Solar Photovoltaic Engineering

REG 6112 (3-2-2)

Negash Alemu (PhD)

Department of Metallurgical & Materials Engineering, College of Engineering,
Defense University, Bishoftu, Ethiopia.
nebabuji@gmail.com
 Unit-II
PV Fundamentals
3. Basic Semi Conductor Physics
3.1 Introduction Why do we need semiconductor materials for
 What is a semiconductor material? solar cells?
3.2 Semiconductor Materials
 Materials can be categorized in terms of their electrical properties.
 We know that metals can conduct electricity very well.
The origin of the high conductivity of metals is based on the fact that the outer
electrons of the atoms in a metal are weakly bound.
This results in an ocean of free mobile electrons in the material indicated by the red
dots

 Electrons are negatively

charged and therefore the
conduction in a metal is
based on mobile negative
charge.
 These electrons move
around in a background of
atoms indicated by the blue
dots.
 As many of the atoms
donated an electron, they
can be considered as fixed
positively charged ions.
 Materials which do not conduct electricity are called insulators.
In insulator materials the ocean of free moving electrons are missing.
All electrons are bounded to the background atoms.

 As you can see in the figure, the red dots represent the electrons and are glued to the blue
atoms.
 Semiconductors are materials which have a conductivity between that of a metal
and insulator.
 The outer electrons of the atoms are more strongly bound to the background atoms
than in metals, but under certain conditions some of the electrons can leave their
background atoms and become freely mobile electrons as well.

 These few electrons that are

separated from its atom, leave a
positively charged entity behind.
 This positively charged entity is
called a hole.
 The small blue dots in the
illustration represent the holes.
 These holes are able to move
Perpendicular
around, just to
likethe direction of propagation
electrons.
and the oscillating electric field, a magnetic
field B is oscillating.
 As a result the charge transport in a semiconductor is facilitated by negatively
charged electrons and positively charged holes.
The properties of metals, insulators and semiconductors can easily be illustrated
using the electronic band structure of a material.
 An electronic band reflects the potential energy levels an electron could occupy in
the material.
Metals have a broad
electronic band which
is not fully filled with
electrons.
This electronic band
corresponds to the
energy levels in which
the electrons can freely
diffuse around in the
metal.
An insulator and a
semiconductor, to the
contrary, have two
distinct bands with a
large forbidden gap
between them.
3.3 Band Gap
Most electrons fill the lower electronic band, the so-called valence band.
If electrons reside in the valence band, they are not mobile, they are well bound to
the atoms in the lattice.
The upper electronic band is the so-called conduction band.
Electrons in the conduction band are free and mobile and contribute to the
conduction, just like the mobile electrons in a metal

 The forbidden
energy gap between
the valence and
conduction band is
called the band
gap.
 In this gap no
energy states exist,
which can be
occupied by
electrons.
 The difference between insulators and semiconductors is that the band gap of an insulator is
much larger than the band gap of a semiconductor
The band gap of an insulator is typically larger than 3 eV.
The larger the forbidden gap, the smaller the probability that an electron can have
enough energy to occupy a state in the conduction band.
For a semiconductor, the band gap is smaller.

If the band gap of

a material is
smaller than 3 eV,
the material can be
considered to be a
semiconductor.
In a
semiconductor,
some electrons can
have enough
thermal energy to
jump from the
valence band to
the conduction This energy can also be provided by light, if the photon has an
band. energy equal or larger than the band gap.
This means that when you shine light with photons having an energy larger than the
band gap, you can make a semiconductor more conductive.
The blue dots located in the valence band represent a positively charged hole.
While electrons in the valence band are glued to their background atoms, the
positively charged holes can diffuse through the valence band, just like the electrons
in the conduction band.

 So, up to this point I have introduced the basic properties to describe

semiconductor materials.
 The conductivity properties are determined by the electrons in the conduction
band and the holes in the valence band.
 The energy gap between the conduction and valence band is called the band gap.
 The most important element for photovoltaic applications: Silicon.
 90% of the commercially available solar panels is based on silicon.
 Si has 14 electrons in orbit around its nucleus and fills up to 4 electrons in the 3s
and 3p states
 These four outer electrons are the weakest bounded to the nucleus.
 Chemists might use different terms for the same concepts.
 They might use the expression highest occupied molecular orbital (the HOMO) as
the valence band and the lowest unoccupied molecular orbital (the LUMO) as the
conduction band.
 The HOMO-LUMO gap would be the band gap.
  C, SI & Ge have tetrahedral coordination and
form a diamond cubic crystalline lattice in its
crystalline phase
 Silicon and germanium can be considered as IV-semiconductor materials, the IV
stands for the number of valence electrons.
 In the next graph we plot the band gap of crystalline carbon, silicon and
germanium versus the lattice constant.

