Study and Investigation of The Contact Resistance of Monocrystalline Silicon Solar Cell-10-128

Figure 2.
24: Resistivity as a function of the doping concentration for different

barrier heights (left) and in combination with experimentally
determined values for Al contacts on n-doped silicon (right) [77]….. 52
Figure 2.25: Recombination in semiconductors [90]…………………….………. 55
Figure 2.26: A typical arrangement for a TLM test pattern……….……………... 56
Figure 2.27: TLM-measurement, where the measured resistance RTLM is plotted
as a function of the spacings between the contact pads……………. 57
Figure 3.1: Sequence of the solar cell fabrication process steps……………….. 59
Figure 3.2: Starting p-type monocrystalline silicon wafer……………………… 60
Figure 3.3: Wet-chemical bench………………………….…………………….. 60
Figure 3.4: DI-water plant……………………………………….……………… 61
Figure 3.5: Drying of textured wafer using compressed air…………………….. 62
Figure 3.6: Schematic diagram of the surface reflection measurement system… 63
Figure 3.7: The surface reflection measurement system showing (a) folding
mirror for directing light at near normal incidence to the wafer and
(b) large convex lens to collect reflected and scattered light………… 64
Figure 3.8: The output from the monochromator with (a) zero order and (b) red
color………………………………………………………………… 64
Figure 3.9: Working SRM system (a) inside a cabinet to block external light and
(b) focused light spot reflected from Si surface on the detector plane.. 65
Figure 3.10: POCl3 diffusion furnace used in solar cell fabrication……………... 67
Figure 3.11: POCl3 gas distribution system located at furnace back (left), N2 and
O2 gas cylinder (right)………………………………………………. 67
Figure 3.12: Screen printer……………………………………………..………… 68
Figure 3.13: Contact screen……………………………………..………………... 68
Figure 3.14: Electrical Dryer……………………………..………………………. 69
Figure 3.15: Rapid Thermal Annealing Furnace with exhaust system connected.. 70
Figure 3.16: Different test location for contact resistance measurement………… 70
Figure 3.17: 4 mm x 10 mm paste pads with the distance of 0.1 mm, 0.2 mm, 0.3
mm, 0.4 mm, 0.5 mm, 0.6 mm, and 0.7 mm for TLM pattern……… 71
Figure 3.18: Instrumental setup of contact resistance measurement system…….. 71

Figure 3.19: Rotary pole switches for (a) pattern selection (b) resistance 72
measurement between neighboring contact pads…………………….
Figure 4.1: SEM image (a) at low and (b) at high magnification showing the
surface of textured wafer……………………………….…………… 74
Figure 4.2: Reflectance versus wavelength curve of wafer…………………….. 75

Figure 4.3: Percentage of reflectance values of raw wafer and textured wafer… 76
Figure 4.4: P-type Si wafers (a) before and (b) after Phosphorous diffusion….. 77
Figure 4.5: Solar cell (a) before and (b) after screen printing…………………... 77
Figure 4.6: Resistance data from the TLM measurement system for front side of
sample 1………………………………….…………………………. 79
viii
sample 2…………………………………………….……………… 79
sample 3……………………………………….……………………. 80
sample 4……………………………………………….……………. 80
sample 5………………………………………………….…………. 81
sample 6………………………………………………….…………. 81
Figure 4.12: Linear regression analysis curve for the front side of sample 1……… 82
Figure 4.18 : Contact resistance versus diffusion time curve for front side of solar
cells……………………………………………………………….... 86
Figure 4.19: Resistance data from the TLM measurement system for back side of
sample 1…………………………………………………………….. 87
sample 2…………………………………………………………….. 88
sample 3…………………………………………………………….. 88
sample 4…………………………………………………………….. 89
sample 5…………………………………………………………….. 89
sample 6…………………………………………………………….. 90
Figure 4.25: Linear regression analysis curve for the back side of sample 1……… 90
Figure 4.31: Contact resistance versus diffusion time curve for backside of solar
cells………………………………………………………………..... 95
ix
list of abbreviation
MDGs Millennium Development Goals

