence of a magnetic induction B, the Lorentz force on an electron
moving wi~ velocity v is given by
F = e(v x B) (8~ 11)

Assuming the magnetic field to be perpendicular to the orbit, the magnitude

of this force is

.
F= ep'EB (8.12)
.
If ro is the freqency of electron in the presence of the field, the force equation
. can be written as .

Ze 2
. · 2 -- epro/B .
47tE0 P' . .
•
=:mro 0 2 p /- eproB . ·. ·[Using Eq. (8.10)] (8.13)
where the minus sign with the Lorentz force r~presentS the negative charge.
Thus

or
1 eB eB
ro = 2 [ ~. m ± ( m ) +
2
2 ,
4010 1
t
I eB
=± roo+.( - )
2m ·
2
2
eB
2m

eB ·
For - << ro 0, we obtain
2m .

eB.
co =±·roo- -2 . (8.14)
. m
This shows that the frequency of revolution of an electron changes by·a factpr
232 . _Solid State Physics

eB
of .__,. in the presenc_e of the magnetic induction B. The ± sign in (8.14)
2m
signifies that the electrons with orbital' moments parallel to the field .are
slowed down whereas those with moments anti parallel to the field are speeded
up. This result is called the- La;mor theorem. The change in frequency
produces an additional current which can be written as
I = charge x revolutions per unit time

= (- (
1 eB)
e) 2n· 2m·

(8.15)
4nm
The magnetic moment of the current loop_cOntaining a single electron is giv~n
by the product of the current and the area of the Joop, i.e.,
2 -
e B 2
Jl =- - p (8.16)
e _4m

The negative sign signifies that the· induced magnetic moment points in a
direction opposite to the applied field. If B ~s not perpendicular to the plane
of the orbit, then p in Eq. (8.16) r:epresents the projection of the radius of
the orbit on a plane perpendicular to the magnetic field. If an atom contains
z electrons with their orbits randomly oriented, the total induced magnetic
moment becomes

Ze 2B - 2
Jla =- 4m ~ P > (8.17)

If the field points alon·g z-axis, then

<p2> = <X2> +<y2>
is the mean of the squares of perpendicular distances of electrons from the
axis of the field.-The mean square distance of electrons from the nucleus is
<rl> = <x2> + <y2> + <z2>
For a spherically symmetric charge distribution, we have
<x2> = .<y2> = <z2>·

(8.18)
 233
Magnetism in Solids

Equation (8. 17) now gives

'k2B 2 J.L Ze2H I

(8.19)
Jl = _ <r > = _ o < ,2 >
a 6m 6m
For a solid consis.t ing of N atoms per unit volume, each containing Z electrons,
the expression for the diamagnetic susceptibility becomes

X . = M =- NJJ.o2!!2 <r2> ,(8.20)

dla H 6m
This is the classical Langevin result and shows thauhe diamagnetic s'uscep-
tibility is independent of temperature.
8.3.2 Quantum Theory
Using quantum mecha~ics, it can be shown that, in the presence of a
magnetic induction B, the Hamiltonian <H of an atomic electron changes to
<H + 'H' where the term <H' may be treated as a small perturbation and is.given
by

ieh e2 2
<H' = - - (V.A+2A.V) + - A (8.21)
2m 2m
where A is the magnetic vector potential expressed by
B=VxA
If the magnetic induction is uniform, it can be described by the vector
potential A as

1
A= -Bxr
2

= ~ (i( Byz- Bzy)+ J( Bzx- Bxz) +.k(Bxy- Byx)] (8.22)

