Chapter 7: The Electronic Band Structure of Solids

Bloch & Slater

April 2, 2001
Contents
1 Symmetry of (r) 3
2 The nearly free Electron Approximation. 6
2.1 The Origin of Band Gaps . . . . . . . . . . . . . . . . . . . . . . . . 9
3 Tight Binding Approximation 15
4 Photo-Emission Spectroscopy 24
1
Free electrons -FLT Band Structure
E
E
f
D(E)
V(r)
E
f
E
f
metal
"heavy" metal
insulator
E
D(E)
V(r) = V
0
E
f
Figure 1: The additional eects of the lattice potential can have a profound eect on
the electronic density of states (RIGHT) compared to the free-electron result (LEFT).
In the last chapter, we ignored the lattice potential and con-
sidered the eects of a small electronic potential U. In this
chapter we will set U = 0, and consider the eects of the ion po-
tential V (r). As shown in Fig. 1, additional eects of the lattice
potential can have a profound eect on the electronic density of
2
states compared to the free-electron result, and depending on
the location of the Fermi energy, the resulting system can be
a metal, semimetal, an insulator, or a metal with an enhanced
electronic mass.
1 Symmetry of (r)
From the symmetry of the electronic potential V (r) one may
infer some of the properties of the electronic wave functions
(r).
Due to the translational symmetry of the lattice V (r) is pe-
riodic
V (r) = V (r + r
n
), r
n
= n
1
a
1
+ n
2
a
2
+ n
3
a
3
(1)
and may then be expanded in a Fourier expansion
V (r) =

G
V
G
e
iGr
, G = hg
1
+ kg
2
+ lg
3
, (2)
which, since G r
n
= 2m (m Z) guarantees V (r) =
V (r + r
n
). Given this, and letting (r) =

k
C
k
e
ikr
the
3
Schroedinger equation becomes
H(r) =
_

_
h
2
2m

2
+ V (r)
_

_ = E (3)

k
h
2
k
2
2m
C
k
e
ikr
+

G
C
k
V
G
e
i(k

+G)r
= E

k
C
k
e
ikr
, k

kG
(4)
or

k
e
ikr
_

_
_
_
_
h
2
k
2
2m
E
_
_
_ C
k
+

G
V
G
C
kG
_

_
= 0r (5)
Since this is true for any r, it must be that
_
_
_
h
2
k
2
2m
E
_
_
_ C
k
+

G
V
G
C
kG
= 0, k (6)
Thus the potential acts to couple each C
k
only with its recip-
rocal space translations C
k+G
and the problem decouples in to
N independent problems for each k in the rst BZ. Ie., each of
the N problems has a solution which is a sum over plane waves
whos wave vectors dier only by Gs. Thus the eigenvalues
may be indexed by k.
E
k
= E(k), I.e. k is still a good q.n.! (7)
We may now sum over G to get
k
with the eigenvector sum
4
X
X
X
X
X
X
First B.Z.
Figure 2: The potential acts to couple each C
k
with its reciprocal space translations
C
k+G
(i.e. x x, , and ) and the problem decouples into N indepen-
dent problems for each k in the rst BZ.
restricted to reciprocal lattice sites k, k + G, . . .

k
(r) =

G
C
kG
e
i(kG)r
=
_
_

G
C
kG
e
iGr
_
_
e
ikr
(8)

k
(r) = U
k
(r)e
ikr
, where U
k
(r) = U
k
(r + r
n
) (9)
Note that if V (r) = 0, U(r) =
1

V
. This result is called Blochs
Theorem; ie., that may be resolved into a plane wave and a
periodic function. Its consequences as follows:

k+G
(r) =

G

C
k+GG
e
i(G

kG)r
=
_
_

C
kG
e
iG

r
_
_
e
ikr
=
k
(r), where G

G (10)
5
Ie.,
k+G
(r) =
k
(r) and as a result
H
k
= E(k)
k
H
k+G
= E(k + G)
k+G
(11)
= H
k
= E(k + G)
k+G
(12)
Thus E(k + G) = E(k) : E(k) is periodic then since both