Why is carbon not a semiconductor as it

has the same lattice?
 Materials with semiconductor properties can be made from other materials than
elements with four valence electrons.
 These materials can similar to silicon form a diamond cubic crystalline lattice

 In the crystalline lattice shown

here the gallium are the blue
atoms and the arsenide are the red
atoms.

 The difference with silicon is that every gallium atom

is neighboring four arsenide atoms and every arsenide
atom is neighboring a gallium atom.
 Let's consider the III-V materials based on gallium, like gallium-phosphor (GaP),
gallium-arsenide (GaAs) and gallium-stibium (GaSb).

 Again, the larger the lattice constant of the material, the smaller the band gap will
be.
 Gallium-phosphor has the smallest lattice constant and therefore the largest band
gap.
 Another group of semiconductor materials are the so-called II-VI semiconductor
materials like cadmium-tellurium.
 These materials can form a diamond cubic crystalline lattice as well.

 In the crystalline lattice

shown here the cadmium
atoms are the blue atoms
and tellurium atoms are
the red atoms.

 So, every cadmium atom is bonded to four

tellurium atoms, and every tellurium atom is
neighboring a cadmium atom.
 Let's consider the II-VI materials based on cadmium, like cadmium-sulfur (CdS),
cadmium-selenium (CdSe), cadmium-tellurium (CdTe).

 Again, the larger the lattice constant of the material, the smaller the band gap will
be.
 Cadmium-telluride (CdTe) has the largest lattice constant and therefore the
smallest band gap.
 I hope you have become familiar with the important properties of semiconductors like the
valence band, the conduction band and the band gap.
 And I have shown that we have different semiconductor materials like silicon, germanium,
gallium-arsenide and cadmium-telluride.
 Important to remember is that all these semiconductors have different band gaps.
 So how can we make semiconductor materials conductive?
 Or in other words: how can we fill the conduction band with free electrons?
3.4 Charge Carriers
How do we make semiconductors conductive?
 As discussed so earlier, we need to excite electrons from the valence band to the
conduction band to make semiconductors conductive.
 This can be achieved by three different routes.
1. We can excite charge carriers using thermal energy.
2. we can use impurities in the semiconductor material (doping).
3. We use the energy in light to excite electrons from the valence band to the
conduction band.
 1. Excitation of charge carriers using thermal energy
 T0 demonstrate the behavior of the charge carriers, electrons and holes in a
Semiconductor. Let us use silicon consider it as lattice to be a 2-D squared lattice.
 In this 2-D network, every silicon atom has four bonds with its neighboring silicon
atom, like it has in a 3-dimensional network.

Silicon Structure representation in 2D

 The higher the temperature, the more free

electrons and free holes can be excited.
2. Another approach to increase the density of the charge carriers is using doping.
 Up to now we have considered pure semiconductor materials without any
impurities. These semiconductor materials are called intrinsic.
 It means that the density of the mobile electrons and holes are the same in the
material.
 We can intentionally incorporate impurities in the material. This is called doping.
 Doping can have a significant effect on the charge carrier density

 Materials with
only three
valence  Materials with five
electrons, like valence electrons,
boron, like nitrogen and
aluminum, and phosphorous. (VA)
gallium. (IIIA)
 First, we are going to intentionally put phosphorous impurities in the Si network.
 Phosphorous ( P ) has five valence electrons.
 The P atoms will make molecular bonds with its four neighboring silicon atoms.
 Since the P atom has five valence electrons, it has one electron left.
 This extra electron is easily excited to a free mobile state.
 The P atom left behind, is not neutral anymore & becomes a +vely charged entity.

 This positive charge  The result is that

is fixed to the by adding an
position where the impurity we have
phosphorous atom one extra free
is residing in the mobile electron
lattice. and a fixed
positive charge in
the background.

This is called n-doping.

 For n-doped semiconductors, the electrons are called the majority charge carriers,
as the density of electrons is much higher than that of the holes.
 The holes are called the minority charge carriers in a n-doped semiconductor.
 Here, The phosphorous atoms are represented as donor states.

