Tandem Solar Cells

Demonstration of tandem solar cell based on GaAs/GaInNAs/GaAsBi

Umair Ahmad Nasir
Supervisor: Prof. Naci Balkan
Date: August 2013




A thesis submitted for Masters in Electronic Engineering

Department of Computer Science and Electronic Engineering
University of Essex
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Acknowledgment


In the name of ALLAH, the Most Beneficent and the Most Merciful, Alhamdulillah, all
praises to ALLAH for the strengths and His blessing in completing this dissertation. I would
express my sincere gratitude to my supervisor Professor Naci Balkan, for his supervision,
advice and motivation throughout my research project.
I am very grateful to my family for their support both emotionally and financially. My special
thanks go to Mr. Adrian Boland-Thoms for helping in clean room and the smooth running of
the experiments by providing the benefit of his many years of experience and technical
expertise with semiconductor devices and fabrication. I extend my thanks to the members of
the Optoelectronics Research group whom helped in keeping up my morale when things were
not going smoothly.
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Abstract

The efficiency of the single band gap solar cell is limited to 33% for the standard air mass 1.5
(AM1.5) spectrum according to detailed balance limit given by Shockley and Queisser in
1961. Tandem solar cells solar cells with several junctions of different energy gaps can
improve the efficiency of PV cells. The ability of GaInNAs and GaAsBi semiconductors to
have considerably lower band gaps than GaAs and to remain lattice matched with GaAs
makes them attractive materials for tandem solar cells.
In the first part of this project band anti crossing model is used that enables us to show the
band gap reduction effect in the GaAsN due to downward shifting of the conduction with the
addition of nitrogen content. In addition to this valence band anti crossing model is used to
express the reduction in the GaAsBi band gap due to the upward shifting of valence band and
increment in the spin orbit splitting with the increase in the concentration of bismuth content.
In the end a comparison is also done between band gap reduction effects in dilute nitride and
dilute bismide with the increase in the concentration of nitrogen and bismuth.
In the second part of this work we investigate GaInNAs, GaAsBi multiple quantum well and
GaAs control solar cells. Initially the fabrication of GaInNAs, GaAsBi MQW and GaAs
control cell is carried out in the clean room. After fabrication process current-voltage (I-V)
and spectral response measurement were conducted for all solar cells. The GaInNAs device
exhibit efficiency of 3.6% with the fill factor of 38% at AM1.5 G. The GaAsBi and GaAs
control cells does not shows any diode like characteristics in dark and under illumination.
Spectral response measurements performed on the GaInNAs MQW samples express that their
spectral response is prolonged to the effective band gap of the GaInNAs quantum wells. On
the other side the GaAsBi solar cells exhibits a small response only for wavelength near the
band gap of GaAs and it is also not extended to the higher wavelength, which indicates the
poor quality of the dilute bismide layers in the intrinsic region of the MQW solar cells.


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Table of Contents
Acknowledgment ........................................................................................................................ i
Abstract ...................................................................................................................................... ii
1 Introduction ........................................................................................................................ 1
2 Background ......................................................................................................................... 3
2.1 Solar Spectrum ............................................................................................................ 3
2.2 Semiconductor Basic Concepts ................................................................................... 5
2.2.1 Band Theory......................................................................................................... 5
2.2.2 Fermi Level .......................................................................................................... 6
2.2.3 Band Structure ..................................................................................................... 7
2.2.4 Electrons and Holes Generation........................................................................... 7
2.2.5 Electrons and Holes Recombination .................................................................... 8
2.3 PN Junction Formation.............................................................................................. 10
2.4 Solar Cell Equivalent Circuit .................................................................................... 12
2.5 Single Band Solar Cell .............................................................................................. 15
2.6 Tandem Solar Cell ..................................................................................................... 15
2.6.1 Strategies to Improve Efficiency ....................................................................... 15
2.6.2 Principles of tandem solar cells ......................................................................... 16
2.7 III V Semiconductor ............................................................................................... 17
2.7.1 Doping................................................................................................................ 19
2.8 Dilute Bismide........................................................................................................... 20
2.8.1 Growth of Dilute Bismide .................................................................................. 22
2.9 Dilute Nitride............................................................................................................. 25
2.10 Quantum Wells .......................................................................................................... 27
3 Experimental Techniques ................................................................................................. 30
3.1 Epitaxial Growth Techniques .................................................................................... 30
3.1.1 Molecular beam epitaxy (MBE) ........................................................................ 30
3.2 Fabrication Process ................................................................................................... 32
3.2.1 Cleaving ............................................................................................................. 32
3.2.2 Sample Cleaning ................................................................................................ 33
3.2.3 Mounting ............................................................................................................ 33
3.2.4 Oxide Removal .................................................................................................. 33
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3.2.5 Photolithography ................................................................................................ 33
Spin Coating ..................................................................................................................... 33
Soft Baking ....................................................................................................................... 34
Masking ............................................................................................................................ 34
3.2.6 Developing ......................................................................................................... 34
3.2.7 Oxide Removal .................................................................................................. 35
3.2.8 Evaporation ........................................................................................................ 35
3.2.9 Lift off ................................................................................................................ 35
3.2.10 Annealing ........................................................................................................... 35
3.2.11 Etching ............................................................................................................... 36
Hard Baking ...................................................................................................................... 36
Active Area Etching ......................................................................................................... 36
Contacting Layer Etching ................................................................................................. 36
3.2.12 Contact on the back Side.................................................................................... 37
3.3 Experiments ............................................................................................................... 37
3.3.1 I V Measurements ............................................................................................ 37
3.3.2 Spectral Response .............................................................................................. 39
4 Modelling.......................................................................................................................... 41
4.1 Band Anti-Crossing Model ....................................................................................... 41
4.1.1 Conduction band anti crossing ........................................................................... 41
4.1.2 Valence Band Anti crossing............................................................................... 44
5 Results and Discussion ..................................................................................................... 47
5.1 Structures of Solar Cells ............................................................................................ 47
5.1.1 GaAs Solar Cell ................................................................................................. 47
5.1.2 Dilute Bismide & Dilute Nitride Solar Cells ..................................................... 48
5.2 I V Characteristics and Results .............................................................................. 50
5.3 Spectral Response (SR) ............................................................................................. 56
6 Conclusion ........................................................................................................................ 58
Reference ................................................................................................................................. 59




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1 Introduction
The increase in world energy consumption and the reduction of conventional energy sources
demands a renewable, infinite and economical energy source. World energy consumption is
predicted to grow by 56% between 2010 and 2040. The total world energy use will rise from
1.53 10
18
J (1.53 EJ) in 2010 to 1.84 10
18
J (1.84 EJ) in 2020 and to 2.39 10
18
J (2.39
EJ) in 2040 [1].
Currently fossil fuels supply almost 80 % of world energy while renewable energy sources
account for 14.3 % and nuclear power for 5.7 % [2]. Renewable energy is the world's fastest
growing energy source, increasing by 2.5 % per year [1].
One of the most suitable ways to cope with the worlds energy crisis is to use the solar
energy. The solar energy reaching earth every day is over 1.5 10
22
J (15000 EJ), while the
daily world energy consumption is equal to approximately 1.3 EJ [3]. Photovoltaic devices
specifically are receiving wide attention, as they can convert solar radiation into electrical
power.
The efficiency of the single band gap solar cell is limited to 33% at band gap (E
g
) of around
1.4eV for the standard air mass 1.5 (AM1.5) spectrum according to detailed balance limit
given by Shockley and Queisser in 1961 [13].
The multiband gap solar cells with several junctions of different energy gaps attracted
increasing attention to improve the efficiency of PV cells because each of them can convert
solar energy into electricity more efficiently and permit to achievement of solar cell
efficiencies beyond the Shockley Queisser detailed balance limit for a single junction [3].
Up to the present time the GaAs based tandem cells have the highest efficiency, achieving
efficiencies of 35.8 % for global AM1.5 (1000 Wm
-2
) and 42.3 % for the direct beam AM1.5
spectrum at a cell temperature of 25
o
C [4].
GaAs has the significant property of alloying with other group III and V elements. In 1995
Kondow et al. revealed that incorporation of a small amount of nitrogen in GaAs causes a
large band gap reduction effect by lowering the conduction band. In a similar way to the
dilute nitrides, the addition of Bismuth in III V semiconductors (e.g. GaAs) is expected to
display a valence band anti-crossing effect causing a large band gap bowing [21]. The ability
of dilute nitride (GaNAs) and dilute bismide (GaAsBi) to have significantly lower band gap
and to be lattice matched with GaAs makes them interesting material for III-V tandem solar
cells.
The aim of this thesis is to design, fabricate and study a three junction tandem solar cell,
GaAs /GaAsBi/GaAsN.
This dissertation is structured in the following sections:
Chapter 2 presents most of the key background topics and reviews beginning with the solar
spectra, fundamental concepts of semiconductors, PN junction, solar cell equivalent circuits
and the operation and main design characteristics of single band gap, tandem solar cells. The
growth techniques and properties of dilute nitrides and dilute bismide alloys will be
discussed. In the end, reviews about the design of the GaAs solar cell are presented.
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The fundamental experimental techniques used in this project to investigate both electrical
and optical properties of the GaAs, dilute nitride and dilute bismide solar cells are contained
in Chapter 3. It starts with reviews of epitaxial growth techniques and moves on to molecular
beam epitaxy. The processes used to fabricate a hall bar and mesa structures on the solar cells
and the various experimental techniques used in the research are also explained in detail.

In chapter 4, the theory of the band gap bowing effect in dilute nitrides and dilute bismides is
explained using the conduction band and valence band anti crossing model respectively.
The performance of GaAs/GaAsBi/GaInNAs solar cells is evaluated by AM1.5G IV
characteristics and spectral response measurements in chapter 5. In order to evaluate the
carrier density and mobility in the GaAs solar cells, study is carried out using Hall
measurement.
Chapter 6 presents the conclusions of the work undertaken, and gives suggestions for future
work on dilute bismide and dilute nitride tandem solar cells.



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2 Background
2.1 Solar Spectrum
The photovoltaic cells convert light energy incident on them into electrical energy. According
to Planks theory light is made up of quanta of energy, known as photons. The energy of
photons depends (inverse relationship) only on the frequency of light. In the solar cell
applications, usually the source of light is the sun. The nuclear fusion reactions at the sun are
responsible to produce light ranging from the ultraviolet & visible to infrared wavelengths
portion of the electromagnetic spectrum [5].
The temperature at the surface of the sun is about 6000K. The extra-terrestrial spectrum
resembles black body spectrum at 5760K. A blackbody absorbs all radiation incidents on its
surface and releases radiation depending upon on its temperature. The blackbody sources that
emit light in the visible region are attractive for photovoltaic cells. The spectral irradiance
from a blackbody can be expressed following function [7];


F(2) =
2ahc
2
2
5
|exp[
hu
k2T
-1]

(2.1)
where:
is the wavelength of light, T is the temperature of the blackbody, and h, c and k
are constants.

Figure 2.1 : Black body spectrum compare with AM0 and Am1.5 Spectrum [6]


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The amount of the radiant energy received from the sun per unit area per unit time as a
function of wavelength is called solar irradiance [5]. The solar irradiance is strongest in the
visible wavelength range (300 - 800 nm) with maximum value in the blue to green range. The
power density of the solar radiation on the surface of the Sun is 62 MWm
-2
. This density is
reduced to 1353 Wm
-2
at a point outside the Earths atmosphere. When light passes through
the atmosphere, some portion of light are absorbed and dispersed by numerous atmospheric
elements, so that the spectrum received at the surface of earth has attenuation at different
points. Oxygen, Ozone and Nitrogen filter out the light with wavelength less than 300nm.
Water and CO
2
are mainly responsible for the absorption of the infrared and in consequence
produce the sudden drops in the spectrum at 900, 1100, 1400 and 1900 nm (due to H
2
O) and
at 1800 and 2600 nm (CO
2
) [5].
The attenuation of the spectrum is dependent on the distance the light travels through the
atmosphere, therefore is dependent on the location on the earth surface and the earths
position in orbit. The solar light spectrum is defined by the air mass index (AM). It is the
ratio of the path length of the solar radiation through the atmosphere at a given angle to the
path length when the sun is directly overhead [7].
Air Hoss =

X
=
1
cos (0)
(2.2)


Figure 2.2 : The air mass representing the portion of atmosphere that the light passes (Y) before reaching
the Earth comparative to overhead path length (X) [7]

The standard spectrum is Air Mass 1.5 or AM1.5, when the sun is at angle of elevation of
42
0
.

