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Contents
1 Lattice scattering
1.1 Bloch waves . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2 Band gap formation . . . . . . . . . . . . . . . . . . . . . . . .
1.3 Electron group velocity and effective mass . . . . . . . . . . .
1
2
3
5
12
Lattice scattering
In part I, we have seen how to construct energy band diagrams for an empty
lattice. In an empty lattice, the k values that the electrons can have are
continuous, i.e. there is no effect of the atoms. This is because the atom
potentials have been neglected in the empty lattice model. Now, we will
consider the effect of the lattice.
Let us start with the simple 1D lattice, as seen in figure 1. The atoms in
the lattice have a potential. Also, since the lattice is periodic the potential
is also periodic, given by the lattice constant a. The effect of this periodic
potential is to modify the electron wavefunction in the lattice.
In the FEG, with the empty lattice approximation, valence electrons are
delocalized and form an energy band, with continuous values of energies.
Electrons in these bands have an energy or wavevector distribution and are
represented by a plane wave equation and these electrons are called free
1
electrons.
(x) = A exp(ikx)
(1)
1.1
Bloch waves
(2)
~ = u(~r), where
The term, u~k (~r), has the periodicity of the lattice i.e. u(~r + R)
~ is a general lattice vector. This gives (~r + R)
~ = exp(i~k R)
~ (~r). This
R
theorem, which uses the periodicity of the lattice to construct electron wavefunctions, is called Bloch theorem, and these electrons are called Bloch
waves. They can be contrasted with plane waves, that are solutions for the
free electrons.
1.2
(3)
(4)
These two waves, have different energies in the presence of a lattice potential.
This is because + concentrates the electrons at the atomic cores and
concentrates the electrons between the atomic cores, see figure 2. + has
a lower energy than , since the negatively charged electrons are located
closer to the positively charged atomic cores. Thus, for the same value of k,
there are two standing waves with different energies i.e. a energy gap is
created at the Brillouin zone boundary.
This process can be extended to higher values of k i.e. /a, 2/a, 3/a and so
on. Thus, the continuous Evs.k band diagram for 1D becomes discontinuous
at the boundaries. This is shown in figure 3. The magnitude of the gap
depends on the atomic potentials. The reasoning that we developed for 1D
3
2
2
Figure 2: Schematic of +
and
along the 1D solid. In both cases the value
of k = /a. The two wavefunctions have different energies, since the spatial
distribution of the electron wave is different. This leads to the formation of
a band gap.
Figure 4: Formation of band gap for a 2D lattice in a reduced zone scheme (a)
Continuous k values. (b) Discontinuities are created at the BZ boundaries.
These open up forbidden energy gaps in the system.
can be extended to 2D lattices, figure 4. For the 2D lattice, gaps are formed
when the ~k in a certain direction intersects the BZ boundary. Since, this
occurs at different values of ~k, we get band gaps at different directions. These
band gaps can either overlap or not overlap, see figure 5. When there is no
overlap of the gaps, then there is a continuity in E vs. k, the conductivity
is high. If the gaps overlap, there is a certain forbidden energy regionin the
material, where electrons cannot exist. This is called the energy band gap.
The same concept can be extended to 3D lattices.
1.3
Consider a solid where there is a specific relation between E vs. k. For such a
system, it is possible to define a quantity called group velocity (vg ), which
defines the velocity of the wave packet that represents the electron. Group
velocity is given by the formula
vg =
1 dE
~ dk
(5)
For an electron obeying the free electron gas (FEG) model, i.e. E =
~2 k 2 /2me , equation 5 given vg = ~k/me . Since, ~k represents the momentum, dividing that by the electron mass, gives the velocity, and it increases
linearly with k. For systems that do not obey the FEG model, equation 5
can be used to calculate vg .
Starting with equation 5, it is possible to relate a mass term with the energy
5
and wavevector.
dvg
1 d2 E
=
dt
~ dk dt
2
dvg
1 d E dk
=
dt
~ dk 2 dt
(6)
The left hand term, dvg /dt, is the acceleration, a, (time derivative of the
velocity). which can be written as a force term divided by the mass. Rearranging the right had side,
1 d2 E
dk
a = 2
~
(7)
~
dk 2
dt
The term ~ dk/dt represents the force acting on the electron, hence the mass
term in the above equation is given by
me =
~2
d2 E
dk 2
(8)
This mass term, me , is called the effective mass of the electron. It represents the effect of the atoms on the motion of the electrons in the lattice.
Effective mass depends on the energy of the electron (and hence the wavevector). In the FEG model, me = me , i.e. the effective mass is equal to the rest
mass of the electron. But, under the NFEG model, effective mass deviates
from the rest mass of the electron.
For a 1D solid, the relation between E vs. k, group velocity, and effective
mass, in the BZ is plotted in figure 6. For low k, the FEG model is valid.
In such cases, vg is a linear function of k and me is a constant and equal to
me . As k approaches the BZ boundary, the effect of the lattice is felt by the
electrons. Hence, the group velocity starts to decrease and reaches zero at
the boundary (standing waves). Correspondingly, me also increases and has
an inflection point when vg is maximum. The argument for a 1D crystal can
be extended to 2D and 3D, but it is important to note that for these solids
vg and me are direction dependent.