For the magnetic field pointing along the z-direction, we have

Bx = BY'= 0, Bz = B,
·and Eq. (8.22) gives

1 1
AX =- -yB A -= --xB A = 0 (8.23)
2 'Y 2 'Z

Also,
 235
Magnetism in Solids
. . .
requires the deteimination of electronic charge oistribution within the atom.
It may, however, be noted that in the calculations ·involvingquantum mechan-
ics, the concept of orbits is replaced by the wave. function and the quantity
<fl> has a different significance. The experimental results agree .fairly welJ.
with the theoreticaUy calculated values particularly for light elements'and rare
gases, whereas large deviations exist for ions containing a very 1..-ge number
of electrons. The typical value for helium is about -l.9x10~ which shows
that the diamagnetism is a very weak 'effect.
8.4 PARAMAGNETISM
Paramagnetism occurs in those atoms, ions and molecules which have
permanent magnetic moments. In the absence of a magnetic field, these
n1:agnetic moments are oriented randomly and no n.e t magnetization is pro..
duced. w_hen a magnetic field is applied, 'these moments orient themselves
in the direction of the field which results in some net magnetization paralle~
to the applied field. The paramagnetic materials have small, positive and
temperature-dependent susceptibility. The permanent magnetic moments of
ions result from the followi~g contributions : .
(i) The spin or intrinsic moments of the electrons.;
(ii) The orbital motion of t~e electrons,
(iii) The spin magnet~c moment of the nucleus.
' " '

Paramagnetism is ·Observed in :
(i) Metals
' .
(ii) ·Atoms and molecules possessing an odd r,mmber c;>f electro~~·.
e.g., free sodiuf11 atoms, g~seous nitric oxide, etc.
(iii) A few compounds having an even number of electrons, e.g.,
· oxygen molecule. . ·
r'
(iv) Free atoms and ions hav- B
ing a partially filled inner
shell, e.g.; rare ·earth and
actinide ·elements,. ions' of · · '
some transition el~ments ''
such as Mn2+, etc.
''
''
8.4.1 Langevin's Classical Theory '
I
Lang-evin considered a paramag~
0
netic gas containing· N atoms per unit
volume each having a permanent mag- Fig. 8.1. Magnetic dipole with
netic moment Ji. The mutual .interaction moment .J.l oriented at an angle a to
between the magnetic dipoles was as- the applied magnetic field.
236 Solid State Physics

sumed ·to be negligible. In the presence of a magnetic induction B, these

dipoles tend to orient themselves in the direction of the .field in order to
minimize their energy. The thermal energy at ordinary temperatures, how-
ever, resists such an alignment of dipoles. In thermal equilibrium, the dipoles
orient themselves at an angle e with the direction ofthe applied field as shown
in Fig. 8. 1. The pQtential energy of each dipole in this position is given by
E = - J..l.B =.- fJ[J cos e
Using Maxwell-Boltzmann distribution law, the number of magnetic dipoles
having this particular orientation is proportinal to

exp
·
(-_!___)
kT or exp ( .
J.!Bcos e)
·kT .

Also, according to statistical mechanics, the probability for·a magnetic dipqle

to make an angle between e and e + de with the magnetic field, or the number
of dipoles, dn, 'having axes within the solid ar:tgle dro lying .between two
hollow ·.cones of semiangles e and e + de (Fig. 8.1) is given by

·flB cos e )
dn ex: exp .( kT . dro

·
= k exp .
( J.1Bcos
kT
e) ·27t sine d~ (8.29)

where k is a constant. Each one of these dipoles contributes a component of

magnetic moment f.1 cos 0 to the magnetization, whereas the components
perpendicular to the field direction cancel each other. Hence the ·average
component of the magnetic moment of each atom along the field direction
multiplied by the number of atoms p~r unit volume, N, gives. the magneti-
zation M, i.e.,

pt ed . 9 exp(
J.1 J.01tcos 8 sm 11B cos e )de
10 J.1 cos n · kT
M = NJ.!<cose> =N =N .
J~dn . cos e)de
. 1sm e exp( J.tBkT
,
1t •
0

(8.30)

Let J.!B
kT =X,
and cose = y
-sine de= dy
MagMJism in Solids 237
Therefore, Eq. (8.30) becomes

M = NJl r•ye~dy = NJl [ex +e~x _ _!_] = NJl [coth x-_!_]

rJ eX>' dy ex- e x X X

= NJl L(x) (8.31)

1.0 x/3
I
I
•
I
I
I
0.8

i-
I
I
I
I
. I
I
I /

0.6 I
I

,'I
)( I
I
I
-.1 I
0.4 I
I
I
.
I
I
I
I.
~
0.2

X • .

