Semiconductor Optoelectronics

Prof. M. R. Shenoy
Department of Physics
Indian Institute of Technology, Delhi

Lecture - 10
Semiconductor Materials

In this talk we discuss about semiconductor materials. Our focus will be on semiconductor
optoelectronic materials, as this course is Semiconductor Optoelectronics.

(Refer Slide Time: 00:51)

Shown above is a part of the periodic table that shows elements of group II to VI. Don’t
worry about the ‘A’ and ‘B’ right now.
(Refer Slide Time: 01:33)

The most common elemental semiconductors comprise of group IV elements, like Silicon,
Germanium and Tin. These are semiconductors as an element itself, which means the basic
definition of semiconductor holds good. We also have binary semiconductors, or compound
semiconductors; these are stable compounds formed by one element from group III and one
element from group V.

(Refer Slide Time: 03:45)

If you see the table here, the elemental semiconductors are shown in group IV, i.e., Silicon,
Germanium, Tin. As mentioned above, the Binary semiconductors are formed by 1 element
from group III and 1 element from group V. The most commonly used binary compounds are
Gallium Arsenide, Aluminum phosphide, and Indium phosphide. These are also sometimes
called as III-V semiconductors.

You could also have one element from group II and one element from group VI forming a
compound. These are called II-VI compounds. For example, Cadmium from group II and
Tellurium from group VI make Cadmium Telluride, a widely used semiconductor. Zinc
Selenide, Cadmium Selenide, Mercury Selenide, Mercury Telluride are all II-VI
semiconductors.

So you may have III-V semiconductors or II-VI semiconductors. What I have shown in the
last row of the table above table is the electronic configuration in the outermost shell of the
element. For example, mercury’s outermost shell has 5d 10 6s2; it is in group II because there
are 2 electrons in the outermost shell.

In group III, Thallium has 6s2 6p1. All elements in group III have a configuration in the
outermost shell similar to 6s2 6p1. For example, for Indium, it is 5s2 5p1. For Gallium it is 4s2
4p1, and if you go to Aluminum, it is 3s 2 3p1. If you come to Boron, it is 2s 2 2p1. Boron has
atomic number 5, which means there are 5 electrons in a Boron atom; the electronic
configuration is 1s2 2s2 2p1.

(Refer Slide Time: 06:26)

In group IV, there are four electrons in outermost valence shell, and therefore they form
covalent bonds sharing four electrons with an adjacent atom to make an Octet, i.e., eight
electron shell, which completes the Octet. If you take one element from III and one from V,
there are three electrons in the outermost shell and five electrons in the outermost shell
respectively, and therefore you again have a complete Octet. Similarly, in II-VI compound,
we have two and six electrons, completing the Octet.

(Refer Slide Time: 07:36)

If the outer shell has an Octet, which means it is a complete shell, it is a stable compound.
Shown above are some of the typical Binary semiconductors and their Band gaps. For,
Gallium arsenide, the bandgap is 1.42 eV and lattice constant is 5.65 Angstroms. The given
refractive index is approximately near the cut off wavelength, or near the bandgap
wavelength.

You can see some of the common binary compounds which are used: Gallium Arsenide,
Indium Phosphide: Indium Antimonide, Indium Arsenide, Aluminum Nitride. There are also
wide bandgap semiconductors: Gallium Nitride has a bandgap of 3.39 electron volts. This is
nowadays a very important substrate; to get blue LEDs and blue lasers, it is Gallium Nitride
substrate which is used.

What you see in the image is the last three have lattice constants 3.1, 3.1, 3.5 Angstroms. But
if you see the other common binary compounds like Gallium Arsenide and Indium
Phosphide, they have 5.6 and 5.8 as the lattice constant respectively. This has some important
implications, which we will discuss shortly. The compounds that I have listed above here are
all direct bandgap materials.

(Refer Slide Time: 09:15)

I have also shown a second list of common indirect bandgap semiconductors above:
Germanium, Silicon, Aluminum Antimonide, Aluminum Arsenide, Gallium Phosphide,
Aluminum Phosphide and Silicon Carbide. You can find these numbers in books and
references. Silicon Carbide is also today an important material used for UV detectors. You see
its bandgap is very large, 2.42 electron volts, and lattice constant is about 3 Angstroms. All of
them have high refractive indices. As you can see, unlike the normal glass, most of them have
refractive indices 3 to 4.

Now, when we have so many semiconductors, how does one choose the required
semiconductor for an application? This is determined by the bandgap wavelength, or the cut
off wavelength. In optoelectronics, most of the material properties which are essential for the
device functioning depends on emission and absorption. And it is the bandgap which
determines the wavelength that the semiconductor material can emit and absorb.
(Refer Slide Time: 11:05)

Consider the band diagram of a semiconductor. I have shown E v, Ec, and Eg. There are
electrons in the valence band and vacant states in the conduction band. Consider an energy
level E1 in the valence band and E2 in the conduction band. If a photon of energy hν is
incident on the semiconductor, the incident photon can be absorbed, provided hν = E2 – E1,
and the electron sitting at energy level E1 makes an upward transition to the energy level E2.
Therefore, the smallest energy photon which can be absorbed by an electron intra-band
transition is hν = Eg.

Similarly if there are electrons in the conduction band which can make a downward
transition, the difference in the energy will be emitted in the form of a photon. So the smallest
energy photon which can be emitted will correspond to hν = Eg. We can write this as

hc hc
=E g λ=
λ , or E g , and this is called the bandgap wavelength λg.

As we know, h is the Planck’s constant, and c is the velocity of light in vacuum, which is a
constant. So you can substitute values into the expression, and you get the approximate value

1.24
λ g=
Eg where λg is in micrometers (μm) and Eg is in electron volts (eV). This is a very

useful formula. If I give you a material say, for example, Gallium Arsenide, with bandgap
1.42 eV, and ask what the bandgap wavelength λg is, you can immediately find out. It is
important because we normally don’t talk in terms of energy, but in terms of wavelength.

(Refer Slide Time: 15:09)

Gallium nitride has a bandgap of 3.39, or say 3.4. What is the maximum wavelength of
photons it can absorb or emit? You can immediately find out. For Gallium Nitride,

1.24 1.24
λ g= =
Eg 3.4 , which is approximately 0.35 or 0.36 μm. Instead of substituting h, which

is 6.6*10-34 J-s, and c, which is 3*108 m/s, and then Eg, which you have to convert into Joules,
you can just quickly estimate the wavelength from this formula.

So, depending on the application, you have to choose the compound semiconductor. But we
have a limited number of useful semiconductors. If you want to have materials with
continuously variable bandgap, then we go for the third type of materials. They’re called
Ternary compounds.
(Refer Slide Time: 17:51)

So, Ternary compounds. And also, Quaternary compound. In Ternary compound, as the name
indicates, there are 3 elements, and in Quaternary compound there are 4 element. In Ternary
compound we can have 2 elements from group III and 1 element from group V.

(Refer Slide Time: 18:37)

For example, from group III, we take Aluminum and Gallium, and Arsenide from group V. Or
you can have 1 element from group III and two from V, then they are still III-V compounds.
How do we represent a ternary compound? We represent this as Al xGa1-xAs, where x is the
alloy composition. These Ternary compounds are also called alloy semiconductors.
x can lie anywhere between 0 and 1, so 0 ≤ x ≤1 . Usually x lies between 0.1 to 0.5. If you

put x = 0, we simply have GaAs, Gallium Arsenide. If you put x = 1, we get Aluminum
Arsenide, AlAs, as 1-x is then 0, so there is no Gallium atoms present in the compound.

AlxGa1-xAs is an alloy where x fraction of Gallium atoms are replaced by Aluminum atoms, at
the fabrication/formation stage.

(Refer Slide Time: 21:12).

In Quaternary compounds, there are 2 elements from group III and 2 elements from group V.
For example, Indium Gallium Arsenide Phosphide. This is a very widely used material in
optoelectronics and optical communication. Most of your laser diodes for optical
communication are fabricated by this material. Indium and Gallium are from group III, and
Arsenic and Phosphide are from group V. So even the Quaternary compound is a III-V
compound. Now, it could be written as In 1-xGaxAsyP1-y, or it could also be written as In xGa1-
xAs1-yPy. What is the difference between these?

I mentioned that in the formation of Aluminum Gallium Arsenide Al xGa1-xAs, the fraction x
could be typically 0.1, 0.2, 0.3, in that range, i.e., 0.1 to 0.4. It means that x fraction of
Gallium atoms are replaced by Aluminum atoms. So our starting material was Gallium
Arsenide, and you have replaced x fraction of Gallium by Aluminum. This indicates that
Gallium Arsenide was the substrate. This complete material system is very often indicated
like this: Aluminum Gallium Arsenide oblique Gallium Arsenide, i.e., AlGaAs/GaAs, which
means the starting substrate is Gallium Arsenide. Usually, you start with a substrate, which is
a binary compound, and then you get the alloys, like AlGaAs.

So, in the case of In1-xGax Asy P1-y and InxGa1-x As1-y Py, what is the difference between this
two? The substrate in the first case is Indium Phosphide; we started with Indium Phosphide,
and x fraction of Indium was replaced by Gallium, and y fraction of Phosphorus was replaced
by Arsenide. In the second case, the starting substrate was Gallium Arsenide, and you can
understand the rest. So the x, y, 1 – x and 1 – y tells you which is the starting material or the
substrate. If x or y is equal to 0.5, then it is difficult to tell which is the starting material, but
normally x and y remain small. Also, Ternary and Quaternary compounds are in general III-V
semiconductors, but they can be II-VI also.

(Refer Slide Time: 24:52)

So, we can have two elements from group II and one from group VI. For example, Zinc
Cadmium Telluride and Mercury Cadmium Telluride, which is a widely used compound. This
is a Ternary compound. Similarly, you can have II-VI Quaternary compound. As I said,
Ternary and Quaternary compounds are generally called Alloy semiconductors. Now, the
question arises, why do we need to go for Ternary and Quaternary compounds, i.e., alloy
semiconductors?
(Refer Slide Time: 26:01)

There are two important reasons for that:

1. Bandgap modification
2. Growth or formation of lattice matched heterostructures.

We will discuss the second point in the next class. Lattice matching basically means that
lattice constant of the compounds which are used to form heterostructures have to be the
same. We will discuss this later. First, we discuss bandgap modification. Let’s take an
example and discuss what bandgap modification is.

