Doping and devices - Open Solid State Notes 22/05/2024, 10:40

Doping and devices

Expected prerequisites

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

Compute the electron/hole carrier densities and the Fermi level of an intrinsic semiconductor

Compute the intrinsic carrier density of a semiconductor

Describe how these quantities scale with temperature, effective mass, and bandgap

Learning goals

After this lecture you will be able to:

Compute the carrier density and Fermi level of doped semiconductors

Describe the functioning principles of semiconducting devices

In the previous lecture, we learned how to deal with partially Alled bands. The concept of electrons/holes established the
foundations needed to understand semiconductors. We saw that the carrier density, and thereby the electrical conductivity, of
semiconductors can be controlled by tuning the temperature. However, such temperature control is too constrained for many
applications, and leads to equal electron and hole densities ne = nh . The full utility of semiconductors is achieved through
another Fermi-level control method: doping. In today's lecture, we will take a look at how doping allows Ane control of the Fermi
level and the practical applications that come with it.

Adding an impurity to semiconductor

In order to understand doping, we need to remember some basic chemistry. Most semiconductors are made up of group IV
elements (Si, Ge) or binary compounds between group III-V elements (GaAs). In both cases, there are 4 valence electrons per
atom. If we want to increase the average number of electrons per atom, we can add a group V element that has an extra valence
electron. However, the extra electron is bound to the impurity because group V elements also have an extra proton. In order to
estimate the binding strength, we treat the lattice as a background and only consider the system of an electron bound to a proton.
We immediately recognize that this system can be modeled as a Hydrogen atom with energy levels

me e4 2 13.6eV
En = − 2 3 2 2 = −RE /n = − .
8π ℏ ε0 n n2

The spatial extent of the bound state is given by the Bohr radius:

rB = 4πε0 ℏ2 /me e2 .

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However, we have to remember that the above equations are valid for a hydrogen atom in free space. In our case, the extra
electron moves in the semiconductor. Therefore, there are a couple of differences from the Hydrogen model. One difference is that
the electron's mass is determined by the conduction band's effective mass. Another difference is that the interaction between the
electron and the nucleus is screened by the lattice. As a result, we need to introduce the following substitutions: me → m∗e ,
ϵ0 → ϵϵ0 . This turns out to yield the following estimation of the energy of the bound state associated with the impurity:

m∗e
E=− RE = −0.01eV (in Ge),
me ε2

with Bohr radius rB = 4 nm (vs rB = 0.5Å in hydrogen). The electron is very weakly bound to the impurity! Therefore, at room
temperature (0.026 eV), the donor electron is easily thermally excited into the conduction band. We therefore refer to group V
elements as donor impurities.

Instead of adding a group V element, we can add a group III element to reduce the average number of electrons in the system.
Group III elements have 1 electron and proton less. In this case, we treat the lacking electron as a hole that is weakly bound to the
negative charge associated with the lacking proton. As a result, we again have a hydrogen-like atom, except this time the charges
are Yipped (the hole circles around a negative center charge). That allows us to use the previous results and to conclude that the
group III element creates a weakly bound hole state that is easily ionized into the valence band. Because the group III elements
easily inject holes into the valence band, and thereby accept an electron from the valence band, they are called acceptors.

We conclude that we can control the number of holes in the valence band by implanting acceptors into the semiconductor.
Likewise, we can control the number of electrons in the conduction band by implanting donors. We will now analyze this control in
more detail.

Density of states with donors and acceptors

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In order to model multiple donor states, we assume that they are all degenerate at energy ED , which is located at a (very small)
binding energy's distance from the conduction band edge Ec . Similarly, we call the energy of the acceptor states EA , which is just
above the valence band edge Ev . Because of the degeneracy, the density of states of the donors/acceptors are Dirac delta
functions:

gD (E) = ND δ(E − ED ), gA (E) = NA δ(E − EA ),

where ND and NA are the donor and acceptor concentrations, respectively.