Fig. 8.2: Variation of IJ.x) with x..

where L(x) is called the Langevin function.. The variation
.
of L(x). with

x = JlB is shown in Fig. 8.2. For x << 1, i.e., at normal field strengths and
kT
ordinary temperatures, the curve is almost linear and coincides with the
tangent to the curve at th~ origin which is equal to x/3. ~us, we have

L(x)lx=O X = J.1B.
(8.32)
3 3kT
Therefore, Eq. (8.31) gives·
2
· NJ.1 B
M:--
3kT
The paramagnetic susceptibility is given as

- P.oM - J.loNJ.12
Xpara - B - 3kT (8.33)

which shows that the s.usceptibility is inversely proportional to temperature.

It cari be written as
238
Solid State Physics

c
Xpara = T (8.34)

N 2
where C = f.1<? : is a constant. The expression (8.34) is called the Curie
3
/my and C is called the Curie constant. Thus we find that the Curie law holds
good for t-tB << kT. ·
For large values of i , i.e., for high flux densities and low temperatures,
L(x) approaches un~ty and Eq. (8.31) gives
A1 =IV~ =A1s (8.35)
This i~~ the saturation condition. whi_~h corresponds to the complete alignment
of the magnetic dipoles in the field direction· A1 is called the saturation
' s
magnetization. · ·
8.4.2 Quantum Theory
The classical theory assumes that the permanent magnetic moment of
a given atom or ion rotates freely and can possess any orientation w!!h respect
to the applied magnetic field: According to quantum theory, since these
magnetic moments _are quantized, the magnetic dipole .moment f..l and its
component j..Lz in the direction of the applied field cannot have arbitrary values.
We have, in general, ·a . direct relationship between the magnetic dipole
moment J.l of an atom or ion in free space and its angular momentum J as
J.l = -KJlsJ . (8.36)
. . - . ~
The ·q uantity ~a. is called the Bohr magneton and is equal to m in SI system
2

a~d __!!!__ in CGS system of units; g is known as the Lande's g-factor and
2mc
is equal .to 2 if the net angular momentum of the-dipole is due t? electron
spin and 1 if it is due to orbital motion only. In general, it has mixed origin
and ·is obtained from the expression :
1(1 + 1) + s(s + 1) ~ L(L + 1)
(8.37)
1
g = + 21 (1 1)+
where S and L represe~t the sp~ and orbital quantum numbers of the dipole
respectively. The orientations/of the magnetic -moment J.l with respect to the
direction of the applied magnetic field :ye. spe.cified by. the r~le that the
possible COJVponents of J.l along the field dtrectton are.gtven by
Jlz = - K'JlamJ (8.38)
where m1 = - J, -J+ 1, .... , J-1, J is the magnetic quantum number associ~ted
 -.
241 . Solid State Physics

canriot be neglected in comparison with the externally applied··field. In

paramagnetic materials where .the crystal field is negligible~ Eq. (8.48) holds
good. But when it is strong, it may break the rotational symmetry of the dipole
and affect its total angul~ momentum. ~lso, the average value of Lz may ·
reduce to zero which is kn~wn as quenching of the orbital angular momentum.
In such a case, Eq. (8.39) should be written as ·
E = 2ms~BB [As g = 2]

(8.50)

eli) · ·
(
For -;; .msB << kT, it yields

2 .
X=- (
·'tJ, 0 N
S(S+l)
eli
-· (8.51)
3kT m )
I .
For example, for Mn3+ ions, the value of x as obtained from the above
expression with S = 2 is in- conformity with the ·experimental observations
where Eq. (8.48) prediCts a zero susceptibility ..
8.5 FERROMAGNETISM
Like paramagnetism, ferrotnagnctism is also associated with the pres-
ence of permanent magnetic dipoles~ but unlike paramagnetism, the magnetic
moments of adjacent atoms in this case are aligned in a particular direction
even in the absence of the applied m~gnetic field. Thus a ferromagnetic
material exhibits a magnetic moment in the absence of a magnetic field. The ·
magnetiz_ation existing in a ferromagnetic material in the absence of an
" . .
.app1ied magnetic field is ·called the spontaneous magnetization. It exists
'

below a certain critical temperature called the Curie temperature, T 0 The

alignrpent of magnetic .moments below the Curie temperature is due to the
exchange interaction between the magnetic ions and will be described later.
Above the Cutle .temperature, the thermal effects offset ·the spin alignment
and the ferromagnetic substance becomes paramagnetic.
The ferromagnetic substanc:;es acquire a large magnetization in the
presence of even a weak external magnetic field. They possess a large and
positive value of susceptibility which, in general, is not constant but varies
with field strength. The variation of magnetization~ field strength exhibits
the well-known hysteresis curve. The exa~ples of ferrorpagnetic materials
are the elements such as Fe, Ni, Co, Gd and Dy. and a riumber ?f alloys and
oxides such as MnBi. MnAs, Cr02, etc.
 · Magnetism in Solids 243