k
(r) and E(k) are periodic in reciprocal space, one only needs
knowledge of them in the rst BZ to know them everywhere.
2 The nearly free Electron Approximation.
If the potential is weak, V
G
0 G, then we may solve the
V
G
= 0 problem, subject to our constraints of periodicity, and
treat V
G
as a perturbation.
When V
G
= 0, then
E(k) =
h
2
k
2
2m
free electron (13)
However, we must also have that (if V
G
,= 0)
E(k) = E(k + G)
h
2
2m
[k + G[
2
(14)
Ie., the possible electron states are not restricted to a single
parabola, but can be found equally well on paraboli shifted by
6
First BZ 2/a
E
Figure 3: For small V
G
, we may approximate the band structure as composed of N
parabolic bands. Of course, it is sucient to consider this in the rst Brillouin zone,
where the parabola centered at nite G cross at high energies. To understand the
eects of the perturbation V
G
consider this special k at the edge of the BZ. where the
paraboli cross.
any G vector. In 1-d Since E(k) = E(k + G), it is sucient
to represent this in the rst zone only. For example in a 3-D
cubic lattice the energy band structure along k
x
(k
y
= k
z
= 0)
is already rather complicated within the rst zone. (See Fig.4.)
The eect of V
G
can now be discussed. Lets return to the 1-d
problem and consider the edges of the zone where the [paraboli
intersect. (See Fig. 3.) An electron state with k =

a
will
involve at least the two G values G = 0,
2
a
. Of course, the
7
a a k
x
First B.Z.
a -a
Figure 4: The situation becomes more complicated in three dimensions since there are
many more bands and so they can cross the rst zone at lower energies. For example
in a 3-D cubic lattice the energy band structure along k
x
(k
y
= k
z
= 0) is already
rather complicated within the rst zone.
exact solution must involve all G since
_
_
_
h
2
k
2
2m
E
k
_
_
_ C
k
+

G
V
G
C
kG
= 0 (15)
We can generally take V
0
= 0 since this just sets a zero for the
potential. Then, those G for which E
k
= E
kG

h
2
k
2
2m
are
going to give the largest contribution since
C
k
=

G
V
G
C
kG
h
2
k
2
2m
E
kG
(16)
C
k
V
G
1
C
kG
1
h
2
k
2
2m
E
kG
1
(17)
8
C
kG
1
=

G
V
G
C
kG
1
G
h
2
k
2
2m
E
kGG
1
(18)
C
kG
1
V
G
1
C
k
h
2
k
2
2m
E
k
(19)
Thus to a rst approximation, we may neglect the other C
kG
,
and since V
G
= V
G
(so that V (r) is real) [C
k
[ [C
kG
1
[
other G
kG

k
(r) =

G
C
kG
e
i(kG)r

_
(e
iGx/2
+ e
iGx/2
) cos
x
a
(e
iGx/2
e
iGx/2
) sin
x
a
(20)
The corresponding electron densities are sketched in Fig. 5.
Clearly
+
has higher density near the ionic cores, and will
be more tightly bound, thus E
+
< E

. Thus a gap opens in

E
k
near k =
G
2
.
2.1 The Origin of Band Gaps
Now lets reexamine this gap at k = G
1
/2 in a quantitative
manner. Start with the eigen value equation shifted by G.
C
kG
_
_
_E
k

h
2
2m
[k G[
2
_
_
_ =

G

V
G
C
kGG
=

G

V
G

G
C
kG

(21)
9
V(x)
(x)

(x)
+
E
k
Gap!
E
D(E)
Figure 5:
+
cos
2
(x/a) has higher density near the ionic cores, and will be more
tightly bound, thus E
+
< E

. Thus a gap opens in E

k
near k =
G
2
.
C
kG
=

G
V
G

G
C
kG

_
E
k

h
2
2m
[k G[
2
_
(22)
To a rst approximation (V
G
0) lets set E =
h
2
k
2
2m
(a free-
electron energy) and ignore all but the largest C
kG
; ie., those
for which the denominator vanishes.
k
2
= [k G[
2
, (23)
10
or in 1-d
k
2
= (k
2
a
)
2
or k =

a
(24)
This is just the Laue condition, which was shown to be equiv-
alent to the Bragg condition. Ie., the strongest perturbation
to the free-electron picture occurs for states with energies at
the edge of the rst B.Z. Thus the equation above also tells us
highly perturbed
essentially free electrons
Figure 6: We can satisfy the condition E
k
E
kG
only for k on the edge of the B.Z..
Here the lattice potential strongly perturbs the electronic states (i.e. more than one
C
kG
is nite).
that C
k
and C
kG
1
are the most important coecients (if this
electronic state was unperturbed, only C
k
would be important).
Thus approximately for V
G
0, V
0
0 and for k near the
11
zone boundary
G = 0 C
k
_

_
E
h
2
k
2
2m
_

_
= V
G
1
C
kG
1
(25)
G = G
1
C
kG
1
_

_
E
h
2
[k G
1
[
2
2m
_

_
= V
G
1
C
k
, (26)
Again, ignore all other C
G
. This is a secular equation which
has a nontrivial solution i