The solar spectrum is attenuated to a mean irradiance value of almost 900Wm
-2
due to
the atmospheric thickness. However, the standard spectrum (AM1.5) is regulated to
1000Wm
-2
because of the convenience of the round number and due to the fact that there are
natural variations in incident solar light [5].
The performance of a PV cell depends on both the power and the spectrum it receives. The
American Society for Testing and Materials defines different standard (AM0, AM1.5G and
AM1.5D) spectrums. The standard spectrum AM0 is used to evaluate the performance of
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solar cells for space applications. The AM1.5G and AM1.5D spectrums are used to predict
the solar cells performance on the Earths surface. The letter D (direct) declares that this
spectrum contains only the direct radiations and letter G (global) includes the direct as well as
the scattered radiation. AM1.5G is used for conventional terrestrial cells; while when
designing a concentrator system, the AM1.5D spectrum is used [7].

2.2 Semiconductor Basic Concepts
2.2.1 Band Theory
When a couple of atoms are combined together to form a molecule, their atomic orbits
combine together to create the molecular orbits. When a large numbers of atoms combine
together in a solid, then the mutual electrons of atoms combine together to form a crystal
structure, also known as a crystal lattice. The orbit of each atom splits into a large number of
energy levels close enough that they produce an energy band. The highest occupied band is
known as the valence band (VB), whereas the lowest unoccupied band is known as the
conduction band (CB) [5].

Figure 2.3 : Energy Band Gap Diagram of Semiconductor

If the lowest occupied band (VB) is partially occupied or if it overlaps with conduction band
(CB) then the solid is known as metal. If the valence band is fully occupied and does not
overlap with the conduction band (separated by an energy gap), then the solid is a
semiconductor or insulator. The minimum amount of energy required to excite an electron
from the highest occupied band to the lowest unoccupied band is called the band gap (E
g
).
Semiconductor materials usually have a band gap between the 0.5 to 3 eV [5].
Semiconductor conductivity in the dark is minute because a smaller number of electrons
transfer from the valence band to the conduction band in the dark. The conductivity of the
semiconductor decreases with the increase in the band gap whereas the conductivity of the
insulator is negligible because of the large band gap [5].


Conduction band
Valence band
Band gap
E
n
e
r
g
y

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2.2.2 Fermi Level
The electrons always attempt to be energy efficient. They always try to keep their energy as
low as possible. At absolute zero temperature the electrons contain no kinetic energy and
always try to reside in the lowest available energy levels. The energy up to which the
available states are filled is called the Fermi energy, E
F
. In a semiconductor the valence band
is fully occupied and the conduction band is fully empty, at the absolute zero temperature.
This indicates that the Fermi level lies in the centre of the band gap E
g
[5].


The vacuum level, E
vac
, is the energy to which electron must to be shifted to free from all
forces of the solid. The electron affinity is the minimum amount of energy required to
remove an electron from solid [5].
The concentration and nature of semiconductor carriers can be changed by adding a certain
amount of impurities by a process, known as doping. A semiconductor which is doped to rise
the concentration of electrons with respect to holes is known as n-type and if it is doped to
increase concentration of holes relative to electrons, then is known as p-type. After doping
the semiconductor the Fermi level is shifted from the middle of the band gap, nearer to the
conduction band E
c
in n type doped materials and nearer to the valence band E
v
in p type
doped materials [5].







Figure 2.4 : Intrinsic Semiconductor Fermi Level [5]
Figure 2.5 : Fermi Level of N and P type semiconductor [5]
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7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
7

2.2.3 Band Structure
The graph of the band energies against the wavevector k is known as the crystal band
structure. If the valence band maximum and conduction band minimum are present at same
value of wavevector k then the semiconductor is known as direct band gap material [8].
GaAs is the most important semiconductor with the direct band gap structure.
If the valence band maximum and conduction band minimum occur at different values of
wavevector k, then the semiconductor is known as an indirect band gap materials [8]. The
Silicon (Si) is the well-known semiconductor material with the indirect band gap. The figure
2.6 shows the band structures of GaAs and Si.



2.2.4 Electrons and Holes Generation
Generation is the electronic excitation process which results in the increase in the amount of
mobile carriers (electrons and holes) available to carry the charge, through the absorption of
light. Generation may include the shifting of the electron from the valence band to the
conduction band, which creates both electron and hole, or from valence band into the
localised state in the band gap, which generates only a hole, or from a localised state into
condition band which generates only electrons [5].

Figure 2.6: Band Structure GaAs and Si [8]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
8


The basis of a solar cell is to generate the photocurrent by absorbing the light. The efficiency
of the solar cell is calculated equilibrium between light absorption, current generation
and the charge recombination processes [5]. When light impinges upon the surface of the
solar cell it is either reflected or absorbed. On the other hand if it fails to do the above process
then it is transmitted through the material. The reflection and transmission processes do not
contribute to the photocurrent and result in a loss for the solar cell efficiency. The energy of
the photon is the main factor responsible for the absorption or transmission of the photon.
When the electron has enough energy (equals or greater than band gap) to stimulate the
electron from the valence band to the conduction band then it is absorbed. This absorption of
photons creates the electron and hole pair. The electron and hole pair releases their excess
energy in a very small time (femto seconds) by emission of phonons and relaxes to the edges
of the bands. If the energy of photon is less than band gap of the solar cell then photon will
pass through the semiconductor considering it as a transparent material [9].

2.2.5 Electrons and Holes Recombination
Recombination processes are known as the loss of free electrons or holes through the shifting
of an electron from the higher energy level to a lower energy level. The recombination may
include a decay from conduction band to the valence band, eliminating an electron-hole pair,
or it may be from conduction band to localised state (trap) removing an electron or from
localised state (trap) to the valence band resulting in the loss of a hole. The excited electron
in the conduction band remains there for limited period of time, known as the life time,
before it stabilizes to the lower energy state (valence band) by recombining with the hole.
The energy released can be given up as photon (radiative recombination), as heat through
phonon emission (non radiative recombination) or as kinetic energy to another free carrier
(Auger recombination) [5]. The important forms of recombination are shown in figure 2.8.



Figure 2.7: Photon absorption and electron and hole pair generation process [9]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
9




The band to band recombination process (Radiative recombination) dominates in direct band
gap semiconductors materials (e.g. GaAs). In this process an electron moves directly from the
conduction band to the valence band, recombines with the hole and generates the photon. The
trap assisted recombination also known as Shockley-Read-Hall or SRH recombination
happens because of the impurities in the material. This recombination process involves a trap
or localized energy level in the band gap. If the trap state captures a free carrier and this
carrier can be escaped by thermal activation. On the other hand, if another carrier of reverse
polarity is transported to the same energy level before the previous carrier is released then the
two carriers recombine. The Auger recombination comprises of three carriers when two
carrier of similar polarity collide then one carrier is excited to a higher kinetic energy, and the
recombination of other carrier occurs across the band gap. Auger recombination is significant
in low band gap materials with higher carrier densities [5]. The average distance a carrier
travels between the generation and recombination process is known as the diffusion length. It
can be expressed by the following formula:


L = VDz
(2.3)

where D is the diffusivity in m/s and is the lifetime in seconds.




Figure 2.8 : Band to band, trap assisted and Auger Recombination [5]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
10

2.3 PN Junction Formation
The photon generated current in the photovoltaic cells is achieved by the process of electron-
hole pair generation, their separation and transportation. The charge separation requires some
driving force to move the carrier. This purpose is accomplished by the formation of a p-n
junction which is created by combining n-type and p-type semiconductor materials, as shown
in figure 2.9.


The work function of the p-type semiconductor is higher than the n-type semiconductor
therefore the electrostatic potential is greater on the p-side than the n-side, and an electric
potential is established at the junction. The density of electrons comparative to holes is higher
in the n-type region while the density of positive charge carrier (holes) comparative to
negative charge carrier (electrons) is higher in the p-type region. The holes (electrons) from
the p-type (n-type) region diffuse into the n-type (p-type) side and this diffusion process will
last until the concentration of electrons and holes on the two sides becomes equal [5].






Figure 2.9 : (a) Band profile of n-type and p-type semiconductor. (b) Band profile of
the p-n junction in equilibrium. [5]
Figure 2.10 : An ideal model of p-n Junction without bias [10]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
11

In the p-n junction carriers diffusion across the junction leaves behind a layer of fixed ionised
atoms on the both sides as shown in figure 2.10. These space charges establish an electric
field which opposes the further diffusion across the junction. This region is known as the
"depletion region" because it is depleted of free carriers. A built in voltage I
b
due to this
electric field is produced at the junction. The p-n junction region always presents a high
resistance to majority carriers and a small resistance to the minority carriers. The movement
of minority carriers across the depletion region causes a drift current. The net current is equal
to zero for both electrons and holes because of the fact that the diffusion current
counterbalances the drift current for both carriers [10].
The built in voltage at the junction can be expressed by the equations
I
b
=
k
B
I
c
ln_
p
p
p
n
] (2.4)

I
b
=
k
B
I
c
ln_
n
n
n
p
_ (2.5)

where n
n
and n
p
are the electron densities in the n-type and p-type regions and k
B
is
Boltzmanns constant.
The width of the depletion in the n-type and p-type regions can be given by the following set
of expressions:


w
p
(I
b
) = _
2eI
b
c
_
N
d
N
u
(N
u
+ N
d
)
__
1
2
,

(2.6)


w
n
(I
b
) = _
2eI
b
c
_
N
u
N
d
(N
u
+ N
d
)
__
1
2
,

(2.7)

where N
a
and N
d
are the uniform doping densities of the acceptors and donors.






U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
12

2.4 Solar Cell Equivalent Circuit
The solar cell can be modelled electrically as a current source in parallel with a nonlinear
device, such as a diode. When there is no light, the solar cell behaves like an ordinary diode.
When the solar cell is illuminated with light, excess electron and hole pairs are generated and
hence photocurrent relative to the intensity of light and temperature flows through the device
[12]. This current is divided between the diode resistance and the load resistance. When the
load resistance is high, a small amount of current flows through the load, and the majority of
photocurrent will flow through the diode that will result in a higher potential difference
across the solar cell terminals.








The potential difference across the terminals of the cell produces a current which flows in the
reverse direction to the photocurrent and the total current is decreased by its short circuit
current value. This reverse current is known as the dark current. This current is analogous to
the current which flows through the device under an applied voltage in the dark [5].

[
duk
(I) = [
o
(c
qv
k
B
1
-1)
(2.8)









Figure 2.11 : Ideal Solar Cell Model and I-V characteristics [5]
Figure 2.12 : Dark and Light Current [5]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
13


The net current can be expressed as:

[ = [
sc
- [
o
(c
qv
k
B
1
-1)
(2.9)

The fill factor is a essential parameter to measure the quality of the solar cell. The fill factor
is defined as the ratio of maximum power to the theoratical power (Product of open circuit
voltage and short circuit current density) [5].

FF =
[
m
I
m
[
sc
I
oc

(2.10)
where:
J
sc
is the short circuit current density.
V
oc
is the open-circuit voltage.
The efficiency is the most important factor to examine the performance of the solar cell. It is
defined as the ratio of electrical power output from the solar cell to input power from the sun
[5].

p =
[
m
I
m
P
s

(2.11)
The characteristic resistance is known as the output resistance of the PV cell at which it gives
maximum power. If the load resistance is equivalent to the characteristic resistance, then the
maximum power is delivered to the load and the PV cell functions at its maximum power
point [11].

Figure 2.13 : Characteristic Resistance of solar cell [11]


U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
14


It is given by the expression:

R
CH
=
I
0C
I
SC


(2.12)
In a practical solar cell power is dissipated through the contact resistance and through leakage
currents of the solar cells. These effects can be expressed by the equivalent parasitic
resistance in series and in parallel [12]. The series resistance represents contact resistance and
the cell material resistance to the flow of current from the front surface to the contacts. The
shunt (parallel) resistance expresses the leakage current around the boundaries of the device
and between contacts with different polarity [5].







The increase in the series and decrease in the parallel resistance cause a decrement in the fill
factor and thus efficiency as shown in figure 2.15










Figure 2.14 : Solar Cell Model with series and shunt resistance [5]
Figure 2.15 : Effect of Series and Shunt Resistance on Efficiency and Fill Factor [5]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
15

2.5 Single Band Solar Cell
The main function of a photovoltaic cell is to convert the solar radiation into the electrical
power. In this quantum energy conversion method packets of light energy (photons) are used
to produce the electron hole pairs and these electron hole pairs are separated by the p-n
junction to make them work in the external circuit [14]. The solar cell efficiency is an
important factor to compare the performance of solar cells. In the ideal case (only radiative
recombination) the efficiency of the solar cell depend on band gap (E
g
) and the incident
spectrum. If the solar spectrum is stable then the PV cells efficiency depends only on the
band gap. The efficiency of the single band gap solar cell is limited to 33% for a band gap
(E
g
) of around 1.4eV for the standard air mass 1.5 (AM1.5) spectrum according to the
detailed balance limit given by Shockley and Queisser in 1961 [13].