8.5.1 Weiss Theory of Ferromagnetism

The theory of ferromagnetism put forward by Wei~~ is centred about
the following two hypotheses :
(i) A specimen of ferromagnetic material contains a number .of .
small regions called domains which are spontaneously magne.:
tized. The magnitude of spontaneous magnetization of the spec-
imen as a whole is determined by the vector sum of the magnetic
moments of individual domains. . · ·
'
(ii) The spontaneous magnetization of each oomain is due to the
presence of an exchange fieid, B E• which tends to produce a
parallel alig.nment of the atomic dipoles. The field BE is as- .
sumed to be proportional to the magnetization M of each do-
mam, t.e.,
(8.52)
a
where 'A. . is constant called the Weiss-field constant and is
independent of temperature.
It may be noted that, in the above expression,- we always use the
average values of BE and M for a domain. The field-BE is also --~-ailed the
molecular field or the Wei_ss field and is generally quite strong as compared
to the applied field B. For iron, for example, BE~ 1000 T. Thus the effective
mangetic field on an atom or ion becomes ·
Beff= B + BE= B + AM (8.53)
In order to develop the theory of ferromagnetism, y~e shall use the quantum
theory of magnetization rather than the classical Langevin theory used by
Weiss originally.
C<msider a ferromagnetic solid containing N atoms -per unit volume
each having a total angular momentum quantum number 1. By analogy to -
Eq. (8.46), we can write the· expression for magnetization as ·
(8.54)
where
g is the Lande's g-factor,
21 + 1coth ( 21 + 1) x--coth
1

Brillouin function, Bjx) = 1 ( -X ) .

(8.55)'
21 21 21 21
and

x = g1JJ.sBeff = g1p.s (B + ~ , (8.56)

kT kT

~ .
- ·
I .

244 Solid State Physics

In case of spontaneous magnetization, B = 0 and Eq. (8.56) becomes r

glJlsAM (8.57)
x= kT
xkT
:. M<n.= 'A.glJls (8.58)
As T ~ 0 or x ~ oo, B jx) ~ 1; Jhe maghetic moments align themselves
parallel to the field and the magnetization M becomes the saturation mag-
netization, M/0). Thus, from Eq. (8.59) give
M 5 (0) = NglJliJ (8.59)
From Eqs. (8.58} and (S.59), we obtain
M(T) xkT
(8.60)
Ms(O) - A.Ng 2J\1 ~
Also, Eqs. (8.54) and (8.58) give
M(T)
. ~ws(O) =Bjx) (8.61)

T > Tc
1.0

--::------- ------------ p------\--------· ·.

Plot of Eq. ( 8.61 )
0.6
' i
0.4 -

--
0
.....
V)
~- ~ Plot of Eq. ( 8.60 )
0.2

0 L-----~------------------------------

Fig. 8.3. Graphical solution of the sim1,4ltaneous equations (8.60) and"(8.61).

A point of irttersection P determines the spontaneous magnetization MsfTJ
at a ·given temperature. No solution exists for T > Tc
The magnetization M(n
at a given temperature can be obtained by
solving Eqs. (8.60) and (8.61) simultaneously. The plots of M(niMs<O) versus
 --
Magnetism in Solids

x representing Eqs.
(8.60) and (8.61) are
shown in Fig. 8.3. 1.0
Note that the Eq.
(8.60) represents a
straight line passing
through the origin and
having slope propor-
r 0.8