_
h
2
k
2
2m
E
_
V
G
1
V
G
1
_
h
2
|kG
1
|
2
2m
E
_

= 0 (27)
or

E
0
k
E V
G
1
V
G
1
E
0
kG
1
E

= 0 (28)
(V
G
= V

G
, so thatV (r) 1)
(E
0
k
E)(E
0
kG
1
E) [V
G
1
[
2
= 0 (29)
E
0
k
E
0
kG
1
E
_
E
0
k
+ E
0
kG
1
_
+ E
2
[V
G
1
[
2
= 0 (30)
E

=
1
2
_
E
0
kG
1
+ E
0
k
_

_
_
_
1
4
_
E
0
kG
E
0
k
_
2
+ [V
G
1
[
2
_
_
_
1
2
(31)
At the zone boundary, where E
0
kG
1
= E
0
k
, the gap is
E = E
+
E

= 2[V
G
1
[ (32)
12
-/a
/a
0
k
2 V
G
E
k
k
e

Figure 7:
And the band structure looks something like Fig. 7. Within this
approximation, the gap, or forbidden regions in which there are
no electronic states arise when the Bragg condition (k
f
k
0
=
G) is satised.
[ k[ [k + G[ (33)
The interpretation is clear: the high degree of back scattering
for these k-values destroys the electronic states.
Thus, by treating the lattice potential as a perturbation to
the free electron problem, we see that gaps arise due to enhanced
electron-lattice back scattering for k near the zone edge. How-
13
ever, in chapter one, we considered band structure qualitatively
and determined that gaps could arise from perturbing about
the atomic limit. This in fact, is another natural way of con-
Separation
State
Energies
Figure 8: Band gaps in the electronic DOS naturally emerge when perturbing around
the atomic limit. As we bring more atoms together (left) or bring the atoms in the
lattice closer together (right), bands form from mixing of the orbital states. If the
band broadening is small enough, gaps remain between the bands.
structing a band structure theory. It is called the tight-binding
approximation.
14
r r
E
i i
V (r)
A
Valence electrons Atomic cores
Figure 9: In the tight-binding approximation, we generally ignore the core electron
dynamics and consider only the ionic core potential. For now lets assume that there
is only one valence orbital
i
on each atom.
3 Tight Binding Approximation
In the tight-binding approximation, we generally ignore the core
electron dynamics and treat consider only the ionic core poten-
tial. For now lets assume that there is only one valence orbital

i
on each atom. We will also assume that the atomic prob-
lem is solved, and perturb around this solution. The atomic
problem has valence eigenstates
i
, and eigen energies E
i
. The
unperturbed Schroedinger equation for the nth atom is
H
A
(r r
n
)
i
(r r
n
) = E
i

i
(r r
n
) (34)
15
There is a weak perturbation v(rr
n
) coming from the atomic
potentials of the other atoms r
m
,= r
n
H = H
A
+ v =
h
2

2
2m
+ V
A
(r r
n
) + v(r r
n
) (35)
v(r r
n
) =

m=n
V
A
(r r
m
) (36)
We now seek solutions of the Schroedinger equation indexed by
k (Blochs theorem)
H
k
(r) = E(k)
k
(r) (37)

E(k) =

k
[H[
k
)

k
[
k
)
(38)
where

k
[
k
)
_
d
3
r

k
(r)
k
(r)

k
[H[
k
)
_
d
3
r

k
(r)H
k
(r) (39)
Of course, this problem is almost hopelessly complicated. We
cannot solve for
k
. Rather, we will solve for some
k

k
where the parameters of
k
are determined by minimizing

k
[H[
k
)

k
[
k
)
E(k). (40)
16
This is called the Raleigh-Ritz variational principle.
Consistent with our original motivation, we will approximate

k
with a sum over atomic states.

k

k
=

n
a
n

i
(r r
n
) =

n
e
ikr
n

i
(r r
n
) (41)

k
(r) = U
k
(r)e
ikr
,
k
(r) =
k+G
(r)
Where
k
must be a Bloch state
k+G
=
k
which dictates our
choice a
n
= e
ikr
n
. Thus at this level of approximation we have
no free parameters to vary to minimize
k
[H[
k
) /
k
[
k
)
E(k).
Using
k
as an approximate state the energy denominator

k
[
k
), becomes

k
[
k
) =

n,m
e
ik(r
n
r
m
)
_
d
3
r

i
(r r
m
)
i
(r r
n
) (42)
Lets imagine that the valance orbital of interest,
i
, has an
very small overlap with adjacent atoms so that

k
[
k
)