How good is this Dirac delta approximation? That depends on the concentrations. If we keep on adding impurities, then at some
point the weakly bound states will begin to overlap. The overlap will create an effective tight-binding model that leads to a
formation of an "impurity" band which breaks our approximation. We must therefore prevent the overlap of impurity bound states.
From the previous section, we know that the extent of the bound state is roughly 4 nm and thus the distance between impurity
atoms cannot exceed that. As a result, the impurity concentration is bounded to ND ≲ (1/4nm)3 .

Number of carriers
We now have the necessary tools to determine how we can control the Fermi level using doping. The algorithm to determine the

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Fermi level of a semiconductor was outlined in the previous lecture and we continue to use it here. The process is the same up
until the third step—charge conservation. The semiconductor now contains dopant atoms that become ionized, and therefore
charged. For example, if a donor impurity bound state loses an electron, it becomes positively charged. To solve the problem let us
introduce all the necessary concentrations:

Symbol Concentration of

ne electrons in the conduction band

nh holes in the valence band

nD donor-bound electrons

nA acceptor-bound holes

ND donor atoms

NA acceptor atom

The concentrations of the donor-bound electrons and the acceptor-bound holes are given by the Fermi-Dirac distribution:

1 1
nD = ND , nA = NA .
e(ED −EF )/kT +1 e−(EA −EF )/kT +1

(This follows from nD = ∫ gD (E)nF (E)dE and corresponding equation for holes). Keeping track of all electrons and holes, we
obtain the charge balance equation:

ne − nh + nD − nA = ND − NA .

The equation is not easy to solve: all of the terms on the left-hand side depend non-trivially on EF . In order to solve it, we require
several approximations:

Firstly, we assume that the Fermi level is far from both bands EF − Ev ≫ kT and Ec − EF ≫ kT . The approximation
allows us to use the law of mass action from the previous lecture:

ne nh = NC NV e−EG /kT ≡ n2i .

We highlight that this equation is still valid as it is independent of the Fermi energy, and the Fermi energy is the only thing that
changes by introducing dopants.

Secondly, we determined that electrons/holes are weakly bound to the impurities. Therefore, at ambient temperatures, we
assume that all the dopants are fully ionized and therefore nD = nA = 0.

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These approximations allow us to simplify the charge balance equation:

ne − n2i /ne = ND − NA ,

which is simply a quadratic equation for ne that we can solve. Note that only ne depends on the Fermi energy. So, once we know
ne , we can extract the Fermi energy.

When ∣ND − NA ∣ ≫ ni the semiconductor is extrinsic. In this case, if ND > NA (n-doped semiconductor), ne ≈ ND − NA
and nh = n2i /(ND − NA ). I.e., the electron density in the conduction band is set by the dopant concentration (and not by
temperature). If, on the other hand, ND < NA (p-doped semiconductor), the hole concentration is nh ≈ NA − ND and ne =
n2i /(NA − ND ).

We can now easily And the Fermi level. From the Arst approximation, we know that the simpliAed relation between ne/h and EF is:

ne ≈ NC e−(Ec −EF )/kT ,

nh ≈ NV e(Ev −EF )/kT .

We substitute the solutions for ne and nh found above and solve for the Fermi level:

EF = Ec − kT ln[NC /(ND − NA )], for ND > NA ,

and

EF = Ev + kT ln[NV /(NA − ND )], for NA > ND .

When is a semiconductor intrinsic, and when it is extrinsic?

By deAnition the semiconductor is intrinsic when ∣ND − NA ∣ ≪ ni , so kT ≳ EG / log[NC NV /(ND − NA )2 ].

Temperature dependence of the carrier density and Fermi level

It is instructive to consider how EF , ne and nh depend on temperature. Below we show what happens in an n-doped
semiconductor. The same logic applies to p-doped semiconductors.

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As we go from highest to lowest temperature, we observe several regimes:

Intrinsic limit . If the temperature is suaciently large, then ni ≫ ∣ND − NA ∣ and therefore ne ≈ nh ≈ ni . Additionally, if
holes are heavier than electrons, then EF grows with temperature in this limit.

