Basic principles - Open Solid State Notes 22/05/2024, 10:40

Semiconductor physics

(based on chapters 17–18 of the book)

Expected prior knowledge

Before the start of this lecture, you should be able to:

Simplify integral expressions by Taylor expansion

Compute the density of states of the free electron model

Apply the concepts of group velocity and effective mass to solve problems

Learning goals

After this lecture you will be able to:

Describe the concept of holes, and apply this concept to describe the properties of semiconductors

Compute the density of states of electrons in semiconductors

Compute the density of charge carriers and chemical potential as a function of temperature

Up until this point, we focused on calculating and understanding the band structures. However, the dispersion
of a band is only part of the story. An empty band is not going to lead to any interesting physical properties no
matter how sophisticated it is. Therefore, it is also important how bands are Clled by the particles. By carefully
controlling the distribution of particles in the bands, we are able to engineer material properties that we
require. Without a doubt, the greatest example is semiconductors—the bedrock of modern electronics. In this
lecture, we shall grasp the basics of semiconductors by learning how to treat bands at different levels of Clling.

Review of band structure properties

Before proceeding further, let us remind ourselves of important band structure properties.

Group velocity v = ℏ−1 dE(k)/dk . Descibes how quickly electrons move within the lattice.
−1
Effective mass m∗ = ℏ2 (d2 E(k)/dk 2 ) . Tells us how hard it is to accelerate the particles and is
related to the curvature of the band.

Density of states g(E) = ∑(dn/dk) × (dk/dE), where the sum runs over all states at the same
energy. The amount of states per inCnitesimal interval of energy at given energy. The quantity is vital in
order to calculate any bulk property of the material such as conductivity, heat capacity, etc.

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In order to check that everything makes sense, we apply the concepts to the free electron model:

ℏ2 k 2
H=
2m

The velocity is ℏ−1 ∂E(k)/∂k= ℏk/m ≡ p/m.

−1
The effective mass is m = ℏ (d2 E(k)/dk 2 ) = m.
∗ 2

So in this simplest case the deCnitions match the usual expressions.

Filled vs empty bands

We distinguish three different band Clling types: Clled, empty and partially Clled. Despite being two opposite
extreme extreme cases, Clled and empty bands are very similar. For example, both Clled and empty bands carry
no electric current:

π/a π/a
1 1 dE
j = 2e ∫ v(k)dk = 2e ∫ × dk =
2π −π/a 2πℏ −π/a dk
1
2e [E(π/a) − E(−π/a)] = 0.
2πℏ

On the other hand, a Clled band has an equal number of electrons going forwards and backwards which thus
cancel and lead to zero current. Similar results apply to many other physical quantities such as heat capacity
and magnetization. Therefore, Clled and empty bands do not affect most physical properties and can be
disregarded. As a result, rather than to consider hundreds of bands that a material contains, we neglect most
of them and just focus on the handful of partially Clled bands around Fermi level.

From electrons to holes

Because completely Clled or completely empty bands have simple properties, we may search for a convenient
way to describe a band that only has a few electrons missing or extra. While keeping track of a few electrons
has no tricks, even a few electrons missing from a band seem to require considering all the other electrons in a
band.

A more eOcient approach to describing a nearly Clled band is motivated by the following analogy. Let us say
we have 100 boxes: 99 are occupied and 1 is empty. To keep track which box is occupied/empty, we could
write down the numbers of all 99 occupied boxes. If, on the other hand, we only keep track which single box is

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empty, we solve the problem with a lot less book-keeping.

The same approach applies to band Clling. Instead of describing a lot of electrons that are present in an almost
Clled band, we focus on those that are absent. The absence of an electron is called a hole: a state of a
completely Clled band with one particle missing.

In this schematic we can either say that 8×2 electron states are occupied (the system has 8×2 electrons
counting spin), or 10×2 hole states are occupied. Electron and hole pictures correspond to two different, but
equivalent ways of describing the occupation of a band. Naturally, dealing with electrons is more convenient
whenever a band is almost empty and with holes when a band is almost full.