n
_
d
3
r

i
(r r
n
)
i
(r r
n
) = N (43)
The last identity follows since
i
is normalized.
17
(r-r )
i 1 (r-r )
i 2
Figure 10: In the tight binding approximation, we assume that the atomic orbitals
of adjacent sites have a very small overlap with each other.
The energy for our approximate wave function is then
E(k)
1
N

n,m
e
ik(r
n
r
m
)
_
d
3
r

i
(rr
m
) E
i
+ v(r r
n
)
i
(rr
n
) .
(44)
Again, in the rst part (involving E
i
), we may neglect orbital
overlap. For the second term, involving v(r r
n
), the over-
lap should be included, but only to the nearest neighbors of
each atom (why?). In the simplest case, where the orbitals
i
,
are s-orbitals, then we can use this symmetry to reduce the
complexity of the problem to just two more integrals since the
hybridization (B
i
) will be the same in all directions.
A
i
=
_

i
(r r
n
)v(r r
n
)
i
(r r
n
)d
3
r ren. E
i
(45)
18
A
i
B
i
B
i
B
i
B
i
Figure 11: A simple cubic tight binding lattice composed of s-orbitals, with overlap
integral B
i
.
B
i
=
_

i
(r r
m
)v(r r
n
)
i
(r r
n
)d
3
r (46)
B
i
describes the hybridization of adjacent orbitals.
A
i
; B
i
> 0, since v(r r
n
) < 0 (47)
Thus
E(k) E
i
A
i
B
i

m
e
ik(r
n
r
m
)
sum over m n.n. to n
(48)
Now, if we have a cubic lattice, then
(r
n
r
m
) = (a, 0, 0)(0, a, 0)(0, 0, a) (49)
19
so
E(k) = E
i
A
i
2B
i
cos k
x
a + cos k
y
a + cos k
z
a (50)
Thus a band centered about E
i
A
i
of width 12B
i
is formed.
Near the band center, for k-vectors near the center of the zone
we can expand the cosines cos ka 1
1
2
(ka)
2
+ and let
k
2
= k
2
x
+ k
2
y
+ k
2
z
, so that
E(k) E
i
A
i
+ B
i
a
2
k
2
(51)
The electrons near the zone center act as if they were free with
a renormalized mass.
h
2
k
2
2m

= B
i
a
2
k
2
, i.e.
1
m

curvature of band (52)

For this reason, the hybridization term B
i
is often associated
with kinetic energy. This makes sense, from its origins of wave
function overlap and thus electronic transfer.
The width of the band, 12 B
i
, will increase as the electronic
overlap increases and the interatomic orbitals (core orbitals or
valance f and d orbitals) will tend to form narrow bands with
high eective masses (small B
i
).
20
First B.Z.
Fermi surface
Figure 12: Electronic states for a cubic lattice near the center of the B.Z. act like free
electrons with a renormalized mass. Hence, if the band is partially lled, the Fermi
surface will be spherical.
The bands are lled then by placing two electrons in each
band state ( with spins up and down). A metal then forms
when the valence band is partially full. I.e., for Na with a
1s
2
2s
2
2p
6
3s
1
atomic conguration the 1s, 2s and 2p orbitals
evolve into (narrow) lled bands, but the 3s
1
band will only
be half full, and thus it evolves into a metal. Mg 1s
2
2s
2
2p
6
3s
2
also metal since the p and s band overlaps the unlled d-band.
There are exceptions to this rule. Consider C with atomic con-
guration of 1s
2
2s
2
2p
2
. Its valance s and p states form a strong
sp
3
hybrid band which is further split into a bonding and anti-
21
a
E
E
1
E
1
E
2
2
E
1
A
2
A
2
12 B
1
12 B
k = 0
- /a /a
k
k
k
k
111
111
111
Atomic Potential
Tight Binding Bands
Figure 13: In the tight-binding approximation, band form from overlapping orbitals
states (states of the atomic potential). The bandwidth is proportional to the hy-
bridization B (12B for a SC lattice). More localized, compact, atomic states tend to
form narrower bands.
bonding band. (See Fig.14). Here, the gap is not tied to the
periodicity of the lattice, and so an amorphous material of C
may also display a gap.
The tight-binding picture can also explain the variety of fea-
tures seen in the DOS of real materials. For example, in Cu
(Ar)3d
10
4s the d-orbitals are rather small whereas the valence
s-orbitals have a large extent . As a result the s-s hybridization
22
a
P
sp antibonding
3
sp bonding
3
S
a
E
r
Figure 14: C (diamond) with atomic conguration of 1s
2
2s
2
2p
2
. Its valance s and p
states form a strong sp
3
hybrid band which is split into a bonding and anti-bonding
band.
B
ss
i
: is strong and the B
dd
i
is weak.
B
dd
i
B
ss
i
(53)
In addition the s-d hybridization is inhibited by the opposing
symmetry of the s-d orbitals.
B
sd
i
=
_

s
i
(r r
1
)v(r r
2
)
d
i
(r r
2
)d
3
r B
ss
i
(54)
where
s
i
is essentially even and
d
i
is essentially odd. So B
sd
i