 At typical room temperatures many to all of the electrons in the donor states can
be excited to the conduction band.
 As a result we have more free mobile electrons than mobile holes in an n-type
semiconductor.
 We call the states donor states, because they donate an electron to the
conduction band.
 The electrons are the majority charge carriers, the holes are the minority charge
carriers.
 Now, we are going to intentionally put boron impurities in the silicon network.
 Since the boron atom has only three valence electrons, it is missing one electron
to make a molecular bond with its four neighboring silicon atoms.
 As a consequence one molecular bond is filled with only one electron. This
entity is the same as the hole.
 This extra hole is easily excited to a free mobile state as well.
 The boron atom
left behind is not
neutral anymore,
but becomes  The result is that
negatively by adding a
charged. boron impurity
 This negative we have one
charge is fixed to extra free mobile
the position hole available
where the boron and one fixed
atom is residing in negative charge .
the lattice.
This is called p-doping.
 These states are called acceptors as it accepts one electron from the valence
band.
 For p-doped semiconductors, the electrons are called the minority charge
carriers as the density of electrons is much smaller than the density of the holes.
 The holes are the majority charge carriers in p-doped materials.

P-doping.
 Let's get a feeling for the typical concentrations for majority and minority charge
carriers in doped silicon networks in the dark.

 This shows that the density of the majority charge carriers can be many orders of
magnitude higher than that of the minority charge carrier.
 Note that the silicon density in crystalline silicon is 5*10^22 cm^-3.
 This means that the total number of charge carriers is much lower than the
typical density of silicon atoms, the ratio majority charge carriers to silicon atoms
in this example is 1 to 5 million.
 The densities of charge carriers can be described by the law of mass action
 This law tells us that at a given temperature the product of the electron density
and the hole density is constant, independent of the doping concentration.

So let's consider intrinsic silicon

 We incorporate 10^16 cm^-3 phosphorous atoms in the lattice, or in
other words: we have a donor density N_D of 10^16 cm^-3.
 Assume that all donors give a free electron to the lattice the electron
density n0 =N_D.
 Now we consider a third approach to excite charge carriers, which is by light absorption.
 Let's consider the electronic band diagram again and photon with an energy equal to the
band gap, indicated by the green arrow.

 This photon can be absorbed in a semiconductor material and can be used to excite an
electron from the valence band to the conduction band.
 So, light can make a semiconductor material more conductive .
 However, if we have a photon with an energy smaller than the band
gap, this photon is lacking the energy to excite an electron from the
valence band to the conduction band.

 This photon cannot be absorbed by the semiconductor material.

 Another situation is when the photon has an energy much larger than the band gap.
 This photon can excite an electron at an energy level deeper in the valence band into the
conduction band.
 Or an electron to a higher energy level into the conduction band.

 In these situations the hot electrons or holes very fast relax back to the lower energy
positions.
 For the electron this is the bottom of the conduction band and for the hole this would mean
the top of the valence band.
 This extra energy is released as heat and will heat up the semiconductor material.
 So the rest energy, which is the photon energy minus the band gap energy, ends up as heat.
 How light absorption affects the charge carrier density in doped materials.
 Let's consider again the situation with a density of majority charge carriers of 10^16 cm^-3
and density of minority charge carrier of 10^4 cm^-3.
 Now let's assume we generate electron-hole pairs by light absorption.
 We generate 10^11 cm^-3 electron-hole pairs.
 What will happen to the density of the majority and minority charge carriers?
 So we will simply add up the numbers.
 What you can see is that the majority charge carrier density is not affected by the
light absorption.

 10^11 is much smaller than 10^16.

 On the other hand the density of minority charge carriers is drastically affected.
 10^11 is much larger than 10^4. Its density is increased with 7 orders of
magnitude.
 This is an important conclusion, which we will need later to understand the
working principle of solar cells.
 In doped semiconductor materials, light absorption has only effect on the density
of minority charge carriers.
Q.1 Understanding Questions
Q.2
Q.3
Q.4
Q.5
 Summarized, in this section we have discussed
how to excite charge carriers in a semiconductor
material, by temperature, doping and light
absorption.
 The next question is: how do those charge
carriers move around and what makes them
move around in a semiconductor material?
 We will talk about that in the next block, where
we are going to discuss transport of charge
carriers.