SOLAR PHOTOVOLTAIC TECHNOLOGIES AND

SYSTEMS ( ES61002 )
LTP- 3-1-0

Chirodeep Bakli
Assistant Professor
School of Energy Science & Engineering
Indian Institute of Technology Kharagpur, India
Email: chirodeep@iitkgp.ac.in

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 Photovoltaics (PVs)
• Defined: A material or device that converts photons of light
energy to electrical voltage and current

• A photon with short enough wavelength can cause an electron

in a PV material (semiconductor, such as Si) to break free of
the atom that holds it

• If a nearby electric field is provided, electrons can be swept

toward a metallic contact, where they can become part of an
electric current
Sun Earth Relationship
 Solar Radiation
Spectral distribution of extraterrestrial radiation
Terrestrial radiation
 Photovoltaic (PV) Scheme
• Highly purified silicon (Si) from sand, quartz, etc. is “doped” with intentional
impurities at controlled concentrations to produce a p-n junction
– p-n junctions are common and useful: diodes, CCDs, photodiodes, transistors
• A photon incident on the p-n junction liberates an electron
– photon disappears, any excess energy goes into kinetic energy of electron (heat)
– electron wanders around drunkenly, and might stumble into “depletion region”
where electric field exists (electrons, being negative, move against field arrows)
– electric field sweeps electron across the junction, constituting a current
– more photons  more electrons  more current  more power
photon of light
Si doped with
electric field n-type silicon
phosphorous, e.g.

Si doped with
boron, e.g.
p-type silicon liberated electron

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 Photovoltaics (PVs)
• Si is a semiconductor

• Metals are conductors

• Metals, semiconductors, and insulators have energy bands:

 Valence band, forbidden band, and conduction band, forbidden band
 Electrons in conduction band contribute to current flow

• With metals, P-N junction can’t form, so free electrons move too randomly

• Insulators require too much energy to add electrons to conduction band

 Band Theory
Useful way to visualize the difference between conductors, insulators and semiconductors is to plot
the available energies for electrons in the materials. Instead of having discrete energies as in the case
of free atoms, the available energy states form bands

where m* is called the effective mass

 Band Theory of Solids

• Consider initially the known wave functions of two hydrogen atoms far
enough apart so that they do not interact.

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 Band Theory of Solids
• Interaction of the wave functions occurs as the atoms get closer:

Symmetric Antisymmetric

• An electron in the symmetric state has a nonzero probability of being

halfway between the two atoms, while an electron in the antisymmetric
state has a zero probability of being at that location.

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 Band Theory of Solids
• In the symmetric case the binding energy is
slightly stronger resulting in a lower energy
state.
– Thus there is a splitting of all possible energy levels
(1s, 2s, and so on).

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Energy Bands in Al
Energy Bands in Cu
Energy Bands in Si
Energy Bands in GaAs
 Electronic properties
The last completely filled (at least
at T = 0 K) band is called the
Valence Band
• The next band with higher energy is the
Conduction Band
• The Conduction Band can be empty or partially
filed
• The energy difference between the
bottom of the CB and the top of
the VB is called the Band Gap (or
Forbidden Gap)

SORAN UNIVERSITY
 Energy Bands for Solids

An important parameter in the band theory is the Fermi level, the top of
the available electron energy levels at low temperatures. The position of
the Fermi level with the relation to the conduction band is a crucial factor
in determining electrical properties.
 Insulator Energy Bands
Most solid substances are insulators, and in terms of the band theory of solids this
implies that there is a large forbidden gap between the energies of the valence
electrons and the energy at which the electrons can move freely through the material
(the conduction band).
 Conductor Energy Bands

In terms of the band theory of solids, metals are unique as good conductors of
electricity. This can be seen to be a result of their valence electrons being
essentially free. In the band theory, this is depicted as an overlap of the valence
band and the conduction band so that at least a fraction of the valence electrons
can move through the material.
 Categories of Solids
• There are three categories of solids, based on their conducting properties:
– conductors
– semiconductors
– insulators

How to calculate the conductivity?

 Electrical Resistivity and Conductivity at 293 K

Conductors: 104 to 107 ohm−1m−1

Semiconductors: 10−6 to 104 ohm−1m−1

Insulators: 10−20 to 10−10 ohm−1m−1

The electrical conductivity at room

temperature is quite different for each
of these three kinds of solids
Metals and alloys have the highest
conductivities
followed by semiconductors
and then by insulators
 Semiconductors
The free-electron model does not apply to semiconductors
and insulators, since these materials simply lack free
electrons to conduct in a free-electron mode, this is due to
the nature of the bond in the crystals

There is a different conduction mechanism for

semiconductors than for normal conductors.
 Semiconductors
The free-electron model does not apply to semiconductors
and insulators, since these materials simply lack free
electrons to conduct in a free-electron mode, this is due to
the nature of the bond in the crystals

There is a different conduction mechanism for

semiconductors than for normal conductors.
 Band Structure Summary
When more atoms are added (as in a real solid), there is a further splitting of
energy levels. With a large number of atoms, the levels are split into nearly
continuous energy bands, with each band consisting of a number of closely
spaced energy levels.

