Chapter 7: The Electronic Band Structure of Solids: Bloch & Slater March 2, 2017
Chapter 7: The Electronic Band Structure of Solids: Bloch & Slater March 2, 2017
Chapter 7: The Electronic Band Structure of Solids: Bloch & Slater March 2, 2017
March 2, 2017
Contents
1 Symmetry of ψ(r) 2
4 Photo-Emission Spectroscopy 16
5 Anderson Localization 20
1
Free electrons -FLT Band Structure
V(r)
V(r) = V
0
E E
Ef metal
E insulator
E f
f
Ef "heavy" metal
D(E) D(E)
Figure 1: The additional effects of the lattice potential can have a profound effect on
the electronic density of states (RIGHT) compared to the free-electron result (LEFT).
In the last chapter, we ignored the lattice potential and considered the effects of
a small electronic potential U . In this chapter we will set U = 0, and consider the
effects of the ion potential V (r). As shown in Fig. 1, additional effects of the lattice
potential can have a profound effect on the electronic density of 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 ψ(r)
From the symmetry of the electronic potential V (r) one may infer some of the prop-
erties of the electronic wave functions ψ(r).
2
Due to the translational symmetry of the lattice V (r) is periodic
V (r) = V (r + rn ), rn = n1 a1 + n2 a2 + n3 a3 (1)
h̄2 2
Hψ(r) = − ∇ + V (r) ψ = Eψ (3)
2m
X h̄2 k 2 X 0
X
⇒ Ck eik·r + Ck0 VG ei(k +G)·r = E Ck eik·r , k0 → k − G (4)
k
2m k0 G k
or
( )
h̄2 k 2
X X
eik·r − E Ck + VG Ck−G = 0∀r
k
2m G
X X X (5)
Since this is true for any r, it must be that
2 2
X X X h̄ k X
− E Ck + VG Ck−G = 0, ∀k (6)
2m G
First B.Z. Thus the potential acts to couple each Ck only with its
reciprocal space translations Ck+G and the problem
Figure 2: The potential acts
decouples in to N independent problems for each k
to couple each Ck with its
in the first BZ. I.e., each of the N problems has a
reciprocal space translations
solution which is a sum over plane waves with wave
Ck+G (i.e. x → x, • → •,
vectors that differ only by G. Thus the eigenvalues
and
→
) and the prob-
may be indexed by k.
lem decouples into N indepen-
dent problems for each k in Ek = E(k), I.e. k is still a good q.n.! (7)
the first BZ.
3
We may now sum over G to get ψk with the eigenvector sum restricted to recip-
rocal lattice sites k, k + G, . . .
!
X X
ψk (r) = Ck−G ei(k−G)·r = Ck−G e−iG·r eik·r (8)
G G
Note that if V (r) = 0, U (r) = √1 . This result is called Bloch’s Theorem; i.e., that
V
ψ may be resolved into a plane wave and a periodic function. Its consequences as
follows:
!
−i(G0 −k−G)·r −iG00 ·r
X X
ψk+G (r) = Ck+G−G0 e = Ck−G00 e eik·r
G0 G00
00 0
= ψk (r), where G ≡ G − G (10)
Thus E(k+G) = E(k) : E(k) is periodic then since both ψk (r) and E(k) are periodic
in reciprocal space, one only needs knowledge of them in the first BZ to know them
everywhere.
First BZ 2π/a
I.e., the possible electron states are not restricted to a single parabola, but can be
found equally well on paraboli shifted by any G vector. In 1-d, since E(k) = E(k+G),
it is sufficient to represent this in the first zone only. For example in a 3-D cubic lattice
the energy band structure along kx (ky = kz = 0) is already rather complicated within
the first zone. (See Fig.4.)
The effect of VG can now be discussed. Let’s return to the 1-d problem and
consider the edges of the zone where the paraboli intersect. (See Fig. 3.) An electron
π
state with k = a
will involve at least the two G values G = 0, 2π
a
. Of course, the
exact solution must involve all G since
2 2
h̄ k X
− Ek Ck + VG Ck−G = 0 (15)
2m G
We can generally take V0 = 0 since this just sets a zero for the potential. Then, those
5
First B.Z.