0.6
tional to T. At tern- I- a
perature equal to the V)
0.4
':?..V)
":?.
critical temperature
Tc• this line is tangent 0.2
to the Brillouin func-
tion at -the origin. )'he
intersection of the two 0 0.2 0.4 0.6 0.8 1.0
plots at the point 0 TITc IIi' .
represents a positive
solution, but the mag- Fig. 8.4. Spontaneous magnetization versus
netization c~rrespond­ temperature.Jor T < Tc-
.ing to this · point is
· -unstable. Another point of intersection appears for T < Tc which indicates
a non-zero value. of M even for zero external field and hence corresponds to
spontaneous magnetization. It also follows that the spontaneous magnetiza-
tion decreases with increase iq temperature and vanishes beyond th~ temper-
ature Tc which is known as the ferromagnetic Curie temperature. ·The
variation of spontaneous magnetization with temperature is shown in Fig. 8.4.
It becomes maximum at 0 K when all the moments are lined up in a particular
direction under the influence of the exchange field. This variation of M
s
enables one to classify the paramagnetic-ferromagnetic transition as a second
order phase transition, i.e., a transition characterized by an order parameter
(e.g. Ms in this case) which · is non-zero only below TC' .
The Par~magnetic Region
Consider the magnetization in the region weil. above
.....
the Curie tern-
perature. ForT> Tc, the spontaneous magnetization is zero and an external .
field will have to be applied to produce some magnetization. This field should,
however, be weak enough to avoid the saturation state. In such a state, we
f find from Eq. (8.56) that x << 1 and we can write ·

1)
J+
Bj.x):: ( 3J X

Therefore, the expression (8.54) beco'mes

•
 Solid State Physics

M = NgJJ-8 (1+ l)x/3

x= glJJ.s(B+AM)
(8.62)
kT
Thus,

2 2 . .
M = Ng J.LBJ(J +I) (B+ AM) (8.63)
· 3kT ·
which gives

.(8.64)

where

(8.65)

and (8.66) .

The expression (8.64) is· known as : the Curie-Weiss law. It satisfactorily

describes the temperature dependence of susceptibility in the paramagnetic
region provi~ed ·the temperature,. is well above the Curie tempe~ature. The
Curie temperature determined from the theory of spontaneous magnetization
differs by a few degrees from the experimentally determined value for the
parama_gnetic region.
8._5':2 Nature and Origin of Weiss Molecular Field : Exchange Interactions
The Weiss theory of ferromagnetism is based on the concept of
ferromagnetic domains which are spontaneously" magnetized due to the pres-
ence.of an internal molecular fiel.;l called the Weiss .field or the exchange field,
BE· The theory, however, does not explain the origin and nature of this field;
The Weiss field cannot be simply due to magnetic dipole-dipole interaction
betw.een the neighbouring dipoles as this would generate fields of the order
of I 03G on~y whereas the actual field strengths are obs~rved to be quite high.
For example, the Weiss field for iron is of -the order of 107 G. It wa'i
Heisenberg who. first proposed in 1928 that the Weiss field was the conse-
1
quence of the quantum-mechanical exchange interaction between the atoms. .
This interaction arises due to the Pauli's exclusion principle according to
which any change i~ the relative orien~tion of the two·spins would disturb
Magnetism in Solids . 249

8.5.3 Concept of Domains and Hysteresis

According to the Weiss theory d~scribed above, the exchange inter-
actions ·between the neighbouring dipoles in a ferromagnetic material gen-
erate an internal exchange field BE which aligns them i~ a particular direction.
It is, however, observed that a ferromagnetic material such as iron does not
exhibit a net magnetization unless it is placed in an external field. Weiss
explained this by intr:oducing the concept of ferromagnetic domains. Acc~d­
ing to this concept, a single crystal of a ferromagnetic solid is divided into
a number of small regions called domains each one of which is spontaneously
magnetized by the exchange field. The magnetization vectors of different
domains are, however, randomly oriented so that no net magnetization is
produced in the material as a whole. In the presence of an external magnetic
field, the domains pointing in the direction of the field grow ·at the expen~e.
of those pointing. in other direction~. thereby resulting in some non-zero
magnetization in the material. ·