B
ss
i
. Thus, to a rst approximation the s-orbitals will form a
very wide band of mostly s-character and the d-orbitals will
form a very narrow band of mostly d-character. Since both the
23
+ +

+
1
2
+ +

+ +

d
s
D(E)
Figure 15: Schematic DOS of Cu 3d
10
4s
1
. The narrow d-band feature is split due to
crystal elds.
s and d bands are valance, they will overlap leading to a DOS
with both d and s features superimposed.
4 Photo-Emission Spectroscopy
The electronic density of electronic states (especially for oc-
cupied states), and to a less extent band structure, are very
important for illuminating the interesting physics of materials.
As we saw in Chap. 6, an enhanced DOS at the Fermi sur-
face indicates an enhanced electronic mass, and if D(E
F
) = 0,
we have an insulator (semiconductor). The eective electronic
24
h
d
detector
synchrotron
r
material
sample
V
e
Figure 16: XPS Experiment: By varying the voltage one may select the kinetic
energy of the electrons reaching the counting detector.
mass also varies inversely with the curvature of the bands. The
density of states away from the Fermi surface can allow us to
predict the properties of the material upon doping, or it can
yield information about core-level states. Thus it is important
to be able to measure D(E). This may be done by x-ray pho-
toemission (XPS), UPS or PS in general. The band dispersion
E(k) may also be measured using angle-resolved photoemission
(ARPES) where angle between the incident radiation and the
25
detector is also measured.
The basic idea is that a photon (usually an x-ray) is used
to knock an electron out of the system (See gure 17.) Of
E
h - E
b
h - E -
b
D(E)
Intensity(E)
Kinetic Energy of electrons
h -
X-ray
E
b
Figure 17: Let the binding energy be dened so that E
b
> 0, = work function, then
the detected electron intensity I(E
kin
h ) D(E
b
)f(E
b
)
course, in order for an electron at an energy of E
b
below the
Fermi surface to escape the material, the incident photon must
have an energy which exceeds E
b
and the work function of
the material. If h > , then the emitted electrons will have
a distribution of kinetic energies E
kin
, extending from zero to
26
h. From Fermis golden rule, we know that the probability
per unit time of an electron being ejected is proportional to
the density of occupied electronic states times the probability
(Fermi function) that the electronic state is occupied
I(E
kin
) =
1
(E
kin
)
D(E
b
)f(E
b
)
D(E
kin
+ h)f(E
kin
+ h) (55)
Thus if we measure the energy and number of ejected particles,
then we know D(E
b
).
phonon Coulombic
interation
Secondary electrons
e
e
Figure 18: Left: Origin of the background in I(E
kin
. Right: Electrons excited deep
within the bulk scatter so often that they rarely escape. Thus, most of the signal I
originates at the surface, which must be clean and representative of the bulk.
There are several problems with this procedure. First some
27
of the photon excited particles will scatter o phonons and elec-
tronic excitations within the material. Since these processes can
occur over a very wide range of energies, they will produce a
broad featureless background in N(E
k
). Second, due to these
0 1 2 3 4
E
kin
0
2
4
6
I
(
E
k
i
n
)
background subtracted
background
raw data
h-
Figure 19: In Photoemission, we measure the rate of ejected electrons as a function
of their kinetic energy. The raw data contains a background. Once this is subtracted
o, the subtracted data is proportional to the electronic density of states convolved
with a Fermi function I(E
kin
) D(E
kin
+ h)f(E
kin
+ h).
secondary scattering processes, it is very unlikely that an elec-
tron which is excited deep within the bulk, will ever escape from
28
measure
h
E
kin
e
Figure 20: BIS E
kin
= h E
b
, E
b
= h E
kin

the material. Thus, we only learn about D(E) near the surface
of the material. Therefore it is important for this surface to be
clean so that it is representative of the bulk. For this reason
these experiments are often carried out in ultra-high vacuum
conditions.
We can also learn about the electronic states D(E) above the
Fermi surface, E > F
F
, using Inverse Photoemmision. Here,
an electron beam is focussed on the surface and the outgoing
us of photons are measured.
29