-π⁄a π⁄a
−π⁄a π⁄a kx
Figure 4: The situation becomes more complicated in three dimensions since there are
many more bands and so they can cross the first zone at lower energies. For example
in a 3-D cubic lattice the energy band structure along kx (ky = kz = 0) is already
rather complicated within the first zone.
h̄2 k2
G for which Ek = Ek−G ≈ 2m
are going to give the largest contribution since
X Ck−G
Ck = VG h̄2 k2 (16)
G 2m
− Ek−G
Ck−G1
Ck ∼ VG1 h̄2 k2 (17)
2m
− Ek−G1
X Ck−G1 −G
Ck−G1 = VG h̄2 k2 (18)
G 2m
− Ek−G−G1
Ck
Ck−G1 ∼ V−G1 h̄2 k2 (19)
2m
− Ek
Thus to a first approximation, we may neglect the other Ck−G , and since VG = V−G
(so that V (r) is real) |Ck | ≈ |Ck−G1 | other Gk−G
X (eiGx/2 + e−iGx/2 ) ∼ cos πx
ψk (r) = Ck−G ei(k−G)·r ∼ a
(20)
(eiGx/2 − e−iGx/2 ) ∼ sin πx
G a
The corresponding electron densities are sketched in Fig. 5. Clearly ρ+ has higher
density near the ionic cores, and will be more tightly bound, thus E+ < E− . Thus a
G
gap opens in Ek near k = 2
.
6
ρ+ (x)
E
Gap!
ρ− (x)
V(x)
D(E)
Figure 5: ρ+ ∼ cos2 (πx/a) has higher density near the ionic cores, and will be more
G
tightly bound, thus E+ < E− . Thus a gap opens in Ek near k = 2
.
h̄2
X X
2
Ck−G Ek − |k − G| = VG0 Ck−G−G0 = VG0 −G Ck−G0 (21)
2m G0 G0
P
0 VG0 −G Ck−G0
Ck−G = G 2 (22)
h̄
Ek − 2m |k − G|2
h̄2 k2
To a first approximation (VG ' 0) let’s set E = 2m
(a free-electron energy) and
ignore all but the largest Ck−G ; i.e., those for which the denominator vanishes.
k2 = |k − G|2 , (23)
or in 1-d
2π 2 π
k2 = (k − ) or k = − (24)
a a
This is just the Laue condition, which was shown to be equivalent to the Bragg
condition. I.e., the strongest perturbation to the free-electron picture occurs for
7
highly perturbed
Figure 6: We can satisfy the condition Ek ' Ek−G only for k on the edge of the B.Z..
Here the lattice potential strongly perturbs the electronic states (i.e. more than one
Ck−G is finite).
states with energies at the edge of the first B.Z. Thus the equation above also tells us
that Ck and Ck−G1 are the most important coefficients (if this electronic state was
unperturbed, only Ck would be important). Thus approximately for VG ∼ 0, V0 ≡ 0
and for k near the zone boundary
h̄2 k 2
G=0 Ck E − = VG1 Ck−G1 (25)
2m
h̄2 |k − G1 |2
G = G1 Ck−G1 E − = V−G1 Ck , (26)
2m
Again, ignore all other CG . This is a secular equation which has a nontrivial solution
iff 2
h̄ k2
2m − E VG1
2 =0 (27)
h̄ |k−G1 |2
V−G1 − E
2m
or
0
Ek − E
VG1
=0 (28)
0
V−G1 Ek−G −E
1
(V−G = VG∗ , so thatV (r) ∈ <)
(Ek0 − E)(Ek−G
0
1
− E) − |VG1 |2 = 0 (29)
8
Ek0 Ek−G
0 0 0
+ E 2 − |VG1 |2 = 0
1
− E E k + Ek−G 1
(30)
21
1 1 2
E± = E0 + Ek0 ± E 0 − Ek0 + |VG1 |2
(31)
2 k−G1 4 k−G
0
At the zone boundary, where Ek−G1
= Ek0 , the gap is
∆E = E+ − E− = 2|VG1 | (32)
And the band structure looks something like Fig. 7. Within this approximation, the
E
k
e−
2 VG k
-π/a 0 π/a k
Figure 7:
gap, or forbidden regions in which there are no electronic states arise when the Bragg
condition (kf − k0 = G) is satisfied.
| − 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 prob-
lem, we see that gaps arise due to enhanced electron-lattice back scattering for k near
the zone edge. However, 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 constructing a band structure theory. It is called
the tight-binding approximation.