Properties of holes
Let us compare the properties of an electron with energy E and a hole obtained by removing that electron.
Since removing an electron reduces the total energy of the system, the hole's energy is opposite to that of an
electron Eh = −E . The probability for an electron state to be occupied in equilibrium is given by f (E):

1
f (E) = .
e(E−EF )/kB T + 1

Since a hole is a missing electron, the probability for a hole state to be occupied is

1 1
fh (E) = 1 − f (E) = 1 − = ,
e(E−EF )/kB T + 1 e(−E+EF )/kB T + 1

which is the Fermi distribution of particles with energy Eh = −E and EF ,h = −EF .

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The momentum ph of a hole should give the correct total momentum of a partially Clled band if one sums
momenta of all electrons. Therefore ph = −ℏk, where k is the wavevector of the missing electron.

Similarly, the total charge should be the same regardless of whether we count electrons or holes, so holes have
a positive charge +e (electrons having −e).

On the other hand, hole's velocity is the same as that of an electron:

dEh −dE dE
= = .
dph −dℏk dp

Finally, we derive the hole effective mass from the equations of motion:

dv
mh = +e(E + v × B).
dt

Comparing with

dv
me = −e(E + v × B),
dt

we get mh = −me (we could also obtain this by differentiating the hole's velocity).

Semiconductors: materials with two bands.

Semiconductors are materials with all bands either nearly occupied or almost empty. Unlike in insulators,
however, the band gap in semiconductors is suOciently small, for it to be possible to create a few electrons in
the lowest unoccupied band or the highest Clled band. Because in the unoccupied band the charge carriers
(particles carrying electric current) are electrons, it is called conduction band, while in the almost occupied
valence band the charge carriers are holes.

Holes in semiconductors

When introducting holes, we discussed holes obtained by removing any electron. From this point on, similar to
most other discussions of semiconductors in the literature, we will only speak of holes in valence band and
electrons in conduction band.

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The occupation of the two bands is dictated by the Fermi distribution. Furthermore, the Fermi level of a
semiconductor lies between the conduction and the valence bands, and the band gap EG ≫ kB T in most
materials. As a result, only the bottom of the conduction band has electrons and the top of the valence band
has holes. Therefore we can approximate the dispersion relation of both bands as parabolic, like shown below

Or in other words

ℏ2 k 2
Ee = Ec + ,
2me
ℏ2 k 2 ℏ2 k 2
Eh = Ev,h + = −Ev + .
2mh 2mh

Here Ec is the energy of an electron at the bottom of the conduction band and Ev is the energy of an electron
at the top of the valence band. Observe that because we are describing particles in the valence band as holes,
mh > 0 and Eh > −Ev .

The corresponding density of states of the two types of particles is

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g(E) = (2me )3/2 E − Ec /2π 2 ℏ3 ,

gh (Eh ) = (2mh )3/2 Eh + Ev /2π 2 ℏ3 .

A photon gives a single electron enough energy to move from the valence band to the conduction
band. How many particles does this process create?

Two: one electron and one hole.

Semiconductor density of states and Fermi level

Intrinsic semiconductor

Our next task is to Cgure out how many electrons and holes there are, and for that we need to Cnd where the
Fermi level EF is located. Let us plot the density of states, the Fermi distribution function, and the density of
particles at each energy in the same plot:

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We know that by itself, the semiconductor should have no charge, and therefore the total numbers of electrons
and holes must be equal. Since increasing the Fermi level increases the number of electrons and reduces the
number of holes, we will use the charge neutrality condition to determine where the Fermi level is situated.

The key algorithm of describing the state of a semiconductor

1. Compute the density of states of all types of particles.

2. Calculate the number of electrons in the conduction band and holes in the valence band, assuming a certain
value of EF

3. Write down the charge balance condition: the difference between electrons and holes should equal the total
charge of the semiconductor.