M
c

Domain rotation
---- ------- -------- -·
lrre\,lersible wall
displacement

------ -------------- ·
Reversible wall displacement

Fig. 8.6. Typical hysteresis cuTVe for a ferromagnetic material indicating the
predominant magnetization processes in different regions.
According to :Neel, the origin of domain structure of a ferromagnetic
solid rests in the principle of minimization of the total energy of the material
which, apart from exchange en~rgy, comprises the magnetic field energy, ·
anisotropy energy, domain wall energy and magnetostrictive exchange en-
ergy. As an example, the presence of free magnetic poles at the ends of a
magnetized specimen generates an external field H which g~ves ~se to the
magnetic field energy equal to ~ H.B. This energy can be loWered by
250 Solifl State Physics

red~cing the volume of the domain by subdividing it into neighbouring i

subdomai.ns, thereby reducing the field H and hence the magnetic field
energy. However, such a subdivision of domains cannot continue indefinitely
and is restrained by the fact that the formation of domain walls requires
additional energy. Thus, it can be concluded that, whereas the ~r:~sence of
large domains is energetically unfavourable, a ferromagnetic material must
possess a domain structure consisting of a number of smaller domains which
corresponds to a state of minimum energy.
. .

All ferromagnetic materials exhibit the well k-nown hysteresis curves;

a typical one is shown in Fig. 8.6. It is apparent that for T<T0 th~re are two
solutions forM (and hence for B) which trace the boundary of the hysteresis
· curve. These solutions ca~ be obtained from the intersection of ~e plots of
Eq. (8.6n and the expression

(8.75)

where the latter expression has been obtained from Eq. (8.62). The physical .
cause of the ·phenomenon of hysteresis can be understood from the ~oncept
of domains. The magnetization produced in a ferromagn~tic ·solid in the
presence of an external J;llagnetic field may be attributed to
(a) . growth in the size of domains having favourable orientation
with respect to the applied field at the expense of those having
unfavourable orientation, and
(b) rotation of the· directions of magnetization of vario.us domains
along the field direction.
~

These two magnetization processes are illustrated below· :

!'
, ---+. /, I '
,--+
' / !'
'' /'
/
~

t .' >(~ t/~+ I >( . ~

/ /

1/' /
/ '\.
.,__.- '...
H
/
/
+--
' H
1//
/ '
' \ ' ·,
( a ) Unmagnetized ( b ) Magnetization .( c ) Magnetization by
specimen by domain growth domain rotation

Fig. 8.7. The two fundamental processes of magnetization.

a
When a small magnetic field is applied across ferro~agnetic material,
the domains pointing almost along the direction· of the field grow at the
.·expense of the domains having opposite oiien'tation, ~us resulting in a sm811
mag~etization as-indicated by.the i~itial portion (OA) of the hys~resis curve.
Such displacements of domain boundaries are mostly reversible and hence .
-
MagMtism in Solids 251
the portion OA of the curve is also reversible. As the field increases, a greater
-number of domains grow favourably which results in a large incr~e in
magnetization (portion AB). The boundary displacements in this region are
often large and irreversible. The growth of domains continues until the
favourable domains grow up to the maximum extent with their magnetization
vectors still pointing along the so-called easy directions of magnetization. As
the field increases further, the domains rotate from their easy directions to
the direction of the applied field; the magnetization increases slowly (portion
BC) and finally attains a saturation value Ms when·an the domains point along
the direction of the field. On decreasing the field, the·magnetization does no~
follow the same path because the aligned domains do not regain their random
state of orientation easily. There exists some non-zero ma~netization even
after removing the field altogether. This magnetization is called the remanent
magnetization or remanence, M r The magnetization can ·be reduced to zero
by applying a reverse magneti~ field known as the.coercivefield or coercivity,
---.
He. A similar variation-in the-r-ev-erse--ffi.M_!letization is observed as the reverse
,.