9
State
Energies
Separation
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.
V (r)
A
E i ψi
r r
10
eigenstates φi , and eigen energies Ei . The unperturbed Schroedinger equation for the
nth atom is
HA (r − rn ) · φi (r − rn ) = Ei φi (r − rn ) (34)
There is a weak perturbation v(r−rn ) coming from the atomic potentials of the other
atoms rm 6= rn
h̄2 ∇2
H = HA + v = − + VA (r − rn ) + v(r − rn ) (35)
2m
X
v(r − rn ) = VA (r − rm ) (36)
m6=n
11
Where φk must be a Bloch state φk+G = φk which dictates our choice an = eik·rn .
Thus at this level of approximation we have no free parameters to vary to minimize
hφk |H|φk i / hφk |φk i ≈ E(k).
Using φk as an approximate state the energy denominator hφk |φk i, becomes
X Z
ik·(rn −rm )
hφk |φk i = e d3 rφ∗i (r − rm )φi (r − rn ) (42)
n,m
Let’s imagine that the valance orbital of interest, φi , has an very small overlap with
adjacent atoms so that
φ (r-r )
i 1 φi (r-r2 )
Figure 10: In the tight binding approximation, we assume that the atomic orbitals
of adjacent sites have a very small overlap with each other.
XZ
hφk |φk i ' d3 rφ∗i (r − rn )φi (r − rn ) = N (43)
n
Again, in the first part (involving Ei ), we may neglect orbital overlap. For the second
term, involving v(r − rn ), the overlap should be included, but only to the nearest
neighbors of each atom (why?). In the simplest case, where the orbitals φi , are s-
orbitals, then we can use this symmetry to reduce the complexity of the problem to
12
B
i
Bi
B A
i i
B
i
Figure 11: A simple cubic tight binding lattice composed of s-orbitals, with overlap
integral Bi .
just two more integrals since the hybridization (Bi ) will be the same in all directions.
Z
Ai = − φ∗i (r − rn )v(r − rn )φi (r − rn )d3 r ren. Ei (45)
Z
Bi = − φ∗i (r − rm )v(r − rn )φi (r − rn )d3 r (46)
Thus
X
E(k) ' Ei − Ai − Bi eik(rn −rm ) sum over m n.n. to n (48)
m
so
E(k) = Ei − Ai − 2Bi {cos kx a + cos ky a + cos kz a} (50)
Thus a band centered about Ei − Ai of width 12Bi is formed. Near the band center,
for k-vectors near the center of the zone we can expand the cosines cos ka ' 1 −
13
1
2
(ka)2 + · · · and let k 2 = kx2 + ky2 + kz2 , so that
The electrons near the zone center act as if they were free with a renormalized mass.
h̄2 k 2 1
∗
= Bi a2 k 2 , i.e. ∝ curvature of band (52)
2m m∗
For this reason, the hybridization term Bi is often associated with kinetic energy.
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 filled, the Fermi
surface will be spherical.
This makes sense, from its origins of wave function overlap and thus electronic trans-
fer.
The width of the band, 12 Bi , 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 effective masses (small Bi ).
The bands are filled 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 1s2 2s2 2p6 3s1 atomic configuration the 1s, 2s and 2p orbitals evolve into
(narrow) filled bands, but the 3s1 band will only be half full, and thus it evolves into
a metal. Mg 1s2 2s2 2p6 3s2 also metal since the p and s band overlaps the unfilled
14
Atomic Potential Tight Binding Bands
E Ek
2 111
E 111
1
A2
k 12 B
k=0
E 1k
111
E
2
a A1
12 B
k
- π/a π/a
Figure 13: In the tight-binding approximation, bands 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.
d-band. There are exceptions to this rule. Consider C with atomic configuration of
1s2 2s2 2p2 . Its valance s and p states form a strong sp3 hybrid band which is further
split into a bonding and anti-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 features seen in the DOS
of real materials. For example, in Cu (Ar)3d10 4s the d-orbitals are rather small
whereas the valence s-orbitals have a large extent . As a result the s-s hybridization
Biss : is strong and the Bidd is weak.