4. Apply approximations to simplify the equations (this is important!).

5. Find EF and concentrations of electrons and holes

Applying the Crst two steps of the algorithm:

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∞ ∞
(2mh )3/2 1
nh = ∫ fh (Eh )gh (Eh )dEh = ∫ Eh + Ev dEh ,
−Ev −Ev 2π 2 ℏ3 e(Eh +EF )/kB T + 1
∞ ∞
(2me )3/2 1
ne = ∫ f (E)ge (E)dE = ∫ E − Ec dE.
Ec Ec 2π 2 ℏ3 e(E−EF )/kB T +1

Note that whenever calculating the hole dependent quantities, we replace all the relevant physical quantities
with their hole equivalents. Since the hole energy is opposite Eh = −E , we replace the Fermi energy EF →
−EF and the bottom of the valence band by Ev → −Ev in the integration limits.

In the third step, we need to solve the equation under charge balance ne = nh . The equation is not a pleasant
one and cannot be solved analytically unless an approximation is made. Therefore, the fourth step assumes
that the Fermi level is far from both bands EF − Ev ≫ kB T and Ec − EF ≫ kB T . As a result, the Fermi-
Dirac distribution is approximately similar to Boltzmann distribution:

f (E)e/h ≈ exp [(−Ee/h ± EF )/kB T ] .

Now we can move to the last step and calculate ne and nh :

(2mh )3/2 −EF /kB T ∞

nh ≈ e ∫ Eh + Ev e−Eh /kB T dEh = NV e(Ev −EF )/kB T ,
2π 2 ℏ3 −Ev

∞
where we used ∫0 xe−x dx = π /2 and we deCned

2πmh kB T 3/2
NV = 2 ( ) .
h2

We see that holes are exponentially activated into the valence band.

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how large is NV at room temperature? (hard question)

If kB T ∼ 1eV (the typical energy size of a band), then electrons in the whole band may be excited and NV ∼ 1
per unit cell. On the other hand, NV ∼ T 3/2 Therefore NV ∼ (kB T /1eV)3/2 ∼ 1%.

Similarly for electrons:

2πme kB T 3/2
ne = NC e −(Ec −EF )/kB T
, NC = 2 ( ) .
h2

Combining everything together:

nh ≈ NV e(Ev −EF )/kB T = NC e−(Ec −EF )/kB T ≈ ne .

Solving for EF :

Ec + Ev 3
EF = − kB T ln(me /mh ).
2 4

An extra observation: regardless of where EF is located, ne nh = NC NV e−EG /kB T ≡ n2i , where EG =

Ec − Ev is the band gap of the semiconductor.

ni is the intrinsic carrier concentration, and for a pristine semiconductor ne = nh = ni .

The law of mass action

The equation

ne nh = n2i

is the law of mass action. The name is borrowed from chemistry, and describes the equilibrium concentration of
two reagents in a reaction A + B ↔ AB . Here electrons and hole constantly split and recombine.

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Conduction

Earlier, we deduced that empty and Clled bands provide no current. We Cnish the analysis by considering
partially Clled bands of an intrinsic (pristine) semiconductor. To calculate the current, we utilize the Drude
model and sum the electron and hole contributions:

j = −ne eve + nh evh

−me ve /τe = −eE; −mh vh /τh = eE.

We see that despite opposite velocity signs for electrons and holes, they carry electric current in the same
direction:

ne e2 τe nh e2 τh
=( ) = ne eμe + nh eμh .
j
σ≡ +
E me mh

We know that for intrinsic semiconductors, the hole/electron densities are ne = nh = ni ∝ e−EG /2kB T .
Therefore, it is possible to measure the band gap of an intrinsic semiconductor by looking at the temperature
dependant conductivity EG ≈ −(1/2)d log σ/d[kB T ]−1 . Additional information can be obtained using Hall
effect. However Hall effect is much more complex in semiconductors since only the current in the direction
perpendicular to the applied electric Celd must vanish. This, however only means that the electron current is
opposite of the hole current in that direction, not that the electrons and holes move parallel to the applied
current.

