Diluted Magnetic Semiconductors

Prof. Bernhard He-Vorlesung 2005

Carsten Timm
Freie Universitt Berlin

Overview
1. Introduction; important concepts from the theory of magnetism
2. Magnetic semiconductors: classes of materials, basic properties,
central questions
3. Theoretical picture: magnetic impurities, Zener model, mean-field
theory

4. Disorder and transport in DMS, anomalous Hall effect, noise

5. Magnetic properties and disorder; recent developments;
questions for the future

These slides can be found at:

http://www.physik.fu-berlin.de/~timm/Hess.html

Literature
Books on general solid-state
theory and magnetism:

Review articles on spintronics and

magnetic semiconductors:

H. Haken and H.C. Wolf, Atomund Quantenphysik (Springer,

Berlin, 1987)

H. Ohno, J. Magn. Magn. Mat. 200, 110

(1999)

N.W. Ashcroft and N.D. Mermin,

Solid State Physics (Saunders
College Publishing, Philadelphia,
1988)
K. Yosida, Theory of Magnetism
(Springer, Berlin, 1998)
N. Majlis, The Quantum Theory of
Magnetism (World Scientific,
Singapore, 2000)

S.A. Wolf et al., Science 294, 1488

(2001)
J. Knig et al., cond-mat/0111314
T. Dietl, Semicond. Sci. Technol. 17,
377 (2002)
C.Timm, J. Phys.: Cond. Mat. 15,
R1865 (2003)
A.H. MacDonald et al., Nature
Materials 4, 195 (2005)

1. Introduction; important concepts from the theory of magnetism

Motivation: Why magnetic semiconductors?
Theory of magnetism:
Single ions
Ions in crystals
Magnetic interactions
Magnetic order

Why magnetic semiconductors?

(1) Possible applications
Nearly incompatible technologies in present-day computers:
semiconductors: processing

ferromagnets: data storage

ferromagnetic semiconductors: integration on a single chip?

single-chip computers for embedded applications:
cell phones, intelligent appliances, security

More general: Spintronics

Idea: Employ electron spin in electronic devices

Giant magnetoresistance effect:

Spin transistor (spin-orbit coupling)

Datta & Das, APL 56, 665 (1990)

Review on spintronics:
uti et al., RMP 76, 323 (2004)

Possible advantages of spintronics:

spin interaction is small compared to Coulomb interaction
less interference
spin current can flow essentially without dissipation
J. Knig et al., PRL 87, 187202 (2001); S. Murakami,
N. Nagaosa, and S.-C. Zhang, Science 301, 1348 (2003)
less heating

higher
miniaturization

spin can be changed by polarized light, charge cannot

spin is a nontrivial quantum degree of freedom,
charge is not
Quantum computer
Classical bits (0 or 1) replaced by quantum bits
(qubits) that can be in a superposition of states.

Here use spin as a qubit.

new
functionality

(2) Magnetic semiconductors: Physics interest

Control over magnetism

Universal physics construction set

by gate voltage, Ohno et

al., Nature 408, 944 (2000)

Vision:
control over positions and
interactions of moments

Vision:
new effects due to competition of old effects

Theory of magnetism: Single ions

Magnetism of free electrons:
Electron in circular orbit has a magnetic moment

l
ve
re

with the Bohr magneton

l is the angular momentum in units of ~

The electron also has a magnetic moment unrelated to its orbital motion.
Attributed to an intrinsic angular momentum of the electron, its spin s.

In analogy to orbital part:

g-factor
In relativistic Dirac quantum theory one calculates
Interaction of electron with its electromagnetic field leads to a small
correction (anomalous magnetic moment). Can be calculated very
precisely in QED:

Electron spin:

with

(Stern-Gerlach experiment!)

2 states , , 2-dimensional spin Hilbert space

operators are 22 matrices

Commutation relations: [xi,pj] = i~ij leads to [sx,sy] = isz etc. cyclic.

Can be realized by the choice si i/2 with the Pauli matrices

Magnetism of isolated ions (including atoms):

Electrons & nucleus: many-particle problem!
Hartree approximation: single-particle picture, one electron sees potential
from nucleus and averaged charge density of all other electrons

assume spherically symmetric potential eigenfunctions:

quantum numbers:

n = 1, 2, : principal
l = 0, , n 1: angular momentum
m = l, , l: magnetic (z-component)

angular part; same for any

spherically symmetric potential

Ylm: spherical harmonics

in Hartree approximation:
energy nl depends only on n, l with 2(2l+1)-fold degeneracy

Totally filled shells have

and thus

Magnetic ions require partially filled shells

nd shell: transition metals (Fe, Co, Ni)

4f shell: rare earths (Gd, Ce)
5f shell: actinides (U, Pu)
2sp shell: organic radicals (TTTA, N@C60)
Many-particle states:

Assume that partially filled shell contains n electrons, then there are

possible distributions over 2(2l+1) orbitals degeneracy of many-particle state

Degeneracy partially lifted by Coulomb interaction beyond Hartree:

commutes with total orbital angular momentum and total spin

L and S are conserved, spectrum splits into multiplets with fixed

quantum numbers L, S and remaining degeneracy (2L+1)(2S+1).
Typical energy splitting ~ Coulomb energies ~ 10 eV.
Empirical: Hunds rules
Hunds 1st rule: S ! Max has lowest energy
Hunds 2nd rule: if S maximum, L ! Max has lowest energy
Arguments:
(1) same spin & Pauli principle electrons further apart lower Coulomb repulsion
(2) large L electrons move in same direction lower Coulomb repulsion

Notation for many-particle states: 2S+1L

where L is given as a letter:

L 0 1 2 3 4 5 6

...

S P D F G H I

...

Spin-orbit (LS) coupling

(2L+1)(2S+1) -fold degenaracy partially lifted by relativistic effects

v
Ze

in rest frame
of electron:

r
Ze

magnetic field at electron position (Biot-Savart):

energy of electron spin in field B:

This is not quite correct: rest frame of electron is not an inertial frame.
With correct relativistic calculation: Thomas correction (see Jacksons book)

Coupling of the si and li: Spin-orbit coupling

Ground state for one partially filled shell:
less than half filled, n < 2l+1: si = S/n = S/2S (Hund 1)

over occupied orbitals

more than half filled, n > 2l+1: si = S/2S (filled shell has zero spin)

unoccupied orbitals

Electron-electron interaction can be treated similarly.

In Hartree approximation: Z ! Zeff < Z in

L2 and S2 (but not L, S!) and J L + S (no square!) commute with Hso and H:

J assumes the values J = |LS|, , L+S, energy depends on quantum

numbers L, S, J. Remaining degeneracy is 2J+1 (from Jz)
n < 2l+1 ) > 0 ) J = Min = |LS| has lowest energy
n > 2l+1 ) < 0 ) J = Max = L+S has lowest energy
Notation: 2S+1LJ

Hunds 3rd rule

Example: Ce3+ with 4f1 configuration

S = 1/2, L = 3 (Hund 2), J = |LS| = 5/2 (Hund 3)
gives 2F5/2

The different g-factors of L and S lead to a complication:

With g 2 we naively obtain the magnetic moment

?
But M is not a constant of motion! (J is but S is not.) Since [H,J] = 0 and
J = L+S, L and S precess about the fixed J axis:

Only the time-averaged moment can

be measured

S
S
2S+L = J+S

J+S||

Land g-factor

Theory of magnetism: Ions in crystals

Crystal-field effects:
Ions behave differently in a crystal lattice than in vacuum
Comparison of 3d (4d, 5d) and 4f (5f) ions:
Both typically loose the outermost s2 electrons and sometimes some of
the electrons of outermost d or f shell

3d (e.g., Fe2+)
3d
3sp
2sp
1s

4f (e.g., Gd3+)

partially filled

partially filled shell on outside of

ion strong crystal-field effects

5sp
4spd
3spd
2sp
1s

4f

partially filled shell inside of

5s, 5p shell weaker effects

3d (4d, 5d)

4f (5f)

strong overlap with d orbitals

weak overlap with f orbitals

strong crystal-field effects

weak crystal-field effects

stronger than spin-orbit

coupling

weaker than spin-orbit

coupling

treat crystal field first, spin-orbit

coupling as small perturbation
(single-ion picture not applicable)

treat spin-orbit coupling first,

crystal field partially lifts 2J+1
fold degeneracy

Single-electron states, orbital part:

Many-electron states:
multiplet with fixed L, S, J

e
t2

2J + 1 states
vacuum

cubic

tetragonal

vacuum

crystal

Total spin:
if Hunds 1st rule coupling > crystal-field splitting:
high spin (example Fe2+: S = 2)
if Hunds 1st rule coupling < crystal-field splitting:
low spin (example Fe2+: S = 0)
If low and high spin are close in energy spin-crossover effects
(interesting generalized spin models)
Remaining degeneracy of many-particle ground state often lifted by terms
of lower symmetry (e.g., tetragonal)
Total angular momentum:
Consider only eigenstates without spin degeneracy. Proposition:

for energy eigenstates

Proof:
Orbital Hamiltonian is real:

thus eigenfunctions of H can be chosen real.

Angular momentum operator is imaginary:
is imaginary
is real for any state
since
all eigenvalues are real

On the other hand, L is hermitian

Quenching of orbital momentum

orbital effect in transition metals is small

(only through spin-orbit coupling)
0

Lz

With degeneracy can construct eigenstates of H by superposition that are

complex functions and have nonzero hLi

Theory of magnetism: Magnetic interactions

The phenomena of magnetic order require interactions between moments
Ionic crystals:
Dipole interaction of two ions is weak, cannot explain magnetic order
Direct exchange interaction
Origin: Coulomb interaction

without proof: expansion into Wannier functions and spinors

electron creation operator

yields

with

with

and

exchanged

Positive J favors parallel spins ferromagnetic interaction

Origin: Coulomb interaction between electrons in different orbitals
(different or same sites)
Kinetic exchange interaction
Neglect Coulomb interaction between different orbitals ( direct exchange),
assume one orbital per ion: one-band Hubbard model

Hubbard
model
local Coloumb interaction
2nd order perturbation theory for small hopping, t U:

exchanged
allowed

Prefactor positive (J < 0) antiferromagnetic interaction

Origin: reduction of kinetic energy

Kinetic exchange through intervening nonmagnetic ions:

Superexchange, e.g. FeO, CoF2, cuprates

forbidden

 Hopping between partially filled d-shells & Hunds first rule:

Double exchange, e.g. manganites, possibly Fe, Co, Ni
Hund
Higher orders in perturbation theory (and dipolar interaction) result
in magnetic anisotropies:
on-site anisotropy:
exchange anisotropy:

(uniaxial),
(cubic)
(uniaxial)

dipolar:

Dzyaloshinskii-Moriya:
as well as further higher-order terms
biquadratic exchange:
ring exchange (square):

Magnetic ion interacting with free carriers:

Direct exchange interaction (from Coulomb interaction)
Kinetic exchange interaction

tight-binding model (with spin-orbit)

with

Parmenter (1973)

Hd has correct rotational symmetry in spin and real space

t
t

Idea: Canonical transformation

Schrieffer & Wolff (1966), Chao et al., PRB 18, 3453 (1978)

unitary transformation (with Hermitian operator T) same physics

formally expand in
choose T such that first-order term (hopping) vanishes
neglect third and higher orders (only approximation)
set = 1

EF

obtain model in terms of Hband and a pure local spin S:

Jij can be ferro- or antiferromagnetic but does not depend on ,

(isotropic in spin space)

Theory of magnetism: Magnetic order

We now restrict ourselves to pure spin momenta, denoted by Si.
For negligible anisotropy a simple model is
Heisenberg model
For purely ferromagnetic interaction (J > 0) one exact ground state is

(all spins aligned in the z direction). But fully aligned states in any direction
are also ground states degeneracy

H is invariant under spin rotation, specific ground states are not

spontaneous symmetry breaking

For antiferromagnetic interactions the ground state is not fully aligned!

Proof for nearest-neighbor antiferromagnetic interaction on bipartite lattice:

tentative ground state:

but (for i odd, j even)

does not lead back to

not even eigenstate!
This is a quantum effect

Assuming classical spins: Si are vectors of fixed length S

The ground state can be shown to have the form

general
helical order
with

Q = 0: ferromagnetic

arbitrary and the maximum of J(q) is at q = Q,

usually Q is not a special point incommensurate order

Exact solutions for all states of quantum Heisenberg model only known for
one-dimensional case (Bethe ansatz) Need approximations
Mean-field theory (molecular field theory)
Idea: Replace interaction of a given spin with all other spins by interaction
with an effective field (molecular field)

write (so far exact):

thermal average of
expectation values

only affects energy

fluctuations

use to determine hhSiii selfconsistently

Assume helical structure:

then
Spin direction: parallel to Beff
Selfconsistent spin length in field Beff in equilibrium:

Brillouin function:

Thus one has to solve the mean-field equation for :

S
BS
Non-trivial solutions appear if LHS
and RHS have same derivative at 0:

This is the condition for the critical temperature (Curie temperature if Q=0)

Coming from high T, magnetic order first sets in for maximal J(Q)
(at lower T first-order transitions to other Q are possible)

Example:
ferromagnetic nearest-neighbor interaction
has maximum at q = 0, thus for z neighbors

Full solution of mean-field

equation: numerical
(analytical results in
limiting cases)

fluctuations (spin
waves) lead to

Susceptibility (paramagnetic phase, T > Tc): hhSiii = hhSii = B

(enhancement/suppression by homogeneous component of Beff for any Q)

For small field (linear response!)

results in

For a density n of magnetic ions:

Curie-Wei law

T0: paramagnetic Curie temperature

Ferromagnet:
(critical temperature,
Curie temperature)

1/

diverges at Tc like (TTc)1

0

General helical magnet:

T0

Tc

1/

grows for T ! Tc but does not

diverge
(divergence at T0 preempted
by magnetic ordering)

possible T0
(can be negative!)

Mean-field theory can also treat much more complicated cases, e.g.,
with magnetic anisotropy, in strong magnetic field etc.