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SOLID STATE PHYSICS

MODULE 1; PART-II; LECTURE 4
PH101 AUTUMN 2020
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 Outline of the presentation
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 Quantum Free Electron Theory

 Fermi-Dirac Distribution Function

 Effect of Temperature on Fermi Function

 Band Theory of Solids

 Reciprocal Lattice, Wigner-Seitz Cell, Brilluoin

Zones
 Understanding Insulators, Semi-Conductors,
Conductors
 Semi-Conductors – Different types
 Quantum Free Electron Theory
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 It was proposed by Somerfield in 1928.

 The concept of free electrons was retained but, instead of using
Maxwell Boltzmann statistics, Fermi-Dirac Statistics were applied.
 Electrons obeyed laws of quantum theory instead of classical
mechanics.
 It was also postulated here that the potential field inside a metal
was not uniform but varies periodically with the periodicity of the
crystal.
 This theory also failed as it could not explain (1) why some
materials are metals, some are good insulators and (2) why atomic
arrays in crystals including metals, should prefer certain structures
and not others.
 Why we need Fermi Dirac Distribution Function?
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 Fermi Dirac Distribution Function
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 f(E)

T=0
EF
1

E1
E E0
EF
(a) (b)

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 Effect of Temperature on Fermi Function
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 Case-I: Absolute zero and E < EF

1 1
𝑓 𝐸 = = =1
1 + 𝑒 −∞ 1 + 0
 Case-II: Absolute zero and E > EF
1 1
𝑓 𝐸 = = =0
1 + 𝑒∞ 1 + ∞

 Case-III: At temperatures slightly above T = 0 and

E = EF
1 1
𝑓 𝐸 = = = 0.5
1 + 𝑒0 1 + 1

 Case-IV: At high temperatures, kBT >> EF, or T→ ∞,

both classical and quantum statistics give same
results. …A few problems.
 Density of States
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 The ability of a metal to conduct electricity depends on how many

quantum energy states are available to electrons and what the
energies of those states are.
 Number of states in a unit volume of a sample having energies in
the range from E to E+dE. This is N(E)dE, where N(E) is the number
of states at energy E.
 Unit is states per cubic meter per electron volt (m-3eV-1)
 Consider a three dimensional space with
coordinates 𝑛𝑥 , 𝑛𝑦 , 𝑛𝑧 , 𝑛2 = 𝑛𝑥2 + 𝑛𝑦2 + 𝑛𝑧2
 The total number of points inside the sphere
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of radius n is 𝜋𝑛3
3
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 The energy states available within one octant of the sphere of

1 4
radius n and with energy E will be 𝜋𝑛3
8 3
 Similarly, energy states within one octant of the sphere of radius
1 4
n+dn and with Energy E+dE will be 𝜋(𝑛 + 𝑑𝑛)3
8 3
 So number of energy states available within the spheres of radii n
and n+dn having energy values lying between E and E+dE,
1 4 3
1 4 3 𝜋
𝑁 𝐸 = 𝜋(𝑛 + 𝑑𝑛) − 𝜋𝑛 = 𝑑𝑛3 + 3𝑛2 𝑑𝑛 + 3𝑛𝑑𝑛2
8 3 8 3 6
 Neglecting higher powers of dn, we get
𝜋 𝜋 𝜋
 𝑁 𝐸 𝑑𝐸 = 3𝑛2 𝑑𝑛 = 𝑛2 𝑑𝑛 = 𝑛(𝑛𝑑𝑛)
6 2 2
 Suppose a particle (electron) is confined in a
2
cubical
2
metal piece of side a, then the
ℎ 𝑛
energy of electron within the cube is 𝐸 = 2
8𝑚𝑎
1/2
10 8𝑚𝑎2 8𝑚𝑎2
 Rearranging, 𝑛2= 2 𝐸, 𝑛 = 2 𝐸1/2
ℎ ℎ
8𝑚𝑎2
 Differentiating,𝑛𝑑𝑛 = 𝑑𝐸
2ℎ2
 Substituting these values in the earlier equation,
3/2
𝜋 8𝑚𝑎2 1/2 𝑑𝐸
𝑁 𝐸 𝑑𝐸 = 𝐸
4 ℎ2
 Based on Pauli’s exclusion principle, two electrons can occupy a given state (one
with spin up and one with spin down), thus,
3/2
𝜋 8𝑚𝑎2
𝑁 𝐸 𝑑𝐸 = 2 × 2
𝐸1/2 𝑑𝐸
4 ℎ
 And number of energy states present in unit volume (a3=1) having energy values
lying in between E and E+dE, known as density of states is given by,
4𝜋
𝑁 𝐸 𝑑𝐸 = 3 (2𝑚)3/2 𝐸1/2 𝑑𝐸
ℎ
 This equation can be used to find the number of states in metals and also in semi
conductors.
 Carrier Concentration in Metals
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 The carrier concentration, nc, can be obtained as

follows:

𝑛𝑐 = න 𝑁 𝐸 𝑓 𝐸 𝑑𝐸

4𝜋 3/2 1/2
1
𝑛𝑐 = න 3 (2𝑚) 𝐸 × (𝐸−𝐸 )/𝑘 𝑇
𝑑𝐸
ℎ 1+𝑒 𝐹 𝐵
 Failure of the Free Electron Theory
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 Model is too simplified.

 Assumes that electrons move in a constant potential
throughout.

 However, potential is more positive is it is close to

the core of metal atom.
 Thus the picture is very complicated. It can be more
reasonably approximated to a periodic potential,
that extends to infinity in all directions, and is
interrupted only at the surface of the metal.
 Kronig Penny Model
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 It is not the real potential.