IEO International Energy Outlook
Btu British thermal unit
OECD Organization for Economic Cooperation and Development
IPP Independent Power Producers
SREDA Sustainable and Renewable Energy Development Authority
IRENA International Renewable Energy Agency
IDCOL Infrastructure Development Company Limited
SHS Solar Home System
BPDB Bangladesh Power Development Board
GWp Giga Watt peak
BAEC Bangladesh Atomic Energy Commission
TLM Transmission Line Method
SCR Surface Charge Region
IPA Isopropyl alcohol
DI De-Ionized
SEM Scanning Electron Microscope
SR Surface Reflection
SRM Surface Reflection Measurement
PSG Phosphosilicate Glass
RTA Rapid Thermal Annealing
IR Infrared
RCF Refractory Ceramic Fiber
TE Thermionic Emission
TFE Thermionic Field Emission
FE Field Emission
SFRD Solar Cell Fabrication and Research Division
FESEM Field Emission Scanning Electron Microscope
x
abstraCt
In the present study, monocrystalline silicon solar cells are fabricated by the variation of
diffusion time i.e. doping concentration and corresponding front and back contact resistances
are then measurement by Transmission Line Method (TLM) measurement system. At first, p-
type square silicon wafers of 127×127 mm2, 200 μm in thickness and (100) oriented
Czochralski Si (or Cz-Si) are taken. In this research, six sample wafers are taken and each
sample contains one more wafers. These samples are cleaned and textured using a chemical
solution of NaOH + H2O (De-ionized) and KOH + IPA + H2O (De-ionized) respectively at 70°
C temperature. Then the morphology of a sample is studied using the Field Emission Scanning
Electron Microscope (FESEM) and the surface reflectance is measured by the Surface
Reflection Measurement (SRM) system. From the surface morphology, it is found that almost
uniform pyramid structure is formed on the wafer surface. From the SRM result, it is observed
that, before and after cleaning and texturing, surface reflection become about 36.23 % and
15.08 % respectively. The six samples are then doped with phosphorous atoms for 5 minutes,
10 minutes, 15 minutes, 20 minutes, 25 minutes, and 30 minutes respectively in a diffusion
furnace at 875° C temperature to form an n-type layer on the p-type substrate. Following
phosphorous diffusion, screen printing of front and back side of six samples are screen printed
using silver paste and aluminum paste respectively by a TLM pattern screen for the
measurement of contact resistance. The screen printed samples are then dried for 10 minutes
at 150° C temperature in a preheated oven so that the paste gets attached well to the wafer
surface. Finally, Rapid Thermal Annealing (RTA) is performed to form ohmic contacts and
cure the contacts between metal and semiconductor. Contact resistances of the fabricated solar
cells are then measured using TLM measurement system. From the TLM results, it is observed
that front contact resistance decreases with doping time i.e. doping concentration increases.
However, back contact resistance increases with the increase of doping concentration. The
minimum front contact resistance found is 1.105 Ω at 25 minutes of doping time and at the
same doping time, the back contact resistance yields 4.560 Ω. The front and back contact
resistance found in this research are compatible with the high-efficiency solar cells.
xi
Chapter 1: Introduction
Worldwide energy demand has been continuously increasing and is not expected to stop at the
nearest time perspective [1]. Clean, efficient, affordable and reliable energy services are
indispensable for global prosperity. Developing countries in particular need to expand access
to reliable and modern energy services if they are to reduce poverty and improve the health of
their citizens, while at the same time increasing productivity, enhancing competitiveness and
promoting economic growth. Current energy systems are inadequate to meet the needs of the
world’s population and are jeopardizing the achievement of the Millennium Development
Goals (MDGs) [2].
In the International Energy Outlook 2017 (IEO2017) Reference case, total world energy
consumption rises from 575 quadrillion British thermal units (Btu) in 2015 to 736 quadrillion
Btu in 2040, an increase of 28%. Most of the world’s energy growth will occur in countries
outside of the Organization for Economic Cooperation and Development (OECD), where
strong, long-term economic growth drives increasing demand for energy. Non-OECD Asia
(including China and India) alone accounts for more than half of the world’s total increase in
energy consumption over the 2015 to 2040 projection period. By 2040, energy use in non-
OECD Asia exceeds that of the entire OECD by 41 quadrillion Btu in the IEO2017 Reference
case [3]. World energy consumption by country grouping is shown in Figure 1.1.
Figure 1.1: World energy consumption by country grouping [3].
1
Today a large proportion of energy is supplied by burning fossil fuels like oil, coal, and natural
gas [1]. Oil is the world’s primary fuel source for transportation and Coal is primarily used to
generate electricity. Natural gas is most commonly used to produce heat or electricity for
buildings or industrial processes [4]. Like every other thing, fossil fuels too have the negative
effect on our environment [5]. Oil and coal release sulfur dioxide gas when they burn, which
causes breathing problems for living creatures and contributes to acid rain. Fossil fuels also
release carbon dioxide which adds to the greenhouse effect and increases global warming [6]. It
is officially agreed that combustion of fossil fuels is the main reason of global warming. The
correlation between the increase of the global temperature and the increase of anthropogenic
emitted greenhouse gases was proven on a scientific base. With a share of 70% of the so-called
greenhouse effect, carbon dioxide takes up an exceptional position under the greenhouse gases.
It is predicted by the United Nations Intergovernmental Panel on Climate Change that the
warming of the Earth over the next 50 years could induce glacial melting, raise sea level and
change weather patterns. Moreover, their supply is limited and they will eventually run out [1].
Therefore, to alleviate the threat from such environmental catastrophes and to maintain our
planet inhabitable for other generations it is necessary to diversify our energy portfolio as early
as possible, using renewable energy. The renewable energy sources are solar, wind, hydro,
tidal, wave, geothermal, biomass and so on. There are many good reasons for using renewable
energy sources. They are cleaner and less polluting than traditional forms of energy, such as
coal and gas. The word “renewable” means they are replenished resources, so theoretically they
are infinite sources of energy. Renewable energy is providing affordable electricity across the
world right now and can help stabilize energy prices in the future. The costs of renewable
energy technologies have declined steