Refresher lecture in magnetism

Virginie Simonet,
Institut Nel, CNRS-UJF, BP166, 38042 Grenoble Cedex 9 Outline : Introduction Atomic magnetic moment Assembly of non interacting magnetic moments Magnetic moments in interaction From microscopic to macroscopic Applications Modern trends in research

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Introduction
Magnetic materials all around us : the earth, cars, audio, video, computer technology, telecommunication, electric motors, medical imaging Magnetism: science of cooperative effects of orbital and spin moments in matter -> Wide subject expanding over physics, chemistry, geophysics, life science. Large variety of behaviours : dia/para/ferro/antiferro/ferrimagnetism, phase transitions, spin liquid, spin glass, spin ice, magnetostriction, magnetoresistivity, magnetocaloric effect, in different materials : metals, insulators, semi-conductors, oxides, molecular materials Inspiring or verifying lots of model systems : Ising 2D (Onsager) Magnetism is a quantum phenomenon but phenomenological models commonly used to treat classically matter as a continuum
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Atomic magnetic moment

An electric current is a source of a magnetic field

Biot Savart law

A magnetic moment m is equivalent to a current loop (Ampre) m=I.S (coil magnetic moment) creating a dipolar magnetic field

Note : magnetic monopoles so far undetected

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Atomic magnetic moment

Magnetic moment is related to angular momentum : electrical current comes from the motion of electrons and is source of magnetism in matter Example for a one turn coil : orbital magnetic moment

L = r p = mr2 n e l = L = L 2m

e 2 e r2 l = I.S = r n = n 2 2
angular momentum e- orbiting around the nucleus

gyromagnetic ratio

Consequences : magnetic moment and angular momentum are antiparallel Calculations with magnetic moment using formalism of angular momentum Precession of magnetic moment in a magnetic field : Larmor precession
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L = B0

Atomic magnetic moment

Quantum mechanics:

Electronic orbitals are eigenstates of lz operators l2 and Orbital angular momentum and its projection are quantized in units of (Bohr) The component of the orbital angular momentum along the z axis is ml The magnitude of the orbital momentum is

l(l + 1)
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Atomic magnetic moment

Quantum mechanics:
S, spin angular momentum of pure quantum origin The component of the spin angular momentum along the z axis is ms The magnitude of the spin momentum is

s(s + 1)

Classical picture of erotating about itself

With s=1/2, ms=-1/2,+1/2 quantum numbers Magnetic moments

s = gs B s l = gl B l

with gs=2,gl=1
and the Bohr magneton

e B = 2me

Two contributions to the atomic magnetic moment : spin and orbit

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Atomic magnetic moment

= Several e- in an atom: L
ne

= S
ne

Combination of the orbital and spin angular momenta of the different electrons : related to the filling of the electronic shells in order to minimize the electrostatic energy and fulfil the exclusion Pauli principle 1 : 2:

S= L=
ne ne

ms ml

maximum

Hunds rules

maximum in agreement with 1st rule

Spin-orbit coupling : relativistic expression of the magnetic induction effect S = L +S on the spin of the e- from its orbital motion L. J total angular momentum 3: J = |L S | J = |L + S | for less than filled shell for more than filled shell
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Atomic magnetic moment

A given atomic shell (multiplet) is defined by 4 quantum numbers : L, S, J, MJ with -J<MJ<J Application of Hunds rules:

Total magnetic moment

= B (L + 2S ) M = gB J M
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with the Lande g-factor

g =1+ J (J + 1) + S (S + 1) L(L + 1) 2J (J + 1)

Atomic magnetic moment

Magnetism is a property of unfilled electronic shells : Most atoms (bold) are concerned but only 22 magnetic in condensed matter

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Atomic magnetic moment

Atom in matter: chemical bonding -> filled e- shells : no magnetic moments
Except for : in insulator/metals in insulators

Situation more complicated for 3d metals : magnetism due to delocalized 3d electrons

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Atomic magnetic moment

Atom in matter: Influence of surrounding charges -> crystal field (CEF)
3d electrons