A large portion of the suns energy is lost because of solar cell failure to absorb the photons
having energy smaller than the band gap. The efficiency is highest for photons having energy
closer to the band gap and it is zero for photons with energy lower than band gap (E<E
g
) or it
is low for photons with energy larger than the band gap (E>>E
g
). The efficiency of PV cells
with very small (very large) band gaps decreases because of small values of voltage
(photocurrent) [5].
2.6 Tandem Solar Cell
2.6.1 Strategies to Improve Efficiency
The multiband gap system with several junctions of different energy gaps is an ideal
approach to enhance the efficiency of solar cells. Another technique is to increase the number
of electron hole pairs generated by a photon using impact ionisation solar cells [16]. The
efficiency of the photovoltaic cells can be improved by absorbing the photons of different
energies in cells of different band gap. The efficiency of a single band gap solar cell improves
considerably with monochromatic light which is adjusted to the band gap. If the solar
spectrum is divided into different wavelength and guided into photovoltaic cells of different
band gaps then more of the solar spectrum can be coupled and higher power could be
extracted from the same spectrum [15].
Figure 2.16 : Single band solar cell Limited Efficiency at AM1.5 [5]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
16

2.6.2 Principles of tandem solar cells
The tandem solar cells can be arranged in different ways, such as independent spectrum
splitting, mechanically stacked cells and monolithically grown cells, to cover the desired
spectrum [16].









In the first technique the photons of different energies are filtered by using dichroic mirrors
and directed on the respective cells with different band gap. In practice it is very difficult to
efficiently split up the spectrum. A more well-designed strategy is to arrange solar cells with
different band gap junctions in series using mechanical stacking or a monolithical growth
technique. In these strategies larger band gap cells are placed at the top to filter out the
majority of the lower wavelength photons, while higher wavelength photons pass through to
smaller band gap materials below. The mechanically stacked cells method is simplest but the
cells should be thin to minimize the absorption losses and a perfect alignment of grids is
desirable [16].
For the two solar cell tandem system, two different wiring configurations (two, four
terminals) can be achieved. The four terminal arrangements require independent contact to
top and bottom a cell which is difficult to attain in practice. A more well-designed
organization is to connect all the cells in series. The problem with this arrangement is that
same current is flowing through each cell so this limits the band gaps that can be used
because of the need to keep the current as close as possible (current matching) [15].





Figure 2.18 : Two and Four Terminal Solar Cell [5]
Mechanically
Stacked
Monolithical
Configuration
Spectrum Splitting
Figure 2.17: Mechanically stacked, monolithical and optically integrated configuration of solar cells [17]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
17


In monolithically grown cells different layers of materials are grown on the same substrate.
The two junctions are connected in series with help of a tunnel junction or metal deposit.
Series connected cells are easier to fabricate. The lattice constant and thermal coefficient
matching of different materials needs to be considered before monolithical growth. The
optical losses in this configuration are minimized [16].
2.7 III V Semiconductor
The group III atoms of the periodic table combine with the atoms of group V to form
crystalline semiconducting compounds, known as III V semiconductors. III V
semiconductor alloys contains equal numbers of atoms (1:1 atomic ratio) from groups III and
V atoms. The group III and V atoms donate three and five valence electrons respectively to
form a tetrahedral covalent bond. The majority of III V compounds including the GaAs,
InP, AlSb etc. have a zinc blende crystal structure [5].
III V compounds are grown by a variety of epitaxial techniques such as molecular beam
epitaxy (MBE), liquid phase epitaxy (LPE), metal organic vapour phase epitaxy
(MOVPE) and metal organic chemical vapour deposition (MOCVD). The most famous
and extensively used of III V semiconductor is gallium arsenide (GaAs) and other relevant
ternary alloys such as Gallium Arsenide Bismide (Ga
1-x
AsBi
x
) or Gallium Arsenide Nitride
(Ga
1-x
AsN
x
), where a portion x of gallium atoms in GaAs replace the Bismuth (Nitride) atom
[5]. The GaAs semiconductor bonding structure and band gap is shown in figure 2.19.









GaAs has a direct band gap structure with band gap of 1.42 eV, which is close to the ideal
band gap for the standard solar spectrum and has 31 % theoretical efficiency. The absorption
coefficient of GaAs is approximately ten times higher than that of silicon as shown in figure
2.20, therefore a thinner (few m) active layer of the PV cell is required, that makes the
GaAs solar cell suitable for the space activities because of the lower weight.

Figure 2.19 : GaAs Bonding Structure and Band Gap Diagram [5]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
18














Carrier mobilities are also higher in GaAs materials (Electrons: 8500 cm
2
/V s, Holes: 420
cm
2
/V s) [19]. The most significant advantage of GaAs is the possibility of substituting
certain group III atoms with the atoms of other group III elements with the intention of
changing the composition of crystal to vary the band gap. Another benefit is that the majority
of these compounds are direct band gap semiconductors. The lattice constant difference of
different GaAs alloys is very minute therefore these alloys can be grown epitaxially upon
each other to create a highly efficient device.













Figure 2.20 : Absorption Coefficients of Silicon and GaAs at different energy/eV [5]
Figure 2.21 : Lattice Constant and band gap relationship of III-V compounds [18]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
19

Solar cell efficiency has a tendency to decrease with the increase of temperature, due to
increase in carrier recombination and a reduction in the band gap. GaAs also has the better
temperature coefficient as compared to silicon and germanium as presented in the figure 2.22.











2.7.1 Doping
In GaAs, n type doping is done by incorporating a controlled quantity of silicon during
growth process. The silicon atoms usually substitute some of the gallium atoms, and create a
donor state because of the addition of an electron. Another tetravalent element, Tin can be
used for n type doping [5].
On the other hand carbon is the most generally used as an impurity for p type doping.
Carbon, the same as silicon is also a tetravalent element but under particular growth
conditions it has a preference to replace arsenic atoms in the lattice structure, and creates an
acceptor state because of the shortage of an electron. Otherwise beryllium (Group II) can be
used, which forms an acceptor state by replacing Ga atoms. Doping is done by diffusion of
elements or directly during the epitaxial growth techniques [5].





Figure 2.22: Energy Band gap dependence on temperature of GaAs, Si and Ge [20]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
20

2.8 Dilute Bismide

Bismuth is the heaviest (atomic mass of 208 amu) element of group V of the periodic table
with the large atomic radius. The atomic size and core electronic structure of Bi is different
from those of P and As atoms. It is therefore obvious that alloying Bi with III-V materials
results in unusual alloy properties [22].
In recent years different elements (Bi, N, etc.) of group V have been incorporated into the III-
V alloy, which ends up with interesting properties. Bismuth containing materials have caused
remarkable interest because of the fascinating properties such as, band anti crossing effect in
the valence band that cause a large band gap bowing effect, when a small amount of bismuth
is incorporated into III V semiconductors (e.g. GaAs). The incorporation of bismuth in III
V compounds creates Bi defect states close to the valence band edge of the host
semiconductor. The Bi incorporation also increases spin orbit splitting energy due to the large
size of the bismuth atom [21].







The spin orbit splitting energy
SO
, increases rapidly with the increase in the atomic number
of group V elements. Due to the large size of bismuth atom it is theoretically predicted that
GaBi should have the largest spin orbit splitting energy
SO
(2.2 eV), as shown in the figure
2.24.











Figure 2.23 : Group V elements of periodic table
Figure 2.24 : Increase in spin orbit splitting energy of III-V compound
with group elements atomic number [21]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
21

The band gap bowing effects due to Bi can be modelled by using the band anti crossing
model (BAC). In BAC the incorporation of Bi produces a Bi resonant level and its interaction
with the valence band maximum (VBM) leads to band gap bowing effect due to the
formation of E
+
and E

valence sub bands as show in figure 2.25.

The decrease (increase) in the band gap E
g
(
SO
) with the fraction of bismuth in the dilute
bismide is expressed in figure 2.26. The figure shows that the band gap decreases rapidly
with increasing Bismuth content at a rate of 60 meV/Bi% approximately [21].










Figure 2.26 : Effect of increase in bismuth incorporation on the
band gap and spin orbit splitting [21]
Figure 2.25 : Band anti crossing model of GaAsBi [55]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
22

The spin orbit splitting larger than the band gap (
SO
> Eg), has the advantage of reducing
the fundamental carrier losses such as CHSH Auger recombination (in which a recombining
electron-hole pair give their energy to a second hole which is excited to a higher energy band)
or hole leakage and optical losses such as Inter Valence band absorption (IVBA). The carrier
leakage losses (thermal escapes) can be eliminated by higher valence (E
v
) and conduction
(E
c
) band offsets [23]. In figure 2.26 spin orbit splitting
SO
surpasses band gap E
g
with the
Bi fraction of ~9% on GaAs. Thus in the dilute bismide with Bismuth content more than 9%,
the Auger recombination loss is eliminated and therefore optimum band structure is obtained.
The sensitivity of the band gap of dilute bismide (GaAsBi) to temperature is slightly reduced
in comparison with the GaAs [22]. The figure 2.27 indicates that the band gap dependence of
GaAs on temperature is almost similar with the GaAsBi having bismuth contents up to 3.1%,
and has minute effects on the band gap dependence on temperature.









2.8.1 Growth of Dilute Bismide

The growth of GaAs
1-x
Bi
x
with high Bi incorporation by molecular beam epitaxy (MBE)
has some limitations due to the weak reactivity of the bismuth (Bi) with the Gallium (Ga) and
the great tendency of Bi to surface segregate because of the large size of bismuth atom [24].
The growth of GaAs
1-x
Bi
x
alloys, results in the formation of metallic surface droplets under
conventional MBE III-V growth conditions. The sizes and densities of the droplets is
apparently dependent on the Bi flux, growth rate, III-V ratio and growth temperature [27].
The incorporation of Bi content in growth of the GaAs
1-x
Bi
x
depends on following different
parameters.


Figure 2.27 : Effects on band gap of GaAs (without and with Bi
concentration) on temperature [22]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
23

2.8.1.1 Dependence of Bi content on Bi : Ga BEPR

The Bi incorporation is directly proportional with the Bi : Ga beam equivalent ratio pressure
(BEPR). It grows linearly with the Bi:Ga BEPR and then the Bi content becomes constant
and shows no change with the increase in Bi : Ga BEPR, as shown in figure 2.28. After this
phase the Bi incorporation is determined by the As
2
: Ga BEPR and the growth temperature
of devices [26].

Figure 2.28: Bi content as function of Bi : Ga BEPR [26]
2.8.1.2 Dependence of Bi content on As
2
: Ga BEPR

The Bi incorporation is inversely proportional with the As
2
: Ga flux ratio / BEPR [26]. The
figure 2.29 shows that the Bi content becomes constant when the As
2
: Ga BEPR is
decremented below 2.25 and further decrease in BEPR does not affect the Bi concentration.
On the other hand Bi content decreases rapidly with increase in As
2
: Ga BEPR from 2.25 to
3.6. When As
2
: Ga BEPR is increased above 4.5, then no Bi incorporation was detected.




U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
24











Figure 2.29: Bi content dependence on As
2
: Ga BEPR [26]
2.8.1.3 Dependence of Bi content on growth temperature

The Bi incorporation also has an inverse relationship with growth temperature as the Bi
content increases very rapidly with the decrease in the growth temperature. It is clear from
figure 2.30 that the Bi concentration was less than ~10% and then it reaches to ~22% at the
temperature 200
o
C. Lewis et al grew samples at the range of 0.81 1.7 As
2
: Ga BEPR, at
which the Bi incorporation is constant (as shown in figure 2.29). The solid data points were
grown at large Bi : Ga BEPR (0.59), at which Bi incorporation has saturated (as shown in
figure 2.28).







Figure 2.30: Bi content as a function of growth temperature [26]

U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
25

2.8.1.4 Dependence on the Growth Rate:
The Bi incorporation is not affected by the growth rate. But the growth rate is a significant
factor for controlling the development of Bi droplets. The low growth rates enable the growth
of GaAs
1-x
Bi
x
with higher Bi concentrations and smaller Bi droplet density. When the Bi
atoms are incident on the substrate it can do one of following three actions (as shown in the
inset of figure 2.30).
Incorporate into the substrate
Evaporate back into the vapour
Attach to the Bi droplet
In order to minimize the chances of the formation of Bi droplets, the flux rate of Bi should be
less than the sum of the incorporation and the evaporation rate [25]. According to Vardar et
al, Ga- rich GaAs
1-x
Bi
x
growth results in Ga-Bi droplets whereas on the other hand, As-rich,
GaAs
1-x
Bi
x
growth produces a droplet free surface [27].
2.9 Dilute Nitride

When a small quantity of nitrogen is incorporated into GaAs to form dilute nitride alloy a
profound effect on fundamental band gap is exhibited as compared to conventional
semiconductor alloys [28]. Although the GaN band gap is 2 eV higher in comparison to
GaAs, it is monitored that band gap energy decrease with the increasing contents of nitrogen
and reduction of almost 205 meV for 1 % of nitrogen is observed [29].
Semiconductor alloys create by substituting a small percentage of host atoms with the atoms
of other element having different electronegativity and/or sizes are known as highly
mismatched alloys (HMA). The properties of HMAs are intensely changed e.g. they show
large band gap decrement and their electronic structure are extremely different from their
host materials [30]. The lattice constants of GaAs mismatched with GaN by 20%, and the
nitrogen atom has higher tendency to attract electrons in relation to arsenic atom. These
mentioned features encourage a distortion of the electrostatic potential in the crystal and thus
results in the non-linear behaviour of the band energy gap [29].
In 1995 Kondow et. al. revealed that incorporation of small quantity of nitrogen in GaAs
exhibits a band gap reduction effect, due to small size ionic radius of nitrogen. The
dependence of the energy band gap on the nitrogen (N) concentration in the dilute nitride has
been the explained by many theoretical techniques. The band anti crossing (BAC) model is
used to theoretically model the structures of the dilute nitride as show in the figure 2.31.
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
26











The band gap energy of dilute nitride (GaNAs) reduces with the rise in temperature and the
rate of this reduction becomes lower and lower, when the nitrogen concentration is increases.
The addition of 1% of nitrogen (N) content reduces the band gap by ~205 meV at room
temperature, and ~250 meV at lower temperature [29]. The band gap difference for the
temperature 15K and 300K declines from 110 meV in case of GaAs to 70 meV for the
GaAsN with nitrogen concentration of 1.5%, as shown in figure 2.32.