Exercises
Exercise with an asterisk (*) are considered to be at the basic/essential level

Warm-up exercises*

In this set of warm-up exercises we consider a two-dimensional semiconductor.

1. Write down an integral expression for the number of electrons in the conduction band. How does the
dimensionality come in?

2. Write down an integral expression for the number of holes in the valence band.

3. Make a sketch of the density of states (=band structure) of this semiconductor.

4. Solve the integrals of questions 1 and 2 assuming the Fermi energy is in the gap and far away from the

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band edges compared to kb T .

5. Find the Fermi energy

Exercise 1: Energy, mass, velocity and cyclotron motion of electrons and holes

1. Consider the top of the valence band of a semiconductor (see above). Does an electron near the top of the
valence band have a positive or a negative effective mass? Does the electron's energy increase or
decrease as k increases from 0? Does the electron have a positive or negative group velocity for k > 0?
2. Answer the same last 3 questions for a hole in the valence band.

3. We now consider an electron in a 2D semiconductor near the bottom of the conduction band described by
ℏ2 2
an energy dispersion E + ky2 ). The electron's velocity is given by v = ∇k E/ℏ =
= EG + 2m∗ (kx
1 ∂E
^ ∂E y
x ^
ℏ ( ∂kx + ∂ky ). Suppose we turn on a magnetic Celd B in the z -direction. Write down the equation of
motion for this electron (neglecting collisions). What is the shape of the motion of the electron? What is
the characteristic 'cyclotron' frequency of this motion? What is the direction of the Lorentz force with
respect to ∇k E ?

4. Suppose we now consider a hole near the bottom of the conduction band and turn on a magnetic Celd B
in the z -direction. Is the direction of the circular motion (i.e., the chirality) of the hole the same as that of
the electron? Would the chirality change if we instead consider a hole (or electron) near the top of the
valence band?

Exercise 2*: a 1D semiconductor

Suppose we have a 1D semiconductor with a conduction band described by

Ecb = EG − 2tcb [cos(ka) − 1],

and a valence band described by

Evb = 2tvb [cos(ka) − 1].

Furthermore, the chemical potential is set at 0 < μ < EG .

1. Make a sketch of the band structure.

2. Derive an expression for the group velocity and effective mass for electrons in the conduction bands and
holes in the valence band.

3. Assume that the Fermi level is far away from both bands. That is, ∣EG − μ∣ ≫ kB T and μ ≫ kB T . In

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that case, it is acceptable to approximate the bands for low k . Why is it acceptable? Write down an
approximate expression of these bands.

4. Write down an expression for the density of states per unit length for both bands using the approximated
expressions. Compare with the actual density of states per unit length.

5. Calculate the electron density in the conduction band and the hole density in the valence band.

e. What would the chemical potential μ be in case of an intrinsic semiconductor?

Exercise 3*. Holes and electrons in a 1D tight-binding energy band

Recall that the dispersion relation of a 1D single orbital tight binding chain is given by

E(k) = ε + 2t cos(ka),

where a is the lattice constant and ε and t are tight binding parameters.

1. What is the group velocity and effective mass of this band for holes compared to that of electrons?

2. Give an integral expression of the hole concentration in this band given the chemical potential μ and
temperature T .

3. Show that the sum of the electron and hole concentration in this band is constant as a function of the
temperature.

Exercise 4*: The Hall coeOcient when both electrons and holes are present in the system

1. Recall from the Drude model that electrons give rise to a negative Hall coeOcient. Explain why the Hall
coeOcient is positive if holes are the charge carriers in a material.

2. Recall that the Hall coeOcient RH describes the change of the transverse resistivity ρxy due to a change
Ey
in B : ρxy = Jx = RH B . When both electrons and holes are present in a system, the Hall coeOcient is
given by

nh μ2h − ne μ2e
RH = 2.
e (nh μh + ne μe )

What would be the Hall coeOcient if the electrons and holes have equal concentrations and equal
mobilities?

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