Large CEF>>spin-orbit : angular distribution of 5 orbitals -> some favoured by CEF -> quenching of orbital momentum + Spin-orbit coupling : g anisotropy

five 3d orbitals

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Atomic magnetic moment

Atom in matter: Influence of surrounding charges -> crystal field (CEF)
4f electrons
Spin-orbit>>CEF: 4f charge distribution +CEF -> selects some orbitals Spin-orbit-> anisotropy J : alignement of magnetic moments along some directions Charge distribution of rare earths

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Atomic magnetic moment

Summary :
Magnetism is a quantum phenomenon Magnetic moments associated to angular momenta Orbital magnetic moment and spin magnetic moment Localized magnetic moment in 3d and 4f atoms : different behaviour Orbital and spin moments can be strongly coupled (spin-orbit coupling in 4f) Importance of environment, crystal field: quenching of orbital moment in 3d and magnetocrystalline anisotropy in 4f

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Assembly of non-interacting magnetic moments

One atomic moment in a magnetic field B
Energy:
2 e B = B (L + 2S ).B + W 8me

Zeeman energy : coupling of total magnetic moment with field Diamagnetic term : induced orbital moment by the external field

ie

i B )2 (R

Magnetization : derivative of energy wrt magnetic field susceptibility: derivative of magnetization wrt magnetic field or ratio in the linear regime

M =

E B

M M = = B B

lin

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Assembly of non-interacting magnetic moments

Energy:
2 e B = B (L + 2S ).B + W 8me

ie

i B )2 (R

N atomic moments in a magnetic field B:

Boltzmann statistics + perturbation theory

N M = V

Ej B

exp( Ej ) j exp( Ej )

N e2 2 0 < R > Diamagnetic term: = V 4me

Diamagnetic magnetization due to induced moment by magnetic field : negative weak susceptibility, concerns all e- of the atom, T independent
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Assembly of non-interacting magnetic moments

Energy:
2 e B = B (L + 2S ).B + W 8me

ie

i B )2 (R gJ JB B x= kB T

Paramagnetic term:

N M = gJ JB BJ (x) V

with

and the Brillouin function

2J + 1 2J + 1 1 x BJ (x) = coth x coth 2J 2J 2J 2J

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Assembly of non-interacting magnetic moments

Paramagnetic term Brillouin functions compared to Langevin functions from classical calculation

Limit x>>1 i.e. H>>kBT Saturation magnetization:

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N M = gJ JB V

Assembly of non-interacting magnetic moments

Paramagnetic term Limit x<<1, i.e. kBT>>H Curie law:

N (B gJ )2 J (J + 1) C N p2 ef f = = = V 3kB T T V 3kB T
with the effective moment

pef f = gJ

J (J + 1)B

Works well for magnetic moments without interactions, negligible CEF : ex. Gd3+, Fe3+ or Mn2+ (L=0)
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Assembly of non-interacting magnetic moments

At small H/kBT : linear regime

In metals : Pauli paramagnetism (>0, weak, T-independent) <- spin of conduction eLandau diamagnetism (<0, weak, T-independent) <- orbital moments of conduction e2/04/10

Magnetic moments in interaction

Dipolar interaction :

0 3 E= [1 .2 2 (1 .r)(2 .r)] 3 4 r r

much too weak to account for ordering of most magnetic materials

Exchange interaction :
electrostatic origin + Pauli exclusion principle 2 electrons cannot be in the same quantum state many-electrons wavefunctions are antisymmetric with respect to the exchange of 2 electrons

Heisenberg Hamiltonian H =

Jij Si .Sj
ij

J : Exchange coupling constant

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> 0 ferromagnetic < 0 antiferromagnetic coupling

Magnetic moments in interaction

Exchange interaction :
Direct exchange usually weak -> small orbital overlap between magnetic orbitals Superexchange : mediated by the non-magnetic ions between the magnetic ones

Most often antiferromagnetic Explains the magnetism in transition metal oxides

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Magnetic moments in interaction

Exchange in metals
In rare-earth metals
The interaction between 4f localized moments is mediated by 5d and 6s itinerant electrons : Rudermann-Kittel-Kasuya-Yosida (RKKY) interaction