The growth of dilute nitride semiconductor is challenging task, they are usually grown by
either metal organic vapour phase epitaxy (MOCVD) or gas source molecular beam
epitaxy (GSMBE) [28].
Figure 2.32 : Energy band gap response to the temperature and the Nitrogen concentration [29]
Figure 2.31 : Band Anti Crossing model of dilute Nitride [54]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
27

2.10 Quantum Wells

In the order to get higher efficient PV cells the structure of solar cell continues to evolve. The
single band solar cell only absorbs photons with energies larger than or equal to their band
gap. Hence, the remaining lower solar spectrum is lost. Tandem solar cells improve the
absorption characteristics of solar cells. However their efficiency still far short of the
theoretical efficiency of 42% to 52%. One of the limitations of the tandem solar cell is that
the current matching. The other challenge with the tandem cells is the diffusion length is
lower than the depletion layer which reduces the current.
There are several epitaxial growth techniques of changing the band gap of semiconductors by
formation of materials with a different chemical composition. Initially, the development of
the growth techniques focus on the formation of homojunctions comprising of semiconductor
material having the same composition with different impurities and carrier concentrations.
Subsequently, the interest shifted toward heterojunctions, containing two semiconductor
materials of different band gap [33].

A double heterostructure is formed when a thin layer (whose thickness varies from ~250 to
~ 10) of narrow band gap semiconductor placed between the bulk semiconductors of larger
band gaps. A quantum well is created, if the thickness of the thin layer becomes comparable
to the De Broglie wavelength (~10nm) of the carriers. In this case larger band gap act as
barriers to electron flow, which traps the mobile carriers in the resulting quantum well. The
carriers in the thin layer start to behave according to particle in a potential well. Now the
conduction band energy levels are quantised and only definite values are allowed to exist
[33].


The main purpose of quantum well solar cells (QWSCs) is to control the open circuit voltage
by reducing the recombination in the bulk material (barriers), while the lower band gap
material sections, known as the wells, absorb low energy photons that the bulk material
cannot utilise [35]. The carriers produced by the extra photons absorbed in the well escape to
the barriers and produce the additional current. There is some voltage loss, but the
Figure 2.33 : Energy structure and single-particle wave function for single
quantum well solar cell [33]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
28

improvement in current of the QWs is enough to overweight the voltage losses. Hence, the
wells can improve efficiency of solar cells compared with conventional cells [31].
If the quantum well structure repeats itself in a periodic routine it is known as a multiple
quantum well (MQW) [33]. The quantum well solar cell (QWSC) is a diverse technique to
achieve the multi-band gap solar cells where a multi quantum well system is generated in the
intrinsic region of a pin structure [34]. The p-i-n designed addresses the defect of short
diffusion lengths of carriers in tandem solar cells.


The output voltage of the quantum well solar cells depends on the width of barrier, the
recombination rate in the wells and the interface between barrier and wells. Whereas the
short-circuit current is subject to the width and depth of the quantum well. Deeper quantum
wells can absorb longer wavelength light and generate a higher photocurrent. On the other
hand, deeper wells has higher recombination rate that results in a reduction of the output
voltage. Therefore, quantum wells depth creates a trade-off between the output voltage and
the photocurrent [34].
The increment in the thickness of the well increases the absorption per well, but a lesser
number of wells can accommodate in the solar cell. Alternatively, a thinner well absorbs
fewer photons but a larger number of wells can be accommodated in the intrinsic region.
Moreover, the wider quantum well has the higher recombination ratio and as a result the
open-circuit voltage declines. On the other hand increase in the number of the wells can
absorb more photons that results in increment in the photocurrent but the recombination in
the interfaces also rises that cause a reduction in the output voltage. Due to mentioned
reasons, it is essential to enhance the design of QW solar cell so that attain higher efficient
solar cells [34].
Figure 2.34: Schematic energy band diagram of a QWSC [31]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
29

Imperial College of London demonstrated that quantum wells can improve the efficiency of
conventional bulk tandem solar cell by building a tandem quantum well structure which
attained the efficiency of 30.6% under 54 suns AM1.5G [32]. Later they were successful in
showing that both the short circuit current and open circuit voltage can increase for multi
quantum well solar cells [31].




















U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
30

3 Experimental ec!ni"ues
3.1 Epitaxial Growth Techniques
There are four techniques that are most commonly used for the epitaxial growth of elements,
compounds and semiconductors alloy films: molecular beam epitaxy (MBE), metal
organic chemical vapour deposition (MOCVD), vapour phase epitaxy (VPE) and liquid
phase epitaxy (LPE). The word epitaxy originates from the Greek word epi (upon) and
taxis (order), and refers to the well-arranged placements of atoms upon the substrate
crystal. The slow growth rate of the epitaxial growth techniques allows one to accurately
control the growth process [10]. A comparison of these epitaxial growth techniques is
provided in Table 3.1 [36].

Table 3.1: Comparisons of Epitaxial Growth Techniques
Properties LPE VPE MOCVD MBE
All Alloys
Capable Difficult Capable Capable
Range of Growth rate
(m/min)
0.1~10 0.01~0.5 0.005~1.5 few~0.05
Minimum Thickness ()
500 250 20 5
Doping level (cm
-3
)
1014~1019 1014~1019 1014~1019 1014~1019
Productivity
Low High High Very Low
3.1.1 Molecular beam epitaxy (MBE)

Molecular beam epitaxy (MBE) is the most important technique for epitaxial growth of
semiconductors and nearly every semiconductor (except some very large band gap
semiconductors) has been grown using this technique [10]. MBE is considered to be the most
favourable growth technique for the future because it has several important features, such as
precise control of layer thickness, smaller growth temperature compared to other growth
techniques, better dopant control, and more accurate epitaxial layer growth due to the UHV
growth environment [37].

In MBE the elemental, compound and alloy semiconductor films are grown on the substrate
under high vacuum or ultra-high vacuum (<10
-10
Torr) with a low growth rate (0.1 to 1 m/h).
This allows one to accurately control the incorporating atoms or molecules and thus the
thickness of the film. In the growth chamber, an ultra-high vacuum (UHV) is needed to move
the evaporated sources in a beam pattern and to remove any particles present in the growth
chamber that could become incorporated into grown layers resulting in defects. To achieve an
ultra-high vacuum level, the cryopanels with cold nitrogen gas at a temperature of
approximately 77 Kelvin are used to surround the whole growth area with the purpose of
minimizing the residual water vapour and carbon containing gases by condensing them and
allowing them to be quickly removed from the chamber through conventional pumps [36].
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31

An MBE system usually contains three vacuum chambers: a growth chamber, an analysis
chamber and a small sample load lock chamber. The metal sealed or Viton sealed gate
valves are used to separate these chambers from one another [36].

The growth chamber is the most significant module of an MBE system. A growth chamber
usually consists of effusion cells, shutters, a substrate manipulator, cryopanels, and some
surface analysis equipment [36]. The most common sources for molecular beams are effusion
cells, also known as Knudsen Cells. These cells are made of graphite pyrolytic boron nitride
(PBN) [37]. The effusion cells are usually 7.5 12 cm long and have a diameter of 2.5 cm
[36]. In solid phase source MBE, all elements including Bi, group III elements In, Ga and Al,
and dopants Te, Si, Be, in ultra-pure form, are placed in effusion cells and heated by tantalum
(Ta) heating elements, in separate effusion cells until they start to slowly evaporate [37]. The
gaseous elements are then incorporated into the substrate. The effusion cells are surrounded
by the water cooling system to reduce the chances of heat transfer between the cryopanels
and the Knudsen cells. The beam flux is controlled by accurate control of the temperature.
The flux arriving at the substrate is monitored by using a beam flow gauge placed behind the
substrate holder. The substrate is mounted on molybdenum (Mo) holder, and because of its
high thermal conductivity, a constant temperature can be attained across the substrate. Indium
(liquid at the MBE growth temperature) is used to bind the wafer to the molybdenum (Mo)
holder [37].
The rotary substrate manipulator is used to turn the substrate at a speed up to 125 rpm during
growth for uniform epitaxial film thickness and doping uniformity. The substrate outgassing
is achieved by heating the substrate up to 300 C to remove gasses which would otherwise
contaminate the growth chamber.
One of the distinctive features of MBE is its capability to rapidly switch the growth element
from one source to another. This property allows one to accurately control materials of
different layers and their thickness. The switching of the growth elements beam is usually
done with the mechanical control shutters [37].
To avoid contamination, a sample load lock is used to place and remove the wafers from the
MBE growth chamber with minimum disturbance of the vacuum conditions [36].
A majority of analysis devices are used to observe the structure of the epitaxially grown
Figure 3.1: Schematic layout of the main chamber of MBE system [38]
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32

layers throughout the growth process. The analysis chamber comprises of the surface analysis
equipment. An auger electron spectrometer (AES), a secondary ion mass spectrometer
(SIMS), an X-ray photoelectron spectroscope (XPS), and a scanning electron microscope
(SEM) are used to examine the sample surface [36]. The surface analysis of the sample is
performed during growth by using reflective high energy electron diffraction (RHEED)
apparatus. RHEED is used to observe the structure, thickness and surface morphology of the
growing film. In this process an electron gun generates a high energy electron beam (5 50
keV), which strikes the surface of the substrate at a small angle (1 2
o
). Electrons are
reflected from the substrate surface and strike a fluorescent screen forming a diffraction
pattern which allows observation of the growth of the layers [37].

3.2 Fabrication Process

The fabrication process consists of photolithography techniques and several chemical
processes that can produce extremely complicated electronic devices. The metallic contacts
are constructed on the sample for the electrical characterisation of solar cells. Therefore, by
using the photolithography process, either the cylindrical mesa structure or the Hall bars
structure pattern (for Hall Measurements) contacts are made on the solar samples. Figure 3.2
shows the structure of the most common cylindrical mesa [39] and the Hall bars structures.
[40]
3.2.1 Cleaving
The solar cell device (cylindrical mesa structure) used for the experiments has a diameter of
less than 2 mm. Therefore in the first stage of fabrication, a large-sized wafer is cleaved into
the required size of sample (~5mm) to fabricate the desired device.
After measuring the required size (5mm) of the sample with the help of a ruler, a scriber is
used to make a tiny scratch at the edge of the front side of the sample. The sample is then
turned over and a small amount of pressure is applied to the back side (substrate side) in the
exact position of the scratch. This will result in a straight crack across the semiconductor
wafer.



Figure 3.2: Cylindrical Mesa and Hall bars Structure
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33

The four steps of the cleaving process are shown in the figure 3.3.

3.2.2 Sample Cleaning
With the purpose of achieving low resistance contacts, the sample is cleaned before further
processing. The sample is placed in the acetone for 30 seconds and then soaked in ethanol for
1 minute. Once the sample is clean, it is rinsed in deionised water and then dried using
nitrogen gas (N
2
) [50].
3.2.3 Mounting
The handling of the small sample (5mm) is very difficult, and thus, in order to handle the
sample easily during the processing, it is fixed on a glass cover slip. The glass slide is heated
on a hot plate up to 150
o
C and crystal bond is spread onto the slide to stick the sample to the
slide. The sample is then placed on the glass slide with the substrate facing down, and then
the glass is removed from the hot plate so that the sample is firmly bonded to the glass slide
[50].