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 The Fermi Function
The Fermi Function
• Probability distribution function (PDF)
• The probability that an available state at an energy
E will be occupied by an e- f(E)
1

f E  
1
E  E f  kT
1 e 0.5

E  Energy level of interest

Ef  Fermi level
 Halfway point Ef E
 Where f(E) = 0.5
k  Boltzmann constant
= 1.38×10-23 J/K
= 8.617×10-5 eV/K
T  Absolute temperature (in Kelvins)
 Boltzmann Distribution
If E  E f  kT

Then f(E)

  kT 1
f E   e
 EE f

Boltzmann Distribution 0.5

•Describes exponential decrease in the
density of particles in thermal
equilibrium with a potential gradient Ef E
•Applies to all physical systems
• Atmosphere  Exponential distribution of gas ~Ef - 4kT ~Ef + 4kT
molecules
• Electronics  Exponential distribution of electrons
• Biology  Exponential distribution of ions
 Band Diagrams (Revisited) E
EC
Eg
Ef
EV

Band Diagram Representation 0.5 1 f(E)

Energy plotted as a function of position
EC  Conduction band
 Lowest energy state for a free electron
 Electrons in the conduction band means current can flow

EV  Valence band • Virtually all of the

 Highest energy state for filled outer shells valence-band energy
 Holes in the valence band means current can flow
levels are filled with e-
Ef  Fermi Level • Virtually no e- in the
 Shows the likely distribution of electrons
conduction band
EG  Band gap
 Difference in energy levels between EC and EV
 No electrons (e-) in the bandgap (only above EC or below EV)
 EG = 1.12eV in Silicon
 Semiconductor Theory
At T = 0 we expect all of the atoms in a solid to be in the ground
state. The distribution of electrons (fermions) at the various
energy levels is governed by the Fermi-Dirac distribution

β = (kT)−1 and EF is the Fermi energy.

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 Temperature and Resistivity
• When the temperature is increased from T = 0, more and more atoms
are found in excited states.

• The increased number of electrons in excited states explains the

temperature dependence of the resistivity of semiconductors.

Only those electrons that have jumped from the valence band to the
conduction band are available to participate in the conduction process
in a semiconductor. More and more electrons are found in the
conduction band as the temperature is increased, and the resistivity of
the semiconductor therefore decreases.

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 Resistivity vs. Temperature

(a) Resistivity versus temperature for a typical conductor. Notice the linear rise in resistivity with
increasing temperature at all but very low temperatures. (b) Resistivity versus temperature for a
typical conductor at very low temperatures. Notice that the curve flattens and approaches a
nonzero resistance as T → 0. (c) Resistivity versus temperature for a typical semiconductor.
The resistivity increases dramatically as T → 0.

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 Temperature dependence of the energy bandgap
The energy bandgap of semiconductors tends to decrease as the temperature is increased.
The temperature dependence of the energy bandgap, Eg, has been experimentally determined
yielding the following expression for Eg as a function of the temperature, T:
 Semiconductor Conductivity (Parting comments)
• Although it is not possible to use the Fermi-Dirac factor to derive an exact
expression for the resistivity of a semiconductor as a function of temperature, some
observations follow:
The energy E in the exponential factor makes it clear why the band gap is so crucial.
An increase in the band gap by a factor of 10 (say from 1 eV to 10 eV) will, for a given
temperature, increase the value of exp(βE) by a factor of exp(9βE).
• This generally makes the factor FFD so small
that the material has to be an insulator.

Based on this analysis, the resistance of a semiconductor is expected to decrease

exponentially with increasing temperature.
This is approximately true—although not exactly, because the function FFD is
not a simple exponential, and because the band gap does vary somewhat with
temperature.