The nearly free electron gas (NFEG) model is an extension of the FEG model
and explains the formation of energy band gaps in a material. It should be
7
Figure 6: E vs. k, vg vs. k, and me vs. k within the BZ for a 1D lattice. For
small k, the FEG model holds, so that vg is linear with k and effective mass
is constant and equal to me . Deviations start to appear, when the value of
k starts to approach the BZ boundary.
possible to explain the FEG model, as a particular case of NFEG, where the
lattice interactions are neglected. This can be done by comparing the Fermi
wavevector, kF , to the wavevector corresponding to the BZ boundary, kBZ .
This will also help understand, the filling of the energy band with electrons.
Let us go back to a 1D lattice, i.e. a linear chain of atoms. The presence of
the atoms creates gaps in the energy band diagram. There are three schemes
for depicting this, see figure 7. The extended and reduced zone schemes have
been discussed before. The periodic zone scheme is obtained by repeating
the reduced zone scheme throughout the lattice. A horizontal line drawn in
figure 7(c), will mark constant k or constant E lines. This scheme is easier
to visualize electron motion through the lattice.
9
Figure 8: E vs. k for a 1D solid, with electron filling different energy levels,
depending on the valency. Odd number fillings are metals, while even nos
are non-metal.
Let there be N atoms in this 1D lattice. Then, there are N orbitals and each
orbital can take 2 electrons (of opposite spin). Let the valency of the atom
be 1, i.e.each atom contributes one electron. Then, the first band is half full
and there are empty states available in that band, for the electron to occupy.
This makes a 1D chain of atoms, with valency 1, a metal. If the valency is 2,
then the first band is completely full, since there are 2N electrons, and there
is an energy band gap separating the full and empty states, see figure 7, and
the 1D solid with valency 2 is an insulator/semiconductor. The magnitude
of the gap depends on the strength of the atomic potential. If there are 3
electrons, the first band is completely full and the second band is half empty,
once again a metal, and so on. Therefore, for a simple 1D solid, odd valency
atoms are metals, while even valency atoms are non-metals. The electron
filling is shown in figure 8.
The same concept can be extended to 2D and 3D lattices. For these lattices,
there are different E vs. ~k diagrams for the different directions. If the k values
in the different directions do not overlap, there is a forbidden energy gap that
extends in all directions and we have an insulator/semiconductor. If there is
considerable overlap, such that we have continuous values of k, by choosing
different directions, then we get a metal and if there is a small overlap, we get
a semi-metal. Whether a given metal behaves as a free electron gas, depends
10
on the relation between the magnitude of the Fermi wavevector, |kF |, and its
relation to the BZ boundary, kBZ .
Consider two solids that have bcc structure, Na and Ba, with valency 1 and
2 respectively. Let n be electron density per unit volume. If a is the lattice
constant, then n is related to a by
n =
2Z
a3
(9)
where Z is the valency. The factor, 2, comes from the fact that a bcc lattice
has 2 atoms in the unit cell, or the volume of the primitive unit cell is a3 /2.
According to the FEG model, n can be related to kF , the Fermi wavevector
by
(6 2 Z)1/3
(10)
kF = (3 2 n)1/3 =
a
Given that the real lattice is bcc, then the reciprocal lattice is fcc, with a
unit cell vector a~ = 2/a (
x + y). Hence, the distance from the center of
the reciprocal lattice
to the BZ boundary, kBZ is half the magnitude of a~ ,
equal to (/a) 2.
Compare the two quantities, kF and kBZ , for the two elements. For Na,
kF < kBZ . Hence, the Fermi sphere lies within the BZ and is not influenced by
the formation of energy gaps at the BZ boundary. So, the FEG model works
well for Na, with the lattice effect incorporated into the electron effective
mass. For Ba, kF > kBZ and the Fermi level penetrates the BZ boundary and
lies in the 2nd BZ (formed using the second nearest neighbors). Hence, the
Fermi surface is distorted by the energy gap at the BZ boundary. Hence, Ba,
with 2 electrons per atom, has a lower conductivity than Na. The difference
is nearly an order of magnitude, since only those electrons in the second BZ
of Ba can conduct.
The BZ is constructed by taking the vectors from the center to the nearest
neighbors and drawing perpendicular bisectors to them. This is called the
first Brillouin zone. Similarly, vectors can be drawn to the next nearest
neighbors and perpendicular bisectors drawn to those. This would be called
the second BZ and so on. It is easier to see these BZs for a 2D square lattice.
The first and second BZ for a 2D square lattice is shown in figure 9(a). kF
represents the Fermi wavevector for a given solid. In the FEG model, a
constant kF surface would be the surface of a sphere for a 3D lattice and and
the circumference of a circle for a 2D lattice.
When the Fermi surface lies well within the BZ boundary, it is not affected
by the lattice and the Fermi surface remains spherical. This is the case
when the FEG model can be used for that particular material. As kF starts
approaching the BZ boundary, it starts to get distorted due to the lattice
11
Figure 9: (a) The first and second BZ for a 2D square lattice. The second
BZ is marked. (b) Different values of kF and its relation to kBZ . As kF
approaches closer to kBZ , the Fermi surface starts to get distorted.