3.2.4 Oxide Removal
The oxides present on the sample are responsible for an increase in contact resistance, which
causes a reduction in the fill factor and hence in the efficiency of the solar cell. To remove
the oxide layers, the sample is placed in a solution of aqueous ammonia (35% NH
3
) for 45
seconds. The sample is then rinsed with deionised water and dried using nitrogen gas (N
2
).
3.2.5 Photolithography
Spin Coating
In order to transfer a desired pattern onto a sample, the surface of the sample should be made
sensitive to UV light. The surface of the sample is made sensitive by spreading a photoresist
(positive or negative) onto the sample by a process known as spin coating [10]. The desired
sample is placed on the spin coater and two to three drops of BPRS 150 positive photoresist
Figure 3.3 : Four Steps for process of Cleaving [41]
Figure 3.4 : Sample mounted on the glass slide
Sample
Glass Slide
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34

are applied to the sample. The sample is then left to soak in photoresist for 1 minute to
eliminate air bubbles before the sample is spun at 4000 rpm for 30 seconds.






Soft Baking
After the spin coating process, the sample is removed from the spin coater and placed on the
hot plate at 95 C for 60 seconds for soft baking, to make the photoresist thinner and
photosensitive.

Masking
The sample with the photoresist coating is then employed on the mask aligner and a photo
mask with the required pattern is used. The sample is aligned with the pattern using the micro
positioners. When the sample and masking pattern are aligned, the mask is lowered down so
that it touches the sample, to minimize diffraction effects. Then the sample is exposed to ultra
violet (UV) light through the mask for 10 seconds [50].
3.2.6 Developing
After ultra violet (UV) illumination, the sample is developed using a Sodium Hydroxide
(NaOH) and water (H
2
O) solution prepared with 1 and 10 proportions, respectively. The
sample is placed in the solution until the photoresist is developed and the pattern becomes
visible. When the pattern becomes clear, the sample is removed from the developer, rinsed
with deionised water and dried with nitrogen gas (N
2
) [50].




Figure 3.5 : Applying BPRS 150 positive photoresist
Figure 3.6 : Sample with the mask after developing
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D
4
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8
35

3.2.7 Oxide Removal
Before the process of evaporation, oxides are removed again from the sample using the
solution of aqueous ammonia (35% NH
3
). The sample is then rinsed with deionised water and
dried using nitrogen gas (N
2
). At the end, the sample is exposed to UV light for blanket
exposure.

3.2.8 Evaporation
In this process the metallic contacts are evaporated onto the sample using an Edwards E306A
vacuum coating unit. For the n-type materials Au/Au:Ge/Ni/Au contacts are used, whereas for
the p-type materials Au/Zn:Au/Au contacts are most commonly used. The Ti / Au contacts are
used for the heavily doped (because it bond to the top of the device) devices. The required
metals are loaded into Tungsten (W) baskets (Ti, Ni, Zn) or Molybdenum (Mo) boats (Au,
Ge), so that they can be evaporated by heating [50].

Once the sample is loaded within the coating unit, Firstly the system is pumped to 10
-2
millibar with help of rotary pump and then after this it is driven to 10
-6
millibar using a
diffusion pump. When the required vacuum pressure is achieved, the metals are evaporated in
the correct layers order by applying current. At the end of this process, the coating unit is left
to cool down for a minimum of 30 minutes before opening.

3.2.9 Lift off
After the evaporation process the sample and glass slide are completely covered with the
metal. To achieve the desired pattern with the metal on it, the sample is soaked in acetone.
This will dissolve the photoresist, leaving behind a clear area, while the metal contacts
remain on mask pattern areas. After achieving a perfect contact pattern, the sample is rinsed
in deionized water to stop the lift off operation and dried with nitrogen gas (N
2
).



3.2.10 Annealing
Before the annealing process the sample is removed from the class slide by putting it on the
hot plate (150
o
C) and crystal bond is removed with acetone. This process is done to diffuse
the Au/Zn:Au/Au or Au/Au:Ge/Ni/Au contacts into the device. The samples are annealed at
temperature of 350 C for the p-type or 400 C for the n-type contacts for 15 to 30 seconds.


Figure 3.7 : Sample after evaporation and Lift off Processes
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36

3.2.11 Etching
The simplest and most frequently used etching technique is wet chemical etching, in which
the sample is drenched in a chemical that removes the semiconductor material layers from
selected areas [10]. In the etching process steps 3 (Mounting) to 6 (Developing) are repeated
again using the etching mask. The area which needs to be removed is exposed to ultra violet
(UV) light and those not to be etched are covered with positive photoresist. Once the desired
pattern is transferred from a mask to a wafer, the material from selected regions is removed
or etched to define a fixed active area for the solar cell and the contacting layer of the sample
is also removed so that light directly fall on the window layer.

Hard Baking
Once the sample is developed, it is placed on the hot plate at 150 C for 1 minute for hard
baking to make sure that the photoresist is resistant to etchant and to enhance adhesion of
photoresist to the surface of the sample.

Active Area Etching
In order to do the active area etching the etchant H
2
SO
4
:H
2
O
2
:H
2
O is prepared in the ratio
1:8:80 respectively. The H
2
O
2
behaves as the oxidizing agent whereas the H
2
SO
4
dissolves
the resulting oxide [42]. This solution has an etch rate of 500 nm/minute. The thickness of
the photoresist is measured with the help of surface profiler. Then the sample is put in the
etchant for a time long enough, to reach the substrate. The depth of the etched area is then
checked using the surface profiler.

Contacting Layer Etching
In order to make it possible for the light to hit directly the AlGaAs window layer, the GaAs
contacting layer is etched away. The sample is cleaned using acetone and then placed in
solution of Citric acid and H
2
O
2
prepared in the ratio 10 to 1. The etch rate of this solution is
200 nm/minute for GaAs but has an etch rate of 2 nm/minute for AlGaAs.




Figure 3.8 : Spin coating, applying etching mask and expose to UV, developing and etching process

UV
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6
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D
4
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37

3.2.12 Contact on the back Side
After the etching process the front side of the devices is completed and now contacts are
made on the back side of the device. To do this process, step 2(Sample Cleaning), step
3(Mounting), step 4(Oxide Removal) and step 8(Evaporation) are repeated with the substrate
facing up.

3.3 Experiments
3.3.1 I V Measurements

The solar cell characterization comprises measurement of the solar cells electrical
performance characteristics to calculate the conversion efficiency and different parameters of
the equivalent circuit. The Current Voltage (I V) characteristic of a solar cell under light
and in dark are the most important experimental results in order to know about the
performance of the solar cell under normal operational conditions. In this technique the
short circuit current density (J
SC
), open circuit voltage (V
OC
), fill factor (FF) and the
efficiency () of the PV cells are measured. All of these critical performance factors
depend on both the illuminating light spectrum and the temperature of the solar cell [43].
Therefore, for comparison of results, these experiments are performed using standard
operating conditions (spectrum and temperature range). The standard terrestrial solar
spectrum, the AM1.5 regulated to give a total output power of 1000 W/m
2
and the experiment
performed at 25 C temperature. In order to standardize the output of the beam equal to 1000
W/m
2
, initially a GaAs and Si sample solar cells were used as a reference to regulate the
simulator output before doing any measurement [50].
In this experiment a Newport96000 solar simulator is used, which contains a xenon lamp
which produces light in a similar wavelength range to a solar spectrum. The light beam
passes through an AM1.5G filter which filters out part of the xenon lamps spectrum to give a
spectrum closer to the solar spectrum. The figure below shows the comparison of the AM1.5
and Xenon lamp spectrum.

Figure 3.9 : Comparison of AM1.5 (green) , Xenon lamp without filter (blue)
and Xenon lamp with filter (brown) spectrum [44]
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E
D
4
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38

To maintain the solar cell temperature at 25 C during the solar simulator illumination a
conventional approach is used. A block of copper is used to make the back side contact of the
solar cell and also acts as a cooling element. The temperature of this copper block is
controlled by a Peltier Temperature Controller by monitoring the temperature of a thermistor
inserted between two pieces of GaAs substrate. One piece of GaAs is connected with the
copper cooling block and the other is illuminated by the simulator to get the temperature as
close as possible to that of the solar cell [50]. A probe is used to make contact with the rings
of the solar cell, in order to avoid the need for wire bonding. The figure shows the structure
of the probe station.



The IV characteristics measurement is made using a Keithley 238 source measurement unit,
which sweeps a voltage across the terminals of the solar cell and measures the resulting
current. The dark Current Voltage (I V) characteristic of a solar cell is also measured by
simply covering the sample. The experimental setup for this I V measurement is presented
in figure 3.11.

Connection for
temperature controller
Clip for thermistor

Thermistor
Copper Block
Solar Cell
Contacting Probe
Clip to hold solar cell
Figure 3.10: Probe Station for the I-V measurement [50]
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3
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2
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3
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3
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D
4
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8
39


Figure 3.11 : Experimental Setup of I-V measurement [50]

3.3.2 Spectral Response

The spectral response is theoretically analogous to the quantum efficiency. The quantum
efficiency is given by the number of electrons generated by the solar cell relative to the
number of photons incident on the sample, whereas the spectral response is defined as the
ratio of the current produced by the photovoltaic cell to the power of incident radiation on the
PV cell [48].
In the spectral response experiment, light of a specific wavelength is incident on a solar cell
sample and the resultant current is measured. The spectral response not only gives
information about the wavelength range over which the device responds, but is also useful as
an effective diagnostic and analytical technique, specifically in a device research and design
[47].
The experimental setup for the spectral photoconductivity is shown in figure 3.12.
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:
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:
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:
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:
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E
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0
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7
-
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U

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:
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1

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:
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2
0
2
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3
5

C
:
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0
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3
F
4
0
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2
3
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A
0
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0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
40





A Tungsten Halogen Lamp is used as source of light for the wavelength range 500 1200
nm, the spectrum of this lamp is shown in figure 3.13. A Xenon Arc Lamp is used for the
lower wavelengths [47]. A M300 monochromator is used to scan through the preferred
wavelength range.



A chopper is used to chop the light beam from the monochromator at specific frequency and
then the resultant light signal is incident on the sample. The chopper controller is used to set
the chopping frequency of the chopper. The current generated in the solar cell due to the light
is measured with a Stanford research systems SR510 lock in amplifier.
Figure 3.12 : Experimental set up for spectral response [50]
Figure 3.13 : Tungsten lamp spectrum without the filter (left) and with filter (right) [46]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
41

# $odelling
4.1 Band Anti-Crossing Model
The band structure of a semiconductor is most significant for solar cells, as the wavelength
below which it absorbs light is determined by the band gap. Consequently it has a direct
impact on the photocurrent of the solar cell. A band anti-crossing (BAC) model was proposed
by W. Shan et al. to describe the characteristics of IIIV dilute nitrides and other highly
mismatched alloys. This model is used to determine the electronic structure of HMAs by
taking into account the interface between the localized states of the impurity and the extended
states of the host semiconductor [52]. In this project the BAC model is used to calculate the
band gap of GaAsBi and GaAsN with a different concentration of bismuth and nitrogen
respectively.
4.1.1 Conduction band anti crossing
When nitrogen (N) is added to the GaAs, an isolated N atom substitutes an As atom and
creates a localized state with the energy level E
N
,

caused by the large difference in
electronegativity and atomic size of the N and As [54]. In general, this level is positioned
very close (0.25 eV) beyond the conduction band edge in GaAs. The incorporation of a
slightly higher nitrogen content into III-V compounds considerably changes the electronic
band structure that results in decrease of the fundamental band gap, substantial increase in the
electron effective mass and reduction in electron mobility [53]. The interaction between the
localised state at energy level E
N
and the extended conduction band states results in the
reduction of the band gap energy in dilute nitride alloys. This conduction band dispersion
effect can be characterized by the following eigenvalue expression [53].
_
E(k) -E
c
(k) I
MN
I
MN
E(k) -E
N
_ = u (4.1)

E
c
(k) is the energy of the GaAs conduction band, E
N
is the energy of the localized state from
the top of the GaAs valence band and V
MN
is the matrix element, which expresses the
interaction between the localized N state and extended conduction band state. The E
c
(k) and
V
MN
can be written as follow [53].

E
c
(k) = E
g
+
l
2
k
2
2m
-

(4.2)
I
MN
= C
NM
Vx (4.3)
E
g
is the band gap of the GaAs, C
NM
is a constant which characterizes the interaction between
the localized N level and the extended conduction states and x is the concentration of
impurities.


U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
42

The solution to the eigenvalue equation can be given as


E
_
(k) =
E
N
+E
c
(k) _(E
N
-E
c
(k))
2
+4I
MN
2
2

(4.4)

The conduction band edge interface with the resonant defect level is responsible for the
dividing of the conduction band into two non-parabolic sub bands (E_(k) and E
+
(k)). The sub
band edges E_ and E+ depend on the concentration of impurities x and the coupling
parameter C
MN
, as well as the position of the localised state E
N
relative to the conduction
band edge and can be expressed by Eq. 4.4 [53].
In this BAC model we use E
N
= 1.67 eV, E
g
= 1.42 3.5x eV and C
NM
= 2.3 eV [54]. The
figure 4.1 shows CB dispersion (solid lines), conduction band (dashed line) and localized N
state (dotted line).