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 Intrinsic Semiconductor
Silicon has 4 outer shell /
valence electrons

Forms into a lattice structure to

share electrons
Intrinsic Silicon
The valence band is full, and no
electrons are free to move about

EC

EV

However, at temperatures above

T=0K, thermal energy shakes an
electron free
 Semiconductor
For T > 0K
Properties
Electron shaken free and can • Generation – Creation of an electron (e-)
cause current to flow and hole (h+) pair
• h+ is simply a missing electron, which
leaves an excess positive charge (due to
an extra proton)
• Recombination – if an e- and an h+ come
in contact, they annihilate each other
h+ e– • Electrons and holes are called “carriers”
because they are charged particles –
when they move, they carry current
• Therefore, semiconductors can conduct
electricity for T > 0K … but not much
current (at room temperature (300K), pure
silicon has only 1 free electron per 3
trillion atoms)
 Holes and Intrinsic Semiconductors
• When electrons move into the conduction band, they leave behind vacancies
in the valence band. These vacancies are called holes. Because holes represent
the absence of negative charges, it is useful to think of them as positive
charges.

• Whereas the electrons move in a direction opposite to the applied electric

field, the holes move in the direction of the electric field.

• A semiconductor in which there is a balance between the number of electrons

in the conduction band and the number of holes in the valence band is called
an intrinsic semiconductor.

Examples of intrinsic semiconductors include pure carbon and germanium.

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 Impurity Semiconductor
• It is possible to fine-tune a semiconductor’s properties by adding a small
amount of another material, called a dopant, to the semiconductor creating
what is a called an impurity semiconductor.

• As an example, silicon has four electrons in its outermost shell (this

corresponds to the valence band) and arsenic has five.

Thus while four of arsenic’s outer-shell electrons participate in covalent

bonding with its nearest neighbors (just as another silicon atom would), the
fifth electron is very weakly bound.

It takes only about 0.05 eV to move this extra electron into the conduction
band.

• The effect is that adding only a small amount of arsenic to silicon greatly
increases the electrical conductivity.

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 Donor Levels
• The addition of arsenic to silicon creates what is known as an n-type
semiconductor (n for negative), because it is the electrons close to the
conduction band that will eventually carry electrical current.

The new arsenic energy levels just below the conduction band are
called donor levels because an electron there is easily donated to the
conduction band.

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 Acceptor Levels
• Consider what happens when indium is added to silicon.
– Indium has one less electron in its outer shell than silicon. The result is one
extra hole per indium atom. The existence of these holes creates extra
energy levels just above the valence band, because it takes relatively little
energy to move another electron into a hole
– Those new indium levels are called acceptor levels because they can easily
accept an electron from the valence band. Again, the result is an increased
flow of current (or, equivalently, lower electrical resistance) as the electrons
move to fill holes under an applied electric field
• It is always easier to think in terms of the flow of positive charges (holes)
in the direction of the applied field, so we call this a p-type
semiconductor (p for positive).
– acceptor levels p-Type semiconductors
• In addition to intrinsic and impurity semiconductors, there are many
compound semiconductors, which consist of equal numbers of two kinds
of atoms.

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Types of Semiconductors:
 Extrinsic Semiconductors
Those intrinsic semiconductors to which some suitable impurity or doping agent or doping has been added in
extremely small amounts (about 1 part in 108) are called extrinsic or impurity semiconductors. Depending on
the type of doping material used, extrinsic semiconductors can be sub-divided into two classes:

(i) n-type semiconductors and

(ii) P-type semiconductors.
 Doping
• Doping – Adding impurities to the silicon crystal lattice
to increase the number of carriers
• Add a small number of atoms to increase either the
number of electrons or holes
 Periodic Table
Column 3 Column 4 Elements
Elements have 3 have 4 electrons in
electrons in the the Valence Shell
Valence Shell

Column 5
Elements have 5
electrons in the
Valence Shell
 Donors n-Type Material
Donors
• Add atoms with 5 valence-band
electrons
• ex. Phosphorous (P)
• “Donates” an extra e- that can freely
travel around
• Leaves behind a positively charged
nucleus (cannot move)
• Overall, the crystal is still electrically +
neutral
• Called “n-type” material (added
negative carriers)
• ND = the concentration of donor
atoms [atoms/cm3 or cm-3]
~1015-1020cm-3
• e- is free to move about the crystal
(Mobility mn ≈1350cm2/V)
 Donors n-Type Material
Donors n-Type Material
• Add atoms with 5 valence-band
electrons –
• ex. Phosphorous (P) + + – – + –+ + +–
• “Donates” an extra e- that can freely ++ +– – –
– + –+ + +
travel around
• Leaves behind a positively charged – + – – + –
+ + + – – + –
nucleus (cannot move)
• Overall, the crystal is still electrically
neutral Shorthand Notation
• Called “n-type” material (added + Positively charged ion; immobile
negative carriers) – Negatively charged e-; mobile;
• ND = the concentration of donor Called “majority carrier”
atoms [atoms/cm3 or cm-3] + Positively charged h+; mobile;
~1015-1020cm-3 Called “minority carrier”
• e- is free to move about the crystal
(Mobility mn ≈1350cm2/V)
Acceptors Make p-Type Material