field is first increased and then decreased. The closed loop CEFKC is called
the hysteresis loop. A similar loop is obtained.by plotting B versus H except
that the line CI in this curve is never parallel to the field axis. The hysteresis
curves are quite important in determining the quality of _a magnetic;; material _
and selecting the material for a particular apE_lication.
8.6 ANTIFERROMAGNETISM
'
Antiferromagnetism or.iginates when · the spin moments of the
as
neighbouring atoms are ordered in an antipar~llel arrangement shown in:
Fig. 8.8 or when the exchange integral is negative. A crystal exhibiting
antiferromagneti~m may be considered to Qe consisting of two interpenetrat-
ing sublattices A and B, one ·of which is spontaneously magnetized in one
direction and the other is spontaneously magnetized in the opposite direction.
This type of magnetism was frrst observed in the crystals of MnO. In the
absenee of an external magn~tic field, the neighbouring magnetic moments
cancel out each other.and the material as a whole exhibits no magnetization.
However, when a field is applied; a small magnetization ap~ars in. the -
direction of the field which . increases further with temperature. Such a
behaviour is typical of an ·antiferr9magnetic material. The magnetization
becomes the maximum at a critical temperature TN• called the Neel temper-
ature, which is analogous to the Curie temperature in the paramagnetic or
ferromagnetic substance~. Abo~e 'this temperature, the magnetization de-
creases continuously which is in~icative of the paramagnetic state of.the
material. The variation of susceptibility with temperature is shown in Fig. 8.9
and is compared with the corresponding variations for the paramagnetic and
ferromagnetic substances. Unlike_the ferromag~tic case, the susceptibility
 252 Solid State Physics

Q( an antiferromagnetic substance is not

infinite for T equal to TN• but has a weak
cusp. The antiferromagnetic behaviour
can be explained with the help of the
molecular field theory which was ini-
tially developed by Neel. A brief de-
Fig. 8.8. Neighbouring antiparallel
scription of this theory. is given below.
spin moments of A and B sublattices
Consider an antiferromagnetic proqucing antiferromagnetism.
substance consisting of two·sublattices
A and B such that an atom of one type has all the nearest neighbours of the
opposite type. The internal or molecular field acting on an atom can be
obtained by using' the molecular field approximation developed by Weiss in
which the interaction between the various magnetic moments is considered.
In an antiferromagnetic substance, besides the nearest neighbour negative AB
interaction, there also exists the next nearest 'neighbour negative AA (m: AB)
interaction which is quite weak· as compared to the former. : If a and p
representthe interaction pa~ameters, i.e., the Weiss f~ld constants for AA (or
BB) and AB interactions respectively, the internal fields present at A and B
sites, expressed in terms of flux densities, can be written as .
=-a.MA- ~MB
BmA
BmB =- PMA- aMB
J
where M A and M 8 are the magnetizations of the corresponding. sites. In the
(8.76)

BA
BB = B- PMA- aMB ,
J.
presence of an external field B, the;effective fields at A and B sites become
=B - aMA -:- PMB .
(8.77)
To determine the total magnetization, MA+M8 • of the specimen, we consider
the temperature regions below and above the·Neel temperature.
Paramagnetism Ferromagnetism ~ntifem?magnetism

i )(
Q)
....
;:]
0
c. ·s: :
~ n3 i
I
I
I
t
X Q.cl X
X Q) I
U .01
I

: Tc
0
x=-
C T ----+ c -a o
x=T-Tc(T>Tc)
T
( Curie law ) . ( Curie - Weiss law )
Fig. 8.9.
(i) T>TN
· In this region, the specimen behaves as paramagnetic; ·the magnetiza-
tions of the two-sublattices can be written in accordance with Eq. (8.13) as
Magnetism in Solids 2S3 .

(8.78)

where
J.l2 = Jl~g2J(J+l).
ln these e~pressions, it has been assumed that the A-t~pe atoms are identical
w~i th 8-type atoms and their densities are equal, i.e., NA =N8 =N. The total
magnetization M is, therefore, obtained as
M = MA + M8
N 2
= . 3:T (BA +BB)

2
.=· NJl [2B-(a+J3)(MA +MiJ)] [Using Eq..(8.77)]
3kT ·
N 2 .
= ~· [2B-(a+J3)M] (8.79)
3kT
This yields the expression for susceptibility as

(8.80) .
•

where·

and (8.81)