Figure 4.1: Dispersion relation of CB calculated using Eq. 4.4 (Solid lines), conduction band (Dashed line)
and N resonant defect energy level (dotted line) at E
N
= 1.67

The localized states and the conduction band edge interaction has a distinct influence on the
conduction sub bands E_ and E+. This effect is most prominent in the states positioned close
to E
N
. If the localized state is situated within the conduction band (E
N
= 1.67), as shown in
the figure 4.1, then the lower sub band E_ edge almost maintains the character of the
extended CB state, and the E+ edge has a more highly localized behaviour similar to E
N
. If
the localized state is located below (E
N
= 0.9) the conduction-band edge, as demonstrated in
the figure 4.2, then the E_ sub band states show the highly localized behaviour and E+ sub
band states hold the character of the extended CB state [53].

0.5
1
1.5
2
2.5
3
3.5
-20 -16 -12 -8 -4 0 4 8 12 16 20
E
n
e
r
g
y

[
e
V
]
k [10
6
cm
-1
]
GaAsN
Ec
E-
E+
En
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
43



Figure 4.2: Dispersion relation of CB calculated using Eq. 4.4 (Solid lines), conduction band (Dashed line)
and N resonant defect energy level (dotted line) at EN = 0.9

The deviation of the E+ and E- sub bands with different nitrogen concentration x in
GaN
x
As
1x
is calculated by the BAC model. The sharp increment (decrement) is observed in
the upper sub band E+ (lower sub band E-) for nitrogen concentration x 0.2% and
maintains a comparatively sharp increase (decrease) until x = 3%, and with further increase
in the concentration it becomes broad, as shown in figure 4.3.


Figure 4.3: Variations in upper E+ and lower E- sub bands with the nitrogen concentration

0.3
0.8
1.3
1.8
2.3
2.8
3.3
-20 -16 -12 -8 -4 0 4 8 12 16 20
E
n
e
r
g
y

[
e
V
]
k[10
6
cm
-1
]
GaAsN
Ec
E-
E+
En
0.9
1.1
1.3
1.5
1.7
1.9
0 0.5 1 1.5 2 2.5 3
E
n
e
r
g
y

[
e
V
]
Nitrogen concentration [%]
E+
E-
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
44

The conduction sub band E- has a significant importance as this band determines the band
gap of the semiconductor. The band gap bowing effect is more significant with the nitrogen
concentration x=0.02, as it exhibits significant reduction of approximately 150 meV per
x=0.01. This reduction becomes slower with the increase in the N concentration and reduces
to 80meV per x=0.01 with a nitrogen concentration of x = 0.08. The figure 4.4 shows the
band gap reduction with an increase of nitrogen concentration in the GaN
x
As
1x
.


Figure 4.4 : Dilute Nitride band gap dependence on Nitrogen concentration

4.1.2 Valence Band Anti crossing
The valence band anti crossing (VBAC) model gives a fundamental description for the
experimentally experienced large band gap reduction effect and increment in the spin-orbit
splitting energies in GaBi
x
As
1x
. The incorporation of Bi content into GaAs to produce
GaBi
x
As
1x
is responsible for a large decrease in the band gap (~90 meV per x=0.01) and a
significant improvement in the spin-orbit splitting energy [55]. In this project the VBAC
model is used to describe the band gap bowing effect in the GaBi
x
As
1x
. This model computes
that the localized defect state created by the impurity (Bi) of large atomic radius interacts
with the extended states of the host semiconductor and results in a reorganization of the
valence band. If the electronegativity and ionization energy of the impurity are significantly
lower compared to the host semiconductor, then the defect levels are positioned close to the
valence band edge of the host semiconductor [55].
The calculated splitting of valence band is expressed by VBAC model of GaBi
0.04
As
0.96
in
figure 4.5. In GaBi
x
As
1x
, Bi causes a reorganization of the heavy-hole (HH), light-hole
(LH), and spin-orbit split-off (SO) bands into four primary and two spin-orbit split-off, E+
and E- sub bands. The Bi defect levels that E
Bi
and E
Bi-so
are placed at ~0.4 (and 0.1) and 1.9
eV below the valence band maximum (VBM) of GaAs, respectively [56]. In this model we
use valence band offset E
VBM
= 0.6 eV, conduction band offset E
CBM
= 2.3 eV, spin-orbit
split-off band offset E
SO
= 1.3 eV [56] and coupling parameter C
Bi
= 1.6 [55].
0.8
0.9
1
1.1
1.2
1.3
1.4
1.5
0 1 2 3 4 5
E
n
e
r
g
y

[
e
V
]
Nitrogen concentration [%]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
45


Figure 4.5 : Dispersion relation of dilute bismide valence band comprising of light hole (LH), heavy hole
(HH) and spin orbit split off (SO) sub bands
The figure 4.6 shows the theoretically calculated bismuth (Bi) concentration dependence of
the band gap and spin-orbit splitting energies in GaBi
x
As
1x
. Until the Bi concentration of
x=0.03, the band gap of GaBi
x
As
1x
reveals significant bowing effects with a reduction of
almost 60 meV per x=0.01. On the other hand spin-orbit splitting energy rises by almost 40
meV per x=0.01. When the concentration increases to x=0.08, the band gap is reduced by
almost 40meV per x=0.01, whereas the spin-orbit splitting energy rises by nearly 30 meV per
x=0.01.


Figure 4.6: Theoretically calculated dependency of the band gap and spin-orbit splitting energies on
Bismuth concentration with localised state at E
Bi
= -0.4


-2.50
-2.00
-1.50
-1.00
-0.50
0.00
0.50
1.00
-
1
6
-
1
4
-
1
2
-
1
0
-
8
-
6
-
4
-
202468
1
0
1
2
1
4
1
6
E
n
e
r
g
y

(
e
V
)
k [10
6
cm
-1
]
GaAsBi
Elh+(k)
Elh-(k)
Ehh+(k)
Ehh-(k)
Eso+(k)
Eso-(k)
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
1.60
0 1 2 3 4 5 6 7 8 9 10
E
n
e
r
g
y
[
e
V
]
Bi Concentration [%]
Eg
o+
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
46

When the localized state is situated lower than the valence band (E
Bi
= -0.4), then the band
gap reduction and increment in spin orbit splitting energies is relatively slower, as shown in
the figure 4.6, with the incorporation of the Bi content. If the localized state is situated closer
to the valence band (E
Bi
= -0.1) then the band gap reduction and spin orbit splitting increment
is faster, as shown in the figure 4.7, with increase of Bi concentration.

Figure 4.7: Theoretically calculated dependency of the band gap and spin-orbit splitting
energies on Bismuth concentration with localised state at E
Bi
= -0.1
The BAC model investigations of GaN
x
As
1x
alloys reveal a large reduction in the band gap,
which decreases by 110 meV per percent N for x 5%. On the other hands the VBAC
model calculation for GaBi
x
As
1x
alloys indicates that the band gap decreases by 70 meV
per percent Bi for x 5%. The energy of the fundamental band gap of dilute bismide and
dilute nitride are compared with different concentration of Bi and N content respectively, in
the figure 4.8.

Figure 4.8: Comparison of band gap dependence of dilute bismide and nitride on the concentration
bismuth and nitrogen
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
1.60
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
E
n
e
r
g
y
[
e
V
]
Bi concentration [%]
Eg
o+
0.0 1.0 2.0 3.0 4.0 5.0
0.4
0.6
0.8
1
1.2
1.4
1.6
0.4
0.6
0.8
1.0
1.2
1.4
1.6
0.0 1.0 2.0 3.0 4.0 5.0
N concentration
E
n
e
r
g
y

[
e
V
]
E
n
e
r
g
y

[
e
V
]
Bi concentration
GaAsBi
GaAsN
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
47

% &esults and 'iscussion
5.1 Structures of Solar Cells
5.1.1 GaAs Solar Cell

GaAs solar cells can be designed in either p-n or n-p pattern because higher diffusion lengths
as compared to the absorption depth can be accomplished by either doping technique. The
emitter is kept as thin as possible, while considering the series resistance. In practice p
+
-n
designs give the impression of better performance than n
+
-p designs [5].

The first layer of the solar cell is usually the antireflective coating, which is used on the front
side of the solar cell to decrease the optical loss because of sunlight reection. A window
layer (Al
0.8
Ga
0.2
As) of 40nm thickness is deposited to improve the performance of the cells.
The content of Al is kept high (80% or more) to reduce the effect of surface recombination in
the active layer and also because it highly transparent to the incident light. An AlGaAs
window layer with higher band gap produces a front surface field that repels the minority
carriers away from contacts to decrease surface recombination. Similar to the window layer, a
thin (20nm) heavily doped (2x10
18
cm
-3
) GaAs buffer layer is employed at the back, which
acts as a back surface field.
The front layers of solar cells absorb large portion of light. Therefore in a GaAs (R0727)
solar cell design, a 500nm thin layer of p- type emitter is employed so that the illuminated
light generates huge segment of the carriers in a diffusion length of the p-n junction. Increase
in the thickness of this layer cause a rise in the recombination loss, and therefore degrades the
efficiency of solar cell. This layer is heavily doped to 2 x 10
18
cm
-3
to conduct away the
generated current with minimum resistive loss. The figure 5.1 shows the structure of p on n
GaAs solar cell.








Figure 5.1: Structure of GaAs p on n solar cell


p+ GaAs Be 4x10
18
cm
-3
200nm
p Al
0.8
Ga
0.2
As Be 2x10
18
cm
-3
40nm
p GaAs Be 2x10
18
cm
-3
500nm
n GaAs Si 2x10
17
cm
-3
2500nm
n+ GaAs Si 2x10
18
cm
-3
20nm
n+ GaAs substrate
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
48

On the other side a 2500nm n-type base lightly doped to 2 x 10
17
cm
-3
is employed. A
heavily doped base results into a higher open circuit voltage and lower resistance; however a
heavily doped base damages the crystal. The acceptors and donors are added during the
growth process. The p- type emitter is generally doped with beryllium (Be) and the n-type
base is doped with silicon (Si).
Ohmic contacts are important parts of solar cells since they give advantage in maximizing the
open circuit voltage. The front contacts are made on the GaAs cap layer. This is done to
avoid making contact to a wide band gap window layer which generally yields a non-ohmic
contact. The front contact pattern, which takes account of both the shadowing loss and the
series resistance of the cell, was defined by the photolithographic technique. The front
contact consists of evaporated Au, ZnAu, and Au thin films. The back contacts consist of
evaporated Au, AuGe, Ni and Au thin films.
5.1.2 Dilute Bismide & Dilute Nitride Solar Cells

The dilute bismide and dilute nitride solar cells are prepared in n-i(MQW)-p multi quantum
well designs. The emitter is kept slightly thinner (~200nm) relative to the GaAs design,
because of higher n-type conductivity. This layer is heavily doped to 2 x 10
18
cm
-3
with
silicon. The base is slightly thicker (3000nm) but lightly doped to 2 x 10
17
cm
-3
with Be, as
compared to the GaAs base layer.
In the dilute bismide solar cell design, two samples R0728 and R0729 are constructed and
have the same structure. The only difference between these samples is the concentration of
bismuth content (R0728 with 2% Bi and R0729 with 1 % Bi). Ten GaAsBi quantum wells
were constructed in dilute bismide solar cells with thin (10nm) layers of GaAsBi materials
grown epitaxially in the intrinsic region of dilute bismide p-i-n solar cells.
The lattice constant is an important parameter in solar cell design as using materials with
different lattice constant results in strain between the two materials. The incorporation of
trivial amounts of nitrogen (N) in GaAs causes a huge reduction in band gap and the lattice
constant of the alloy. When Indium (In) is incorporated into GaAs it replaces Ga and results
in an increase of lattice constant. The quaternary semiconductor Ga
x
In
1-x
N
y
As
1-y
has the same
lattice constant as GaAs. In the dilute nitride solar cell (VN8515) design, ten quantum wells
were constructed in dilute nitride solar cells with thin (10nm) layers of Ga
x
In
1-x
N
y
As
1-y

materials grown epitaxially in the intrinsic region of dilute nitride p-i-n solar cells. The
structure of dilute bismide and dilute nitride MQW solar cells is shown in figure 5.2.