Acceptors
• Add atoms with only 3 valence-
band electrons
• ex. Boron (B)
• “Accepts” e– and provides extra h+
to freely travel around
• Leaves behind a negatively
h+ charged nucleus (cannot move)
– • Overall, the crystal is still
electrically neutral
• Called “p-type” silicon (added
positive carriers)
• NA = the concentration of acceptor
atoms [atoms/cm3 or cm-3]
• Movement of the hole requires
breaking of a bond! (This is hard,
so mobility is low, μp ≈ 500cm2/V)
 Acceptors Make p-Type Material
p-Type Material Acceptors
• Add atoms with only 3 valence-
+ – +– – –+ band electrons
– – + +
– + + • ex. Boron (B)
– –+
+ – +– – – • “Accepts” e– and provides extra h+
+ – + + – + to freely travel around
– – – + + – + • Leaves behind a negatively
charged nucleus (cannot move)
• Overall, the crystal is still
Shorthand Notation
electrically neutral
– Negatively charged ion; immobile
• Called “p-type” silicon (added
+ Positively charged h+; mobile;
positive carriers)
Called “majority carrier”
• NA = the concentration of acceptor
– Negatively charged e-; mobile;
atoms [atoms/cm3 or cm-3]
Called “minority carrier”
• Movement of the hole requires
breaking of a bond! (This is hard,
so mobility is low, μp ≈ 500cm2/V)
 Effect of Doping on Fermi Level
Ef is a function of the impurity-doping level
n-Type Material

E
EC
Ef

EV
0.5 1 f(E)

• High probability of a free e- in the conduction band

• Moving Ef closer to EC (higher doping) increases the number of available
majority carriers
 Effect of Doping on Fermi Level
Ef is a function of the impurity-doping level
p-Type Material
1  f E 
E
EC

Ef
EV
0.5 1 f(E)

• Low probability of a free e- in the conduction band

• High probability of h+ in the valence band
• Moving Ef closer to EV (higher doping) increases the number of available
majority carriers
Equilibrium Carrier Concentrations
n = # of e- in a material
p = # of h+ in a material

ni = # of e- in an intrinsic (undoped) material

Intrinsic silicon
• Undoped silicon
• Fermi level
• Halfway between Ev and Ec
• Location at “Ei”
E

EC
Eg
Ef
EV
0.5 1 f(E)
Equilibrium Carrier Concentrations
Non-degenerate Silicon
• Silicon that is not too heavily doped
• Ef not too close to Ev or Ec
Assuming non-degenerate silicon
E f  Ei  kT
n  ni e
Ei  E f  kT
p  ni e
Multiplying together

np  ni
2
 Charge Neutrality Relationship
• For uniformly doped semiconductor
• Assuming total ionization of dopant atoms

p  n  ND  N A  0
# of carriers # of ions

Total Charge = 0
Electrically Neutral
Calculating Carrier Concentrations
• Based upon “fixed” quantities
• NA, ND, ni are fixed (given specific dopings for a
material)
• n, p can change (but we can find their
equilibrium values) 1

ND  N A  ND  N A 
2
 2

n     ni 
2

2  2  
1
N A  N D  N A  N D  
2 2

p     ni 
2

2  2  
2
ni

n
 Common Special Cases in Silicon

1. Intrinsic semiconductor (NA = 0, ND = 0)

2. Heavily one-sided doping
3. Symmetric doping
Intrinsic Semiconductor (NA=0, ND=0)

Carrier concentrations are given by

n  ni
p  ni
n  p  ni
 Heavily One-Sided Doping
N D  N A  N D  ni
N A  N D  N A  ni
This is the typical case for most semiconductor applications

If N D  N A , N D  ni (Nondegenerate, Total Ionization)

Then n  N D
2
ni
p
ND
If N A  N D , N A  ni (Nondegenerate, Total Ionization)
Then p  N A
2
ni
n
NA
 Symmetric Doping
Doped semiconductor where ni >> |ND-NA|

• Increasing temperature increases the number

of intrinsic carriers
• All semiconductors become intrinsic at
sufficiently high temperatures

n  p  ni
Determination of Ef in Doped Semiconductor
 ND 
E f  Ei  kT ln   for N D  N A , N D  ni
 ni 
 NA 
Ei  E f  kT ln   for N A  N D , N A  ni
 ni 

Also, for typical semiconductors (heavily one-sided doping)

n  p
E f  Ei  kT ln   kT ln  [units eV]
 ni   ni 