Hij = J(Rij )Si .Sj

with

cos(2kF r) J(r) r3
for r >>
1 2kF

The magnetic arrangement determined by kF, the Fermi wave-vector

In 3d metals
Interaction via overlap of the 3d wavefunctions : its sign depends on the filling of the bands
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Hercules2010

Magnetic moments in interaction

From paramagnetic state at high temperature to ordered state at low temperature kBT>>exchange interactions Several sublattices: directions of magnetic moments -> compensate

All moments //

Several sublattices: directions of magnetic moments -> do not compensate

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Magnetic moments in interaction

Treatment of interacting magnetic moments : Molecular field
Interactions represented by a fictitious field originating from neighbouring moments

H=

Jij Si .Sj + gB
ij j

Sj .B
with

H = gB

Si .(B + Bmf )
i

Bmf

2 = gB

Jij Sj
j

Ferromagnetic case :

Bmf = M

With positive

At low temperature, the moments can be aligned by the internal molecular field without external B

2z J = ng 2 2 B

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Magnetic moments in interaction

Treatment of interacting magnetic moments : Molecular field
Ferromagnetic case : In the low field, high temperature limit Magnetic susceptibility

TC=C Curie temperature At Tc, becomes infinite : the system becomes spontaneously magnetized

(gJ B )2 J (J + 1) C M= (B + M ) = (B + M ) 3kB T T C C = = T C T TC

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Magnetic moments in interaction

Treatment of interacting magnetic moments : Molecular field
Ferromagnetic case : Magnetization below TC Solve simultaneously 2 equations M/Ms For B=0

M = gJ B JBJ (x) gJ B J (B + M ) x= kB T

No solution for T>TC One solution for T<TC : spontaneous magnetization 2nd order transition at TC y
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Magnetic moments in interaction

Treatment of interacting magnetic moments : Molecular field
Ferromagnetic case :

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Magnetic moments in interaction

Treatment of interacting magnetic moments : Molecular field
Antiferromagnetism : same analysis but for each of the 2 sublattices Spontaneous magnetization below the Nel temperature TN on each sublattice Susceptibility

C = T + TN

TN = ||C

More complicated below TN : depend of field orientation

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Magnetic moments in interaction

Treatment of interacting magnetic moments : Molecular field
Generalization:

1/

Curie-Weiss law

C = T

=-TN T>TN

=0

=TC Ferromagnets TC Fe 1043 K Co 1394 K Ni 631 K Gd 293 K

T<TN

Antiferromagnets TN CoO 293 K NiO 523 K MnO 116 K

Shull 1951 Neutron diffraction

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Magnetic moments in interaction

Other types of magnetic orders
Ferrimagnetism, =-TN but spontaneous magnetization ; Spontaneous magnetization on each sublattice may have T dependence ->compensation temperature Ex. Ferrites, garnets Helimagnetism : helical order of moments Ex. Rare earths crystals case of a J1/J2 chain

E = 2N S 2 (J1 cos() + J2 cos(2)

Solutions =0 (ferro), = (antiferro) or helix

J2 J1

J1 cos() = 4J2
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Magnetic moments in interaction

Other types of magnetic orders
Complex magnetic structures often due to frustration of interactions Example for a triangle of magnetic moments Antiferromagnetic interactions Ising moments Antiferromagnetic interactions Heisenberg moments -> Non collinear

Example Ba3NbFe3Si2O14 Helix + 120 arrangement

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Magnetic moments in interaction

Magnetic excitations
perfect order at T=0 At T0, order disrupted by spin waves Short range interactions

Allows entropy gain without loosing too much in exchange energy

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Magnetic moments in interaction

Magnetic excitations
Dispersion relation For a cubic crystal Ferromagnetic case Bloch law : Ms (0) Ms (T ) valid at small T, T 3 /2 Ms (0) outside critical region Antiferromagnetic case

E (k ) = 4JS (1 cos(ka))

E (k ) = 4JS | sin(ka)|

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From microscopic to macroscopic