U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
49










n GaAs Si 2x10
18
cm
-3
200nm
n Al
0.8
Ga
0.2
As Si 2x10
18
cm
-3
40nm
n GaAs Si 2x10
18
cm
-3
200nm
UD GaAs 110nm
i GaAsBi 10nm
UD GaAs 10nm
i GaAsBi 10nm
UD GaAs 10nm
i GaAsBi 10nm
UD GaAs 10nm
i GaAsBi 10nm
UD GaAs 10nm
i GaAsBi 10nm
UD GaAs 10nm
i GaAsBi 10nm
UD GaAs 10nm
i GaAsBi 10nm
UD GaAs 10nm
i GaAsBi 10nm
UD GaAs 10nm
i GaAsBi 10nm
UD GaAs 10nm
i GaAsBi 10nm
UD GaAs 110nm
p GaAs Be 2x10
17
cm
-3
3000nm
p+ GaAs Be 2x10
18
cm
-3
20nm
p+ GaAs substrate
n GaAs Si 2x10
18
cm
-3
200nm
n Al
0.8
Ga
0.2
As Si 2x10
18
cm
-3
40nm
n GaAs Si 2x10
18
cm
-3
200nm
UD GaAs 110nm
i GaInNAs 10nm
UD GaAs 10nm
i GaInNAs 10nm
UD GaAs 10nm
i GaInNAs 10nm
UD GaAs 10nm
i GaInNAs 10nm
UD GaAs 10nm
i GaInNAs 10nm
UD GaAs 10nm
i GaInNAs 10nm
UD GaAs 10nm
i GaInNAs 10nm
UD GaAs 10nm
i GaInNAs 10nm
UD GaAs 10nm
i GaInNAs 10nm
UD GaAs 10nm
i GaInNAs 10nm
UD GaAs 110nm
p GaAs Be 2x10
17
cm
-3
3000nm
p+ GaAs Be 2x10
18
cm
-3
20nm
p+ GaAs substrate
Figure 5.2: Structure of GaAsBi and GaInNAs QW solar cell
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
50

5.2 I V Characteristics and Results

In consideration of the strong dependence of solar cell performance parameters on both the
intensity and spectrum of incident light and temperature of the solar cell, and for results
comparisons of PV cells, these experiments were performed using a standard AM1.5G
spectrum regulated to give a total output power of 1000 W/m
2
with the cell temperature at 25
C. In order to standardize the output of the beam equal to 1000 W/m
2
, initially a Si sample
solar cell were used as a reference to regulate the simulator output to 1000 W/m
2
,

before
doing any measurement. The IV characteristics of the reference solar cell are presented in the
figure 5.3.


Figure 5.3 : I-V curves of sample silicon (Si) solar cell
The devices were fabricated using cylindrical mesa structures using the fabrication process
explained in the chapter 3. There is no anti-reflective coating employed on the samples. One-
sun AM1.5G current density-voltage (J V), and dark diode curves were measured to inspect
the one-sun performance and diode quality of the VN1585 devices. The results for dilute
nitride QW (VN1585) are plotted in the figure 5.4.


Figure 5.4 : J-V characteristics of VN1585 MQW solar cell
-8.00E-02
-6.00E-02
-4.00E-02
-2.00E-02
0.00E+00
2.00E-02
4.00E-02
6.00E-02
8.00E-02
1.00E-01
1.20E-01
0 0.2 0.4 0.6 0.8
C
u
r
r
e
n
t

[
A
]
Voltage [V]
Dark
Light
-0.005
0
0.005
0.01
0.015
0.02
0 0.1 0.2 0.3 0.4 0.5 0.6
C
u
r
r
e
n
t

d
e
n
s
i
t
y

[
A
c
m
-
2
]
Voltage [V]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
51

The IV characteristics illustrate that the sample VN1585 has the short circuit current density
J
sc
of 17mAcm
-2
and open circuit voltage V
oc
is equal to 0.55V. In comparison with the
results previously obtained [50] using the same sample (VN1585) and GaAs control cell, the
short circuit current density is larger while the open circuit voltage is slightly lower. It also
becomes clear that the incorporation of GaInNAs wells in the structure has in fact caused a
reduction in the open circuit voltage of the solar cell from 0.9 V (R0727 (Ben Royalls
thesis)) to 0.55 V (VN1585). The inclusion of quantum wells degraded the open circuit
voltage of the cells due to the introduction of strain-induced defects in the emitter and
intrinsic region of the cell. The reduction in open circuit voltage is probably due to the escape
of carriers from the quantum wells, which causes the recombination of the photo generated
carriers. Consequently, they will have no contribution in the photocurrent, and majority
carriers arriving in the depletion region recombine and resulting in an increase of the dark
current [50]. The comparison of the samples is shown in Table 5.1.

Table 5.1 : J-V characteristics for VN1585, VN1585 (ben thesis) and R0727 (ben thesis)
Sample J
sc
(mA/cm2) V
oc
(V) FF (%) (%)
VN1585 17 0.55 38 3.6
VN1585 (ben thesis) 10.6 0.67 69 5
R0727 (ben thesis) 11.63 0.9 83 8.5

A more standard practice in semiconductor device characterization is the measurement of
dark IV characteristics as this will give a basic understanding of p-n junction behaviour.
Indeed, it is obvious from the figure 5.5 that the dark current is higher for VN1585 for all
voltages.


Figure 5.5: Dark J-V characteristics of VN1585 MQW samples
-0.02
-0.01
0
0.01
0.02
0.03
0.04
-3 -2 -1 0 1
C
u
r
r
e
n
t

d
e
n
s
i
t
y


[
A
c
m
-
2
]
Voltage [V]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
52

A smaller fill factor of 38 % is achieved for VN1585 compared to 69 % reported before [50].
The slope of the IV characteristics which result in the low fill factor is due to the series
resistance. A larger fill factor can be obtained by decreasing the series resistance.
Due to the lower open circuit voltage and smaller fill factor, the efficiency of VN1585 solar
cell is equal to 3.6% which is lower compared to the 5% measured by Ben Royall.

Figure 5.6 : The AM 1.5G IV characteristics for VN1585 and a GaAs control cell at T = 25 [50]
The IV characteristics of the VN1585 sample are also calculated with varying intensity of the
incident light. The short circuit current increases linearly with the intensity of light. Whereas
the open circuit voltage changes non-linearly and it tends to saturate at around the band gap
of the semiconductor as shown in the figure 5.8.

Figure 5.7: The AM 1.5G IV characteristics for VN1585 with different intensities of light
-0.2
-0.15
-0.1
-0.05
0
0.05
0.1
0.15
0.2
-3 -2 -1 0 1 2
C
u
r
r
e
n
t

d
e
n
s
i
t
y

[
A
c
m
-
2
]
Voltage [V]
150 W/m^2
500 W/m^2
1000 W/m^2
2000 W/m^2
3000 W/m^2
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
53


Figure 5.8: Open circuit voltage and short circuit current with different intensities of light

The IV characteristics under AM1.5G conditions for R0727 GaAs control cell are plotted in
figure 5.9. The obtained results in for this sample did not look quite as expected. The most
surprising result is that the I-V characteristics seem to be linear, while we expected an
exponential decrease in the current as the voltage increases. The reason for these results is
that during the process of etching the p-type GaAs contacting layer of the sample is removed
so that the light directly strikes the AlGaAs window layer. After the removal of the p-type
contacting layer only n-type layer is left in the sample therefore the sample has no longer a pn
junction thats why it is showing characteristics like a resistor in dark and when it is
illuminated by light. The work on the similar structure cell is done in the Ben Royalls PhD
thesis and the IV results are shown in figure 5.6.



Figure 5.9: The AM 1.5G IV characteristics for R0727 solar cell
0
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
0.75
0 500 1000 1500 2000 2500 3000
I
s
c

[
A
]
V
o
c

[
V
]
Photon Intensity [W/m
2
]
-10
-8
-6
-4
-2
0
2
4
6
8
10
-0.15 -0.1 -0.05 0 0.05 0.1 0.15
C
u
r
e
n
n
t

d
e
n
s
i
t
y


[
A
c
m
-
2
]
Voltage [V]
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
54

The IV measurement for R0727 GaAs control cell is also done using the neutral density filter
as it was suspected that the solar cell gets saturated with the higher intensity of light. The
neutral density (ND) filter reduced the intensity of all wavelengths of light in equal
proportion. After using ND filter the intensity of the AM1.5 standard spectrum is reduced to
~ 400W/m
2
. The IV plot is shown in figure 5.10.

Figure 5.10: The AM 1.5G IV characteristics for R0727 using ND filter
The IV characteristics in dark and light (1000 W/m
2
) conditions for R0728 (2% Bi
concentration) and R0729 (2% Bi concentration) dilute bismide samples are plotted in figure
5.11 and figure 5.12 respectively. These solar cells also show unexpected IV characteristics
in dark and these cells did not give any response with changing intensity of light. The reasons
for this behaviour are the very poor quality of the bismuth layers and there is no X-ray
diffraction (XRD) facility available to determine structural properties of these samples. The
dilute bismide is in the early stage of growth and until now no good epilayer for bismide
devices has been successfully made.

-2
-1.5
-1
-0.5
0
0.5
1
1.5
2
-0.3 -0.2 -0.1 0 0.1 0.2 0.3
C
u
r
r
e
n
t

d
e
n
s
i
t
y

[
A
c
m
-
2
]
Voltage [V]
-10
-5
0
5
10
15
-1 -0.5 0 0.5 1
C
u
r
r
e
n
t

d
e
n
s
i
t
y

[
A
c
m
-
2
]
Voltage [V]
-15
-10
-5
0
5
10
15
-1 -0.5 0 0.5 1
C
u
r
r
e
n
t

d
e
n
s
i
t
y

[
A
c
m
-
2
]
Voltage [V]
Figure 5.11: Figure 5.9: IV characteristics for R0728 in dark (left) and light (right)
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
55


In an attempt to eliminate some possible error the IV measurements were done at three
different levels of light intensity (250 W/m
2
, 900 W/m
2
and 3000 W/m
2
) for both the R0728
and R0729 samples. However the IV plots obtained in all cases had the same linear shape and
the change in intensity did not show any increase in the short circuit current and the open
circuit voltages. The resultant curves have the same pattern and position in the plot as shown
in the figure 5.13.


Figure 5.13: The AM 1.5G IV characteristics for R0728 with different intensities of light


-1.5
-1
-0.5
0
0.5
1
1.5
-0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5
C
u
r
r
e
n
t

d
e
n
s
i
t
y

[
A
c
m
-
2
]
Voltage [V]
250 W/m^2
900 W/m^2
3000 W/m^2
-10
-5
0
5
10
15
-1 -0.5 0 0.5 1
C
u
r
r
e
n
t

d
e
n
s
i
t
y

[
A
c
m
-
2
]
Voltage [V]
-10
-5
0
5
10
-1 -0.5 0 0.5 1
C
u
r
r
e
n
t

d
e
n
s
i
t
y

[
A
c
m
-
2
]
Voltage [V]
Figure 5.12: IV characteristics for R0729 in dark (left) and light (right)
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
56

5.3 Spectral Response (SR)

The quantum efficiencies (QE) of the samples were obtained by measuring the spectral
photocurrent under illumination between the wavelength from 350 nm to 1200 nm using a
M300 Bentham monochromator and a Bentham IL1 white light source.
The quantum efficiency measurements of the MQW dilute nitride sample (VN1585) were
performed in the wavelength range from 350 nm to 1000 nm. The carriers are generated in
the AlGaAs window layer by photons of energy greater than 1.8eV which cause a rise in the
QE curve. These short wavelength photons are most likely to be absorbed near the top of the
device due to their high absorption coefficient, therefore mainly generating minority holes in
the n-type emitter that have to cross the intrinsic region. The high response for this part of the
graph suggests that almost all these minority holes are able to cross the intrinsic region
without recombining.
However from wavelength 650 nm onwards the QE decreases with increasing wavelength.
The photon with wavelengths larger than 665 nm are not absorbed efficiently in the emitter as
compare to their absorption in the barriers, base and wells of the cell. The current generated
in these regions is governed by the minority electrons. Therefore the decreasing quantum
efficiency with increasing wavelength shows that minority electrons are not able to cross the
intrinsic region efficiently. After the cut-off wavelength of GaAs the response is extended up
to wavelength of 1000 nm, related to the control cell. This extension in the QE curve is a
consequence of the absorption of photons in the wells, with the energies smaller than the
GaAs band gap.
It is obvious from the QE curve that the GaInNAs quantum wells prolong the cells spectral
response further than the band gap of a GaAs cell (1.42 eV) to 1.21 eV. The lower response
achieved at higher wavelengths is due to the small number of quantum wells.

Figure 5.14: The quantum efficiency of VN1585
0
5
10
15
20
25
350 450 550 650 750 850 950 1050
Q
E

%
Wavelength(nm)
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
57


The responses of R0728 and R0739 are shown in figure 5.15. Due to the reason mentioned
above this is not the typical response for the dilute bismide solar cells. The quantum
efficiency measurement of these samples was also performed between the wavelength
ranging from 400 nm to 1100 nm. In the beginning the spectral response level remains
constant to the minimum position until the wavelength of 665 nm (R0728) and 780 (R0729).
After this wavelength the spectral response suddenly raises to the peak point at wavelength of
830 nm (R0728) and 855 nm (R0729). After reaching the maximum point the response
suddenly drops to the minimum position at around wavelength 910nm (R0728) and 925 nm
(R0729) and remains constant for the higher wavelengths. The sudden response observed in
these samples is due to the absorption of some photons in the GaAs emitter layer. Although
the samples are showing some response between the wavelengths from 800nm to 900nm it
was very small and picked up by the lock in amplifier. These samples were expected to
extend the response to the higher wavelengths due to the presence of the GaAsBi quantum
wells in the intrinsic region but at the higher wavelength no response is observed for either of
the samples.