 But a close simple model is sued.

 Energy spectrum for electrons consists of allowed and

forbidden bands.
 A potential barrier is formed, which is a function of V, a,
b, . If the potential barrier is large, allowed energy
regions become narrower. If the barrier tends to zero,
ℎ2 𝑘 2
then allowed energy states are 𝐸𝑛 = , similar to
2𝑚
that of a free particle.
 Introduction to Band Theory of Solids
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 In solids, bands result from the overlap

of atomic orbitals.
 Example: When two sodium atoms come
close together, their 3s levels, initially
equal, become two separate levels
because of the overlap of the
corresponding electron wave functions.
 The number of new levels equals the
number of interacting atoms.
 When the number of interacting atoms is
very large, as in a solid medium, the
result is an energy band of very closed
spaced levels.
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The energy band structure of a solid determines whether it is a

conductor, an insulator, or a semi-conductor.
 Metals and Insulators
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 If each atom contributes two valence electrons to

the band, the band can be exactly filled.
 If the valence electrons exactly fill one or more
bands, leaving others empty, the crystal will be an
insulator.
 The materials that have one valence electron per
primitive cell will be metals, because the band will
only be half filled.
 Semi Conductors
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 In semi conductors, although the valence band is

completely filled, the band gap is small.
 At room temperature significant numbers of
electrons can be excited to cross the band gap.
 Electrical conductivity of such materials is in
between conductors and insulators.
 Unlike conductors, the conductivity of semi
conductors increases with increase in temperature.
 Reciprocal Lattice
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 The reciprocal lattice represents the Fourier transform of

another lattice, usually a Bravais lattice.
 Direct lattice exists in real-space, reciprocal lattice exists in
reciprocal space (or momentum space or K-space).
 Use: In X-ray diffraction, due to the Laue conditions, the
momentum difference between incoming and diffracted X-rays
of a crystal is a reciprocal lattice vector. The diffraction
pattern of a crystal can be used to determine the reciprocal
vectors of the lattice. Using this process, one can infer the
atomic arrangement of a crystal.
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 In real space we defined 𝑎Ԧ1 , 𝑎Ԧ 2 , 𝑎Ԧ3 as the translational vectors in

real space for a direct lattice.
 For a reciprocal lattice, we define, 𝑏1 , 𝑏2 , 𝑏3 in reciprocal space,
which relate to the real space as follows:
𝑎Ԧ2 × 𝑎Ԧ3
𝑏1 = 2𝜋
𝑉
𝑎Ԧ3 × 𝑎Ԧ1
𝑏2 = 2𝜋
𝑉
𝑎Ԧ1 × 𝑎Ԧ2
𝑏3 = 2𝜋
𝑉

Where V = 𝑎Ԧ1 ∙ (𝑎Ԧ2 × 𝑎Ԧ 3 ) is the volume of the unit cell in real space.
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By P. Fraundorf - Own work, CC BY-SA 3.0,

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Find the reciprocal lattice of a simple cubic crystal.

Given, 𝑎1 = 𝑎𝑥ෝ , 𝑎2 = 𝑎𝑦,
ො 𝑎3 = 𝑎𝑧,Ƹ find 𝑏1 , 𝑏2 , 𝑏3 .
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 FCC and BCC are reciprocal to one another
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 The main features of the reciprocal lattice are:

1. The reciprocal lattice of a Bravais lattice is again
a Bravais lattice.
2. The reciprocal lattice of a reciprocal lattice is the
(original) direct lattice.
3. The length of the reciprocal lattice vectors is
proportional to the reciprocal of the length of the
direct lattice vectors. This is where the term
reciprocal lattice arises from.
 Wigner Seitz Cell
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 It is the locus of points in space

that are closer to that lattice
point than to any of the other
lattice points.
 A Wigner–Seitz cell is an
example of a primitive cell,
which is a unit cell containing
exactly one lattice point.
 Wigner Seitz Cell in Two Dimensions
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By George Chanturia - Own work, CC BY-SA 4.0,

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 Brillouin Zones
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 The Wigner–Seitz cell in the reciprocal space is called the

Brillouin zone, which contains the information about whether
a material will be a conductor, semiconductor or an insulator.
𝜋 𝜋
 The first Brillouin zone boundaries are at − 𝑡𝑜 .
𝑎 𝑎
 The allowed values of electron wave vector k in the first
±2𝜋 ±4𝜋 𝑁𝜋
Brillouin zone are 𝑘 = 0, , , . The series is
𝐿 𝐿 𝐿
𝑁𝜋 𝜋
truncated at = .
𝐿 𝑎
 With in the crystal, N primitive cells of lattice constant ‘a’
contribute to 2N independent orbitals in each energy band
(Factor 2 is due to spin).
Further Reading: Bieser, Chapter 10; and Kittel, Chapters 6 & 7 (Advanced)
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 Higher Brillouin Zones
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 The second Brillouin zone is the set of points that can

be reached from the first zone by crossing only one
Bragg plane.
 The (n + 1)th Brillouin zone is the set of points not in
the (n ‐ 1)th zone that can be reached from the nth
zone by crossing n ‐ 1 Bragg planes.
 The nth Brillouin zone can be defined as the set of
points that can be reached from the origin by
crossing n ‐ 1 Bragg planes, but no fewer.
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 Brillouin-zone construction by selected area
diffraction, using 300 keV electrons.
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By P. Fraundorf - Own work, CC BY-SA 3.0,

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