(Refer Slide Time: 28:19)

We take the example of Aluminum Gallium Arsenide, AlGaAs, which is a widely used
material. Most of the laser diodes which are used in commercial products like laser printers,
laser pointers, music systems, and CD systems are AlGaAs laser diodes. It usually emits at
780 nanometer, near infrared. The material structure is AlxGa1-xAs/GaAs.

So most of the commercial laser diodes are AlGaAs, except those for optical communication.
This because optical communication takes place in the window of 1550 nm, not 780 nm.
Therefore, for optical communication, the material used is Indium Gallium Arsenide
Phosphide or Indium Gallium Arsenide.

(Refer Slide Time: 30:50)

Depending on the fraction x, the bandgap variation. I plot variation E g with x. At x=0, it is
Gallium Arsenide. At x equal to 1, we have Aluminum Arsenide. Almost all semiconductors
have a direct bandgap and an indirect bandgap. If we plot the E-k diagram or bandgap
diagram for Gallium Arsenide, the direct bandgap is equal to 1.42 eV at 300 K. There is also

a gap corresponding to the stable minima at k ≠ 0. That is the indirect bandgap, equal to

1.90 eV. If I plot E-k diagram for Aluminum Arsenide, we see that the indirect band gap is
2.17 eV, and the direct bandgap is 3.02 eV.

So, in both Gallium Arsenide or Aluminum Arsenide, at k is equal to 0 there is a gap, which is
the direct bandgap, and there is also the indirect bandgap at the minima not at k equal to zero.
Minima refers to stable states; so within the minima there are stable states, which means if an
excited electron comes within the valley of the minima, it can come down and become stable
at the minimum position.

A material is called indirect bandgap semiconductor or direct bandgap semiconductor

depending on which one of the bandgaps (direct or indirect) is smaller. Aluminum Arsenide is
an indirect bandgap semiconductor because the gap between the maxima of the valence band

and minima of the conduction band (at k ≠ 0) is smaller than the direct gap (at k=0). In the

case of Gallium Arsenide, the indirect gap is larger compared to the direct gap, so we say
Gallium Arsenide is a direct bandgap semiconductor.

A question arises, will there always be a local minima at k=0? The answer is no. There are
materials where there is no minima at k=0, i.e., they have no direct bandgap.

(Refer Slide Time: 35:42)

We come back to the plot of Eg vs x. When you change x, you are changing the environment
in the crystal, because you are replacing Gallium atoms by Aluminum atoms. The
electrostatic field and the distribution there changes, and accordingly the allowed values of
electron energies change, which means the E-k diagram changes with the change of x .

So, as you increase x, the bandgap increases, as shown above. As x increases, there is the
situation, say at x=0.4, where the direct bandgap (bold line) and the indirect bandgap (dotted
line) become equal. After this point, when x increases, say to 0.6, the indirect gap is smaller
compared to the direct gap, and this material has now become an indirect bandgap
semiconductor.

It was a direct bandgap semiconductor when we started with GaAs, corresponding to x=0. As
you increased x, it became an indirect bandgap semiconductor. The direct gap goes from 1.42
eV to 3.02 eV (material became AlAs). The indirect gap also increases, but at a rate slower
than the direct gap; after an x equal to approximately around 0.4, it is smaller than the direct
band gap.

Therefore, from x equal to 0 to 0.4, Aluminum Gallium Arsenide is a direct bandgap material,
whose bandgap can be continuously varied with the fraction x, by changing the composition.
And that is the importance of Aluminum Gallium Arsenide alloy. We will continue from here
in the next class.

(Refer Slide Time: 42:06)

Another important material where the bandgap is varied by varying the composition is
Gallium Arsenide Phosphide, GaAs1-xPx. The starting point at x = 0 is Gallium Arsenide, and
at x = 1 we have Gallium Phosphide, instead of the previous Aluminum Arsenide. This
material is used to make all the visible LEDs; the red yellow LEDs are made by Gallium
Arsenide Phosphide, which is also co-doped with nitrogen for certain reasons. We will
discuss this when we come to LEDs, but the principle and methodology of bandgap
modification remains the same.
(Refer Slide Time: 43:16)

We have a quiz today. Normally a quiz should not take more than 3 minutes, and maximum
time is 5 minutes. As you know, every quiz is for 1 mark.

Quiz 3: At room temperature, the energies corresponding to the band edges and the Fermi
level of a particular semiconductor (with mc = mv) are given by –

Ec = –4.2 eV, Ev = –6.0 eV, and Ef = –5.2 eV.

Answer the following parts:

a) Identify whether it is a p-type or n-type semiconductor. Give reason for your answer. Give
just one line reason, no detailed explanations are required.

b) What is the probability of occupation of electrons at the conduction band edge?

All the energy values have a negative sign in front. We will discuss why.