Extrinsic limit. As we decrease the temperature, we decrease the number of intrinsic carriers to the point where most of the
electrons in the conduction band (the charge carriers) originate from the fully ionized donors. As a result, the number of
carriers stays approximately constant in this temperature range.

Freeze-out limit. Once the temperature is suaciently low kT ≪ EC − ED , we expect the electrons to "freeze away" from
the conduction band to the donor band. The charge carriers still originate from the donors, however, not all donors are ionized
now.

Zero temperature. There are no charge carriers in neither conduction nor valence bands. If there are no acceptors, then the
Fermi level goes to halfway between the donor and the conduction bands. Otherwise, the highest energy electrons are in the
donor band and therefore EF should match the donor band.

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Exercise

check that you can reproduce all the relevant limits in a calculation.

Combining semiconductors: pn-junction

What happens if we bring two differently doped semiconductors together (one of p-type, one of n-type)?

Band diagram

Until now we dealt with spatially homogeneous materials. From now on the position coordinate (let's call it x) starts playing a role.
We represent the properties of inhomogeneous materials using the band diagram. The main idea is to plot the dependence of
various energies (EF , bottom of conduction band EC , top of the valence band EV ) as a function of position.

Let us build up the band diagram step by step:

The main difference between n-type and p-type semiconductors is the location of the Fermi level EF (see "n and p" tab above).
The Fermi level of an n-type semiconductor is close to the donor states. On the other hand, the p-type semiconductor has its
Fermi level near the acceptor states. At equilibrium (i.e., in the absence of an external electric Aeld), we do not expect to see any
currents in the system. Therefore, the Fermi level EF must be constant across the system (see "Equilibrium" tab). To achieve a

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constant Fermi level, we bring up in energy the p-type region or bring down the n-type region until the Fermi levels are aligned.
However, a question arises: what happens at the junction?
Band Diagram
We can understand the junction with a simple picture. In physics, most of the time we expect things to change continuously.
Therefore, we expect that the valence EV and conduction EC bands connect continuously in the middle region, as shown in the
"Band Bending" tab. On the contrary, if the bands were to be discontinuous, then an electric Aeld must develop at a single point in
n and p
the middle region to shift the bands in energy. However, we do not expect such point-like electric Aelds to develop because
electrons can move freely in semiconductors.
Equilibrium

On aBand
moreBending
microscopic level, the electrons at the junction in the n-type semiconductor will move into the p-type semiconductor to
recombine with the holes. After the recombination, the n and p-type semiconductors lose an electron and a hole respectively. As a
result, a positive ionized donor dopant is not screened anymore and the n-type semiconductor obtains a positive overall charge.
Similarly, p-type region obtains a negative charge. Therefore, an electric Aeld develops across the junction. As the recombination
process continues, a larger charge density ρ develops and thus the electric Aeld grows until it is large enough to prevent the
electrons/holes from crossing the junction. Inside the region, energy deviates by δφ ≫ kT from the bulk value and thus the
density of electrons/holes drops exponentially fast. Therefore, we refer to the region as the depletion region.

The charge density ρ distribution inside the depletion region is shown below:

p-region depletion region n-region

The typical values of wn + wp are ∼ 1μm at NA , ND ∼ 1016 cm−3 , and ∼ 0.1μm at NA , ND ∼ 1018 cm−3 , so it may be
much larger than the distance between the dopant atoms.

PN-junction diode

What happens if we apply voltage to a junction?

Because the conductivity of the p-region and n-region is much larger than that of the depletion region, most of the voltage
difference will appear in the depletion region:

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The number of majority carriers moving across the junction is proportional to their concentration. Increasing the voltage bias
"pushes" carriers up in energy, it depends exponentially on the voltage.

We therefore get the Shockley diode equation:

I = I0 (exp(eV /kT ) − 1)

Solar cell

Light absorbed in the pn-junction creates electron-hole pairs. The eletric Aeld then moves electrons to the n-doped region, holes
to the p-doped one, and therefore generates a voltage.