Real solids can have a complex Fermi surface, which are hard to visualize.
One way to compare various solids, is to look at the density of states (DOS)
function and its deviation from the FEG model. In the FEG model,
DOS,
g(E), is a monotonically increasing function of energy i.e. g(E) E. In
the NFEG model, this can no longer be true since there are forbidden energy
gaps and as the energy nears the BZ boundary there is electron scattering.
Then, g(E) decreases near the BZ boundary and should reach zero at the BZ
boundary. This is shown in figure 12. It is possible to show the difference
between the different metals, using the density of states plot and the Fermi
energy.
Figure 13 shows the DOS function for alkali metals, valency of one. The
12
Figure 10: The Fermi surface of Cu. Most of the Fermi surface is
a sphere, lies within the first BZ. There is some distortion along the
[111] direction when kF comes close to the BZ boundary. For Cu,
the FEG model works well since this distortion is minimal. Source
https://www.learner.org/courses/physics/unit/text.html?unit=8&secNum=2
Figure 11: The Fermi surface of Al. Al, has a valency of three and the Fermi
surface encloses the first BZ, second BZ, and parts of the third BZ. Source
http://www.phys.ufl.edu/ tschoy/r2d2/Fermi/Fermi.html
13
Figure 12: Change in DOS near the BZ boundary. There is a peak near the
boundary and then g(E) starts to decrease, due to Bragg scattering. At the
boundary g(E) goes to zero.
There are various techniques for measuring the density of states, Fermi surface distribution, Fermi energy, and effective mass. These are used in con14
Figure 13: DOS function, g(E), for a monovalent metal like alkali metals.
The band is half full in this case.
Figure 14: DOS function, g(E), for a bivalent material. (a) If there is an
overlap between the first and second BZ, then it is a metal. (b) If there is
no overlap of the band, then we get an insulator.
Figure 15: DOS function, g(E), for a trivalent material. The first BZ is
completely full and the second BZ is partially full.
15
4.1
Hall measurements
(11)
carriers, in this case electrons, travel in the negative x direction, under the
influence of the potential. An external magnetic field is now applied in the
positive z direction. Using equation 11, this produces a deflection in the
negative y direction.
q = e Electron has negative charge
Electrons are moving in negative x direction
~v = vx x
~ = Bz(z)
B
(12)
(13)
The current density (Jx ), i.e. current per unit area, can be related to the
velocity of the electrons, vx , and the electron density, n, i.e. no. of electrons
per unit volume.
Jx = nevx
(14)
By convention, Jx , is in the opposite direction to the flow of electrons. Using
equations 13 and 14 it is possible to write
eEH =
Jx
Bz
n
1
Jx Bz
ne
EH
1
=
= RH
Jx Bz
ne
EH =
(15)
This quantity, RH , is called the Hall coefficient and can be measured experimentally, from the applied magnetic field, measured current and developed
Hall field. This is then used to calculate the electron density, which can be
used to calculate the valency. Some values for different metals are listed in
table 1. Most metals have negative RH , since the charge carriers are electrons
and the values tabulate well with the known valency. For semiconductors,
RH can be negative or positive. This depends on the type of charge carriers,
electrons or holes. Hall measurements do not provide information about the
density of states or the Fermi surface.
17
RH (exp)
(1011 m3 A1 s1 )
-9.0
-7.2
-5.5
-3.5
-9.4
-25
n
Atomic density valency
(1028 m3 )
(1028 m3 )
6.94
5.85
1.18
8.68
5.90
1.47
11.4
8.45
1.35
17.8
6.02
2.97
6.65
4.30
1.54
2.5
2.65
0.95
Figure 17: (a) Schematic of the photo emission process. The kinetic energy
of the emitted electrons depends on their binding energy and the intensity
depends on the density of occupied states (b) Experimental UPS spectrum
from Cu, compared to the calculated DOS.
4.2
(16)
where is the work function, EF is the Fermi energy and Eb is the binding
energy, with respect to the bottom of the band (taken as reference). The
18
Figure 18: Angle resolved UPS, showing the resolution of the emitted electron wavevector into different components, parallel and perpendicular to the
surface.
19
(17)
Figure 19: (a) Movement of a free electron in a magnetic field (b) Movement
of a nearly free electron in a magnetic field. In both cases, the field causes a
deflection but not a change in energy so that the electron moves in a constant
energy surface.
4.3
Cyclotron resonance
(18)
(19)
T is the time of revolution, and is related to the cyclic integral over the
constant energy surface. Measurement of T , provides information on the
electron effective mass, me . This can be seen by considering the FEG equation, where Fermi velocity is a constant and independent of direction, and
vF = ~kF /me . Then, the cyclic integral in equation 19 becomes
T =
2me
~
(2kF ) =
eBvF
eB
(20)
eB
2
=
T
me
(21)
Thus, measuring the cyclotron frequency gives the electron effective mass at
the Fermi energy.
21