In addition the s-d hybridization is inhibited by the opposing symmetry of the s-d
orbitals. Z
Bisd = φsi (r − r1 )v(r − r2 )φdi (r − r2 )d3 r Biss (54)
where φsi is essentially even and φdi is essentially odd. So Bisd Biss . Thus, to a
first 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
15
E
sp3antibonding
sp3 bonding
ra a
Figure 14: C (diamond) with atomic configuration of 1s2 2s2 2p2 . Its valance s and p
states form a strong sp3 hybrid band which is split into a bonding and anti-bonding
band.
D(E)
d
1 +
− −
2
+ + + +
− −
−
s
+ +
−
Figure 15: Schematic DOS of Cu 3d10 4s1 . The narrow d-band feature is split due to
crystal fields.
the 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 occupied 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 surface indicates an
enhanced electronic mass, and if D(EF ) = 0, we have an insulator (semiconductor).
16
synchrotron
d
hω r
detector
α e
material
sample
Figure 16: XPS Experiment: By varying the voltage one may select the kinetic
energy of the electrons reaching the counting detector.
The effective electronic 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 photoemission
(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 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 figure 17.) Of course, in order for an electron at an energy of
Eb below the Fermi surface to escape the material, the incident photon must have an
energy which exceeds Eb and the work function φ of the material. If h̄ω > φ, then
the emitted electrons will have a distribution of kinetic energies Ekin , extending from
zero to h̄ω − φ. From Fermi’s golden rule, we know that the probability per unit
time of an electron being ejected is proportional to the density of occupied electronic
17
hω - Eb -φ
X-ray
E
hω - Eb
Eb
Intensity(E)
D(E)
Kinetic Energy of electrons hω - φ
Figure 17: Let the binding energy be defined so that Eb > 0, φ = work function, then
the detected electron intensity I(Ekin − h̄ω − φ) ∝ D(−Eb )f (−Eb )
states times the probability (Fermi function) that the electronic state is occupied
1
I(Ekin ) = ∝ D(−Eb )f (−Eb )
τ (Ekin )
∝ D(Ekin + φ − h̄ω)f (Ekin + φ − h̄ω) (55)
Thus if we measure the energy and number of ejected particles, then we know D(−Eb ).
Secondary electrons
phonon Coulombic
interation
e
Figure 18: Left: Origin of the background in I(Ekin . 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 of the photon excited
18
particles will scatter off phonons and electronic 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 (Ek ).
6
background subtracted
background
’’raw’’ data
4
I(Ekin)
0
0 1 2 3 4
Ekin hω-φ
19
5 Anderson Localization
In this chapter, we have seen that electrons do not
scatter off a perfect periodic lattice, unless the Bragg
condition is satisfied opening a band gap. If not, ac-
cording to Bloch, they form extended states composed
of a plane wave multiplied by a periodic function. So,
the electronic wavefunction (and charge!) is spread
over the entire system with equal amplitude on each
site! Such states are characteristic of a metal and are
called “extended states”.
On the other hand, we know that the impact of
disorder on such a system can be significant. As il-
lustrated in Fig. 20 there are many different types of
Figure 20: Examples disorder,
disorder, including substitutional disorder, as in the
including substitution, inter-
replacement of Si by B or P in Si semiconductors used
stitial, vacancies. In addition,
in your laptop which is responsible for roughly one to
not shown, there are exter-
four trillion dollars of the US economy. Disorder is
nal disorder potentials, amor-
not a nuisance, rather it is very often used to tune or
phous systems, etc.
control the properties of materials.
In fact very strong disorder can even destroy the
metal which contains it. This means that Bloch’s theorem, which was derived in the
absence of disorder, breaks down and the extended states that are spread over the
entire system become exponentially localize states centered at one position in the
material. In the most extreme limit, this is obviously true. Consider a single orbital
that you pull down in energy so that it falls below (or above) the continuum in the
density of states. Clearly, such a state cannot hybridize with other states since there
are none at the same energy. Thus, any electron on this orbital is localized, and the
electronic DOS at this energy will be a delta function.