Semiconducting laser

A heavily doped pn-junction so that the Fermi level is in the conduction/valence band produces an extremely high rate electron-
hole recombination with an extremely high rate, and makes the pn-junction function like a laser.

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MOSFET and quantum well

See the book for details.

Summary
Density of states in a doped semiconductor:

Charge balance determines the number of electrons and holes as well as the position of the Fermi level.

If dopant concentration is low, then ne = nh = ni ≡ NC NV e−EG /2kT .

If dopant concentration is high, then in n-doped semiconductor ne = ND − NA and nh = n2i /ne (or vice versa in p-doped one).

Temperature switches between intrinsic and extrinsic regimes, and controls the carrier density

Conductance combines the contributions of electrons and holes, and allows to determine EG .

A pn-junction has a depletion layer in its middle with the potential in a pn-junction having the following shape (where the
transition region is made out of two parabolas):

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

Warm-up exercises*

1. Write down the law of mass action. Does the intrinsic carrier concentration depend on the Fermi energy?

2. Write down the approximate charge balance condition for a doped semiconductor in the intrinsic regime.

3. Write down the charge balance condition in case there are only donors and no acceptors

4. Again considering only donors, compute the Fermi energy in the extrinsic regime

5. Draw the band diagram of the PN diode. Suppose you want to send a current through the diode by a applying a voltage. On
which side should you connect the positive-voltage terminal to get a large current?

Exercise 1*: Crossover between extrinsic and intrinsic regimes

In the lecture we have identiAed the intrinsic and extrinsic regimes. Let us now work out what happens when the semiconductor is
at the border between these two regimes, and the dopant concentration ∣ND − NA ∣ is comparable to the intrinsic one ni .

1. Write down the law of mass action and the charge balance condition for a doped semiconductor.

2. Solve this system of equations for ne and nh only assuming EG ≫ kB T .

3. Verify that your solution reproduces intrinsic regime when ∣ND − NA ∣ ≪ ni and the extrinsic regime when ∣ND − NA ∣ ≫
ni

Exercise 2: Donor ionization

Let us examine when the full donor ionization is a good assumption. For that we consider a doped semiconductor in the extrinsic
regime.

1. Assume that all dopants are ionized, determine the position of the Fermi level.

2. Write down the concentration of dopants that are not ionized.

3. Determine at what donor concentration one cannot assume anymore that all donors are ionized in germanium at room
temperature.

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Exercise 3: Performance of a diode

Consider a pn-junction diode as follows

pn diode by Raffamaiden: Source, CC BY-SA 3.0

The current Yowing through a diode as a function of applied bias voltage is given by the Shockley diode equation:

I(V ) = Is (T ) (e kT − 1)
eV

where Is (T ) is the saturation current.

1. What is the signiAcance of adding dopant atoms to an intrinsic semiconductor? Can two intrinsic semiconductors joined
together make a diode?

2. Discuss which processes carry current in a diode under reverse bias.

3. Based on this, estimate how the saturation current Is depends on temperature.

Exercise 4: Quantum well heterojunction in detail

Consider a a quantum well formed from a layer of GaAs of thickness L, surrounded by layers of Alx Ga1−x As.

Quantum Well

x
z L

Quantum well. Source vectorised by the user: Sushant savla from the work by
Gianderiu, CC BY-SA 3.0 "Creative Commons Attribution-Share Alike 3.0"

Assume that the band gap of the Alx Ga1−x As is substantially larger than that of GaAs. The electron effective mass in GaAs is
0.068 me , the hole effective mass is 0.45 me with me the mass of the electron.

1. Sketch the band diagram of this quantum well.

2. Write down the Schrödinger's equation for electrons and holes

3. Find the energies of electron and holes in the quantum well as a function of kx , ky .

4. Sketch the density of states in the quantum well.

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5. If we want to design a quantum well with a bandgap 0.1 eV larger than that of bulk GaAs, what thickness L do we need?

k. Suppose you use electron-hole recombination in the quantum well to create a laser. How can you tune the color of this laser?

7. What would be the advantage of doping the Alx Ga1−x As compared to the GaAs in this quantum well?

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