-0.01
0.04
0.09
0.14
0.19
0.24
0.29
600 800 1000 1200
Q
E

[
%
]
Wavelenght [nm]
-0.1
0
0.1
0.2
0.3
0.4
0.5
400 600 800 1000 1200
Q
E

[
%
]
Wavelength [nm]
Figure 5.15: The quantum efficiency of R0728 (left) and R0729 (right) solar cell
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
58

( )onclusion

The goal of this work was to investigate three solar cell designs (GaAs/GaInAsN/GaAsBi)
that could lead to obtain efficient tandem solar cells. The two solar cell designs (GaInNAs
and GaAsBi) investigated were multiple quantum well solar cells where ten thin layers (10
nm) of GaInNAs and GaAsBi were grown respectively, in the intrinsic region of a p-i-n solar
cell to extend their absorption response for longer wavelength.
Investigation of lower band gap of GaNAs and GaAsBi began by band anti crossing
modelling. The BAC model was used to find the band gaps of GaNAs and GaAsBi alloys
lattice matched to GaAs that might be of interest for tandem solar cells. The BAC model for
GaN
x
As
1x
alloys reveals that a large reduction (110 meV per percent N for x 5%) as
compare to the GaBi
x
As
1x
(70 meV per percent Bi for x 5%) can be obtain with smaller
concentration of nitrogen and hence, a good quality material can be grown with less number
of trap.
The GaInNAs multiple quantum well devices achieved = 3.6 %, FF = 38 % Voc = 0.55 V,
and Jsc = 17 mA/cm
2
for the AM1.5G spectrum at 25 C. The GaAsBi MQW devices did not
show any response with the changing intensity of light due to the suspected poor quality of
the bismuth layers.
The monochromatic light source is used to investigate the contributions of the different layers
of the devices to the photocurrent. The GaAsBi shows unexpected short response near the
GaAs band gap and which did not extend to the higher wavelength, as expected due to the
addition of quantum wells. The results of GaInNAs samples showed that the addition of
quantum wells did increase the devices response beyond the cut-off wavelength of GaAs.
However, the addition of wells also lead to a large reduction in quantum efficiency for
photons absorbed in the p type GaAs layers which shows that minority electrons are not able
to cross the intrinsic region efficiently.
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&e*erence

[1] International Energy Outlook 2013, US Energy Information Administration, 2013.
[2] Key World Energy Statistics, International Energy Agency, 2012.
[3] R. R. King, 40% efficient metamorphic GaInP/GaInAs/Ge multijunction solar cells,
Appl. Phys. Lett., vol. 90, pp. 183516, 2007.
[4] Martin A. Green, Solar cell efficiency tables (version 37), Progress in photovoltaic:
Research and Applications, vol. 19, pp. 84-92, 2011.
[5] Jenney Nelson, The Physics of Solar Cells, Imperial College Press, 2003.
[6] F.J. Haug, Superstrate, [Online]. Available:
http://www.superstrate.net/pv/illumination/spectrum.html. [Accessed 20 July 2013].
[7] C. H. A. S. Bowden, PVeducation, [Online]. Available:
http://pveducation.org/ . [Accessed 6 August 2013].
[8] S.M.Sze and Kwok K. Ng, Physics of semiconductor devices, Edition 3
rd
, John
Wiley & Sons, Inc., 2007.
[9] C. H. A. S. Bowden, PVeducation, [Online]. Available:
http://pveducation.org/pvcdrom/pn-junction/absorption-of-light. [Accessed 6 August
2013].
[10] Jasprit Singh, Semiconductor Devices, Basic Principles, John Wiley & Sons, Inc.,
2000.
[11] C. H. A. S. Bowden, PVeducation, [Online]. Available:
http://pveducation.org/pvcdrom/solar-cell-operation/charecteristic-resistance.
[Accessed 6 August 2013].
[12] M. Abdulkadir, A. S. Samosir and A. H. M. Yatim, Modeling and simulation based
approach of photovoltaic system in SIMULINK model, ARPN Journal of
Engineering and Applied Sciences, vol. 7, no. 5, 2012.
[13] William Shockley , Hans J. Queisser, Detailed Balance Limit of Efficiency of p-n
Junction Solar Cells, J. Appl. Phys. 32, 510 (1961).
[14] D.M. Chapin,C.S. Fuller and G.L. Pearson, A new silicon p-n junction photocell for
converting solar radiation into electrical power, J. Appl. Phys. 25, 676 (1954).
[15] Matthlas E. Nell, Allen M. Barnett, The spectral p-n Junction model for tandem
solar cell design, IEEE, vol. ED-34, no.2, 1987.
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
60

[16] L.Mayet, M.Gavand, B. Montegu and A.Laugier, High efficiency Al
0.32
Ga
0.68
As
GaAs tandem solar cells with three terminals, IEEE Photovoltaic Specialists
Conference, 1988.
[17] C. H. A. S. Bowden, PVeducation, [Online]. Available:
http://pv.asu.edu/files/EEE598/08-Tandem%20solar%20cells.pdf.[Accessed 6 August
2013].
[18] Devki N. Talwar, Novel Dilute III-V-Ns : From Physics to Applications,
ELECTRO, 2009.
[19] Ioffe Physico-Technical Institute, [Online]. Available:
http://www.ioffe.ru/SVA/NSM/Semicond/GaAs/electric.html. [Accessed 5 July
2013].
[20] David Wolpert and Paul Ampadu, Managing Temperature Effects in Nanoscale
Adaptive Systems, Springer, 2012.
[21] S.J.Sweeney, et al.,The potential role of Bismide Alloys in Future Photonic
Devices, ICTON, 2011.
[22] S. Francoeur, et al., Band gap of GaAs
1x
Bi
x
, 0<x<3.6%, Appl. Phys. Lett. 82,
3874, 2003.
[23] S. J. Sweeney and S. R. Jin, Bismide-nitride alloys: Promising for efficient light
emitting devices in the near- and mid-infrared, J. Appl. Phys. 113, 043110, 2013.
[24] S. Tixier et al., Molecular beam epitaxy growth of GaAs
1-x
Bi
x
, Appl. Phys. Lett. 82,
2245, 2003.
[25] X. Lu, D. A. Beaton, R. B. Lewis, T. Tiedje, and M. B. Whitwick, Effect of
molecular beam epitaxy growth conditions on the Bi content of GaAs
1-x
Bi
x
, Appl.
Phys. Lett. 92, 192110, 2008.
[26] R. B. Lewis, M. Masnadi-Shirazi, and T. Tiedje, Growth of high Bi concentration
Gaas1-xBi-x by molecular beam epitaxy Appl. Phys. Lett. 101, 082112, 2012.
[27] G. Vardar, et al., Mechanisms of droplet formation and Bi incorporation during
molecular beam epitaxy of GaAsBi, Appl. Phys. Lett. 102, 042106, 2013.
[28] W. Shan et al., Reduction of band-gap energy in GaNAs and AlGaNAs synthesized
by N+ implantation, Appl. Phys. Lett. 75, 1410, 1999.
[29] R. Chtourou et al., Effect of nitrogen and temperature on the electronic band
structure of GaAs
1-x
N
x
alloys, Appl. Phys. Lett. 80, 2075, 2002.
[30] K. M. Yu et al., Highly mismatched crystalline and amorphous GaN
1x
As
x
alloys in
the whole composition range, J. Appl. Phys. 106, 103709 (2009).
U
P
:
2
2
/
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8
/
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:
4
9
:
3
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:
2
2
/
0
8
/
2
0
1
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0
8
:
4
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:
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:
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-
7
-
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1
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:
1
2
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4
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C
:
3
0
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4
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5
A
7
8
8
1
3
8
2
3
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0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
61


[31] K.W.J. Barnham et al., Quantum Well Solar Cells, Physica E: Low-dimensional
Systems and Nanostructures, vol. 14, Issues 12, 2002
[32] Ben Browne et al., Tandem Quantum Well Solar Cells, 33
rd
IEEE Photovoltaic
Specialists Conference, 2008.
[33] Li, E.H. Weiss, B.L, Band gap engineering and quantum wells in optoelectronics
devices, Electronic and communication engineering journal, vol. 38 pp. 513-518,
2007
[34] J.C. Rimadaa et al., Conversion efficiency enhancement of AlGaAs quantum well
solar cells Microelectronics journal, vol. 38 pp. 513-518, 2007
[35] S.J. Lade, A. Zahedi A revised ideal model for AlGaAs/GaAs quantum well solar
cells Microelectronics journal, vol. 35 pp. 401-410, 2004
[36] C.Y.Chang and Francis Kai, GaAs High Speed Devices, John Wiley & Sons, Inc.,
1994
[37] Tze Yiu Yong, Molecular beam epitaxy, IEEE Potentials, vol. 8, Issue 3, 1989.
[38] A. R. Barron, Connexions, [Online]. Available:
http://cnx.org/content/m25712/latest/. [Accessed 3 August 2013].
[39] Simone Mazzucato et.al. Dilute nitride and GaAs n-i-p-i solar cells, Nanoscale Res
Lett. , v. 7(1), 2012.
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3523972/
[40] K Pappert et. al. Detailed transport investigation of the magnetic anisotropy of
(Ga,Mn)As, New J. Phys. 9 , 2007.
http://iopscience.iop.org/1367-2630/9/9/354/fulltext/
[41] PrimeWafers, [Online]. Available:
http://www.primewafers.com/Cleave_with_a_diamond_scribe.html. [Accessed 6
August 2013].
[42] Lukas Greuter, Fabrication and Characterization of Ohmic Contacts, University of
Basel, 2009.
[43] Keithly, Measuring Photovoltaic Cell I-V Characteristics with the Model 2420
SourceMeter Instrument, Application Note Series.
[44] Stuart Bell, Geoffrey Will, John Bell, Light intensity effects on photo catalytic water
splitting with a titania catalyst, International Journal of Hydrogen Energy, vol. 38,
Issue 17, pp. 69386947, 2013.
U
P
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
7

W
M
:
2
2
/
0
8
/
2
0
1
3
-
0
8
:
4
9
:
3
9

M
:
C
E
9
0
1
-
7
-
S
U

A
:
1
2
a
1

R
:
1
2
0
2
4
3
5

C
:
3
0
8
3
F
4
0
E
5
A
7
8
8
1
3
8
2
3
E
A
0
C
0
B
2
B
C
D
B
3
6
0
8
3
6
E
D
4
C
8
62

[45] M. J. Morgan, H.Jakovidis and Ian Mcleod, An experiment to measure the I-V
characteristics of silicon solar cell, Phys. Educ. vol. 29, pp. 252, 1994
[46] The University of Manchester, School of Physics & Astronomy, [Online].
Available: http://www.jb.man.ac.uk/~tob/solar/spectra/web.html. [Accessed 2013
July 6].
[47] L. Philippe Boivin, Wolfgang Budde, C. X. Dodd, and S. R. Das, Spectral response
measurement apparatus for large area solar cells, Applied Optics, vol. 25, no. 16,
1986.
[48] C. H. a. S. Bowden, PVeducation, [Online]. Available:
http://pveducation.org/pvcdrom/characterisation/spectral-response. [Accessed 6
August 2013].
[49] C.Hilsum and A.C.Rose-Innes, Introduction to Semiconducting III V Compounds,
Vol. 1, Pergamon Press, 1961.
[50] Ben Royall, GaInNAs / GaAs Multiple Quantum Well and n-i-p-i Solar Cells,
University of Essex, 2011.
[51] Ivor Brodie and Hulius J. Muray, The Physics of Micro fabrication, Plenum press,
1982.
[52] W. Walukiewicz et al., Electronic Band Structure of Highly Mismatched
Semiconductor Alloys, Dilute III-V Nitride Semiconductors and Material Systems,
vol. 105, pp. 65-89, 2008.
[53] W. Shan et al., Band anticrossing in dilute nitrides, J. Phys.: Condens. Matter, vol.
16 No. 31, 2004.
[54] C A Broderick, M Usman, S J Sweeney and E P OReilly, Band engineering in
dilute nitride and bismide semiconductor lasers, Semiconductor Sci. Technology,
vol. 27, No. 9, 2012.
[55] K. Alberi et al., Valence band anti-crossing in GaBi
x
As
1x
, Appl. Phys. Lett., vol.
91, pp. 051909, 2007.
[56] K. Alberi et al., Valence-band anticrossing in mismatched III-V semiconductor
alloys, Physical Review B., vol. 75, Issue 4, 2007.

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