20
Anderson has shown that other
types of disorder can lead to the lo-
calization of electronic states, as il-
lustrated in Fig. 21. Mott argued
that the extended states would be
Figure 21: A periodic potential (left) leads to
separated from the localized states
extended states; whereas, strong disorder will
by a sharp mobility (localization)
lead to exponentially localized states (right).
edge in energy. His argument is
that scattering from disorder is elastic, so that the incoming wave and the
scattered wave have the same energy. On the other hand, nearly all scat-
tering potentials will scatter electrons from one wavevector to all others, since
the scattering potentials are local or nearly so. If two states, correspond-
ing to the same energy and different wavenumbers exist, then the scatter-
ing potential will cause them to mix, causing both to become extended.
These ideas have existed in one form
or another for over fifty years! The main
remaining challenge is to develop a com-
plete theory of localization. This has
been hampered by the lack of a clearly
identified order parameter, akin to m in
the theory of magnetism! Recently, there
has been significant progress along these
ideas, with the local typical density of
Figure 22: To understand localization, di-
states identified as the order parameter.
vide a system up into blocks. The average
To see this, imagine dividing the sys-
spacing of the energy levels of a block is ∆
tem up into blocks, as illustrated in
and the Fermi golden rule width of the lev-
Fig. 22. Here the average level spacing
els is Γ. If Γ ∆ then we have a metal
of the states in a block is ∆ and their
and if Γ ∆, an insulator).
average Fermi golden rule width is Γ. If
21
Γ ∆ then we have a metal since the
states at this energy have a significant probability of escaping from this block, and
the next one. Alternatively if Γ ∆ the escape probability of the electrons is low,
so that an insulator forms. So what does this mean in terms of the local electronic
density of states that are measured (i.e., via STM) at one site in the system? If I
measure the DOS at any site in a metal, it must be a continuum, at least at the
energy at question, since all states at that energy must be extended and therefore
accessible (c.f. Fig. 23). On the other hand, in a insulator, at any one site, the DOS
would “see” only the states that are accessible (within the localization length) and
since the number of these states is necessarily finite, the DOS at any one site would
be composed of a set of delta functions. Of course, if I go to another site, then
the distribution of the delta functions will be different, so if I average over all 1023
sites, then I again recover a continuum. I.e., the arithmatically averaged DOS is a
continuum in both a metal and an insulator.
On the other hand, the typical value of
the local DOS in a metal is very different
than the typical value in an insulator. Con-
sider again the local DOS in the metal and
insulator illustrated in Fig. 23. In the metal,
at any one energy the DOS at each site is a
continuum. It will change as one goes from
site to site, but the typical value, as the aver-
Figure 23: The local DOS in a metal
age value, will be finite. now reconsider the
(left) is a continuum; whereas, that in
local DOS in the insulator. It is composed of
an insulator is composed of a series of
a finite number of delta functions. For any
delta functions (right)).
energy in between the delta functions, the lo-
cal DOS is zero. Since the number of delta functions is again finite, the typical value
of the local DOS is zero. As a result, the order parameter for the Anderson metal-
insulator transition is the typical local DOS, which is zero in the insulator and finite
22
in the metal.
A stronger statement is also possi-
ble. Early on, Anderson realized that
the distribution of the density of states
in a strongly disordered metal would be
strongly skewed towards smaller values.
More recently, this distribution has been
demonstrated to be log normal. Perhaps
the strongest demonstration of this fact
was by the Vollhardt group[1], who illus-
trated the the DOS near the transition
has a log-normal distribution (Fig. 24)
Figure 24: The distribution of the local
over 10 orders of magnitude! Further-
density of states in a single-band Anderson
more, one may also show that the typi-
model with disorder strength γ. Near the
cal value of a log-normal distribution is
localization transition, γ = 16.5 the dis-
the geometric average (the geometric av-
tribution becomes log-normal (see also the √
erage of A and B is AB) which is par-
inset), while for values well below the tran-
ticularly easy to calculate and can serve
sition, γ = 3 is shown, the distribution is
as an order parameter.
normal.[1].
References
[1] Gerald Schubert, Jens Schleede, Krzysztof Byczuk, Holger Fehske, and Dieter
Vollhardt Phys. Rev. B 81, 155106 Published 8 April 2010.
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