Macroscopic behaviour of magnetization, a compromise between 4 interactions:
Exchange interaction : favours uniform magnetization. Very strong but short-ranged Dipolar interaction : tends to avoid formation of magnetic poles. Weak but long-ranged Magnetocrystalline anisotropy : orients magnetic moments along privileged directions Zeeman energy, interaction with an external magnetic field : alignment of magnetic moments along the field For a homogeneous ferromagnetic material, minimization of free energy:

FT = Fex + Fdip + Fan + FH

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From microscopic to macroscopic

Magnetocrystalline anisotropy
-> magnetic moments will prefer to align along certain crystallographic directions (stronger for 4f than for 3d atoms) Ex. metamagnetic transitions in antiferromagnets

Weak anisotropy : spin-flop transition

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Strong anisotropy : spin-flip transition

From microscopic to macroscopic

Magnetocrystalline anisotropy
Magnetization variation against anisotropy in ferromagnets Uniaxial anisotropy easy axis

E = 0 Happ Ms sin + K sin 0 Happ Ms E sin = =0 2K

2

hard axis

for

sin = 1

Happ

2K = HA = 0 Ms

Anisotropy field
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From microscopic to macroscopic

Magnetocrystalline anisotropy
Magnetization variation against anisotropy in ferromagnets Cubic symmetry easy axis <100> easy axis <111>

EA = K1 (2 2 + 2 2 + 2 2 ) + K2 2 2 2 + ...
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, , : cosines of the angles between magnetization and the x, y, z directions// 4-fold axes

From microscopic to macroscopic

Dipolar energy
-> shape anisotropy -> formation of magnetic domains with magnetization along the directions privileged by anisotropy

0 3 E= [1 .2 2 (1 .r)(2 .r)] 3 4 r r

minimising the demagnetising field produced by the material

Explains zero macroscopic magnetization in ferromagnetic materials below TC if they have not been submitted to a magnetic field.
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From microscopic to macroscopic

Cost in exchange and anisotropy energies at the boundaries between domains: domain walls
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From microscopic to macroscopic

Width of the wall : balance between exchange and anisotropy energy
Exchange energy lost:

Eexch = N JS 2 (1 cos ) JS 2 K EA = N K < sin > 2

2

Anisotropy energy lost

Total energy minimization Domain wall width:

Eexch 5-100 nm = 2 a K Energy of the domain wall: = 2 KEexch

Note : other types of domain walls in reduced dimension systems
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From microscopic to macroscopic

Coercitivity represents the magnetization ability to resist reversal against applied magnetic field Coercive field for coherent rotation : Stoner-Wohlfarth model

E = K sin2 + 0 Ms H cos
uniaxial anisotropy

Zeeman term

Energy minimization wrt :

As long as When

H < 2K/0 Ms

, =0 and are 0

two minima separated by a barrier

H = 2K/0 Ms

the energy barrier flattens and the magnetization can rotate to the = minimum
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From microscopic to macroscopic

Stoner-Wohlfarth model works well for nanoparticles The coercive field Hc = 2K/0 Ms

But Hc << 2K/0 Ms for most systems

In macroscopic materials, influence of defects Rotation occurs by nucleation on defects and propagation of domain walls
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From microscopic to macroscopic

Hysteresis cycle of a ferromagnet

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Applications
Applied research -> lots of applications, concerns mostly ferromagnetic materials Hard magnetic materials (reasonable value of remanence, high coercitivity) Soft magnetic materials (high remanence, low coercitivity) Magnetic memory materials (high remanence, moderate coercitivity) Materials for electronics : operate at high frequencies

Recording and reading

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Research in magnetism : modern trends

Frustration : complex magnetic orders, spin liquid, spin ices Molecular magnetism : photoswitshable, molecular magnets From quantum to classical: mesoscopic scale -> Quantum computer Multiferroism : coexistence of two ferroic orders (magnetic, electric, elastic) Low dimension systems: Haldane, BEC, Luttinger liquid Quantum phase transitions Magnetism and superconductivity Nano materials : thin films, multilayers, nano particles ->Spintronics Magnetoscience

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