1be expression (8.80) satisfies the experimental data on susceptibility quite

well. It is analogous to the Curie-Weiss law given by Eq (8.64) for ferromagnetic
materials above the critical temperature except that it contains the term
T + ·9 ~instead ofr--a
(or T-Tc) in the denominator. The 1/x VC(SUS Tcurves
are shown in Fig. 8.10 to compare the anti{erromagnetic behaviour with the
 -
2S4 Solid State Physics

par~magnet'ic and
ferrCi'mag~etic ones. It
can be shown that the
Neel temperature, TN' is
a
not identical with and
the two are related as
i
TN ~-a
-=-- (8.82)
e ~+a
.
Thus the value of
TN depends . on the
strength of AB and AA
(or BB) interactions. For
-e 0· e
a = 0, TN= e. If a is ·T ...
positive, TN< e. Also,
TN increases with ~ . Fig. 8.1 0. Plot of llx. versus T for para-, ferro;. and
These result-s ·h ave been · antiferromagnetic substances above their critical
verified experimentally. temperatures.

(ii) ·T <TN
In ·this temperature r egion, each of the two sublattices A and B is
spontaneously magnetized along its preferred direction of magnetization, but
the net magnetization is still .zero. The application of an external field,
however, results in some
net megnetization. There
are two directions of the
applied field 'Vhich are
of particular interest -
one perpendicular and
the other parallel to the X
preferred direction. The
susceptibility in these
two directions are deter-
mined separately and the
average is t•ken to·
0.5 1.0 1.5
calculate the net suscep-
tibility It can be shown· T I TN
that the susceptibility in
the perpendicular direc- Fig. 8.11 Plot of X. versus TnN for an atftiferromag-
netic single crystal~ F_pr T<TN' X is also a function of
tion, l.i' is independent
direction of external field relative to the preferred
of ~mperature, i.e., re- 1
direction of magnetizo~ .
mains almost constant
· Magnetism in Solids

below the Neel temperature. The susceptibility in the parallel direetion~ Xn' .
decreases continuously with decrease in temperature and approaches zero as
T-+ 0 K. This means that at 0 K, the internal field is so strong that it does
not allow the spins of one sublattice to change their orientation along the sp~·nS
of the other sublattice even when an external field is present. At ·r:-TN,
x
l.1. =~I= X· The variations of X.t• 11 and x with temperature are shown in
Fig. 8.11.
. 8.7 FERRIMAGNETISM .
Ferrimagnetism is identical to antiferromagnetism except that the
magnetization of the two sublattices have different magnitudes·which result
in a non-zero value of net magnetization. This type of magnetism occurs in
materials such as feriites which are basically the· oxides of various metal
elements. The in6st common example is the one of magnetite or ferrous
ferrite, Fe30 4 .or FeO. Fe20 3 . Ithas been found.that for_this particular ferrite,,
one Fe3+ ion occupies tetrahedral o{A-site, i.e., it is tetrahedrally coordinated
to four oxygen anions whi.le the other Fe3+ ion an~ the Fe2+ .ion occupy
octahedral _or ~-sites, each, being octahedra1ly coordinated to six ..oxygen
anions. The ions present at A and B sites constitute A and B sublattices
respectively and have opposite types of magnetizations. The net magnetiza-
.tion of a formula unit of Fe30 4 is, therefore, equal to the magnetization of
a single Fe2+ ion and is represented in Fig. 8.12. However, one unit cell of
magnetite having the spinel structure contains eight formula units of Fe30 4
in jt and accprdingly the net magnetization of a unit cell is equal to the sum
of the magnetizations of eight Fe2+: ions.

+ ___., ·l ~:~getization
. (4J.I.B) .

B
Fig. 8.12. Magnetizations of the individual sites and the net
magnetization in one formula unit of Fe30 4.
It is thus easy to note that a ferrimagnetic solid resembles a ferromag-
netic one in the sense that both possess.spontaneous magnetization. Also, both
exhibit hysteresis and almost identical magnetic properties. Neel attributed
·the antiparallel arrangement of spins of A and B sites to the negative AB
interaction. Besides this, there also exist the negativeM and BB interactions
which are much weaker than AB. interaction. Tht magnetic behaviour of
ferrimagnetic solids is explained on the basis ofNeel's molecular field theory;
the detailed description is beyond the scope of this book. Above the CUrie
~mperature, the magnetization at both the sites obeys the Curie-Weiss law,
whereas below this temperature the saturation effects come into existence and
the magnetizations are obtaine9 ,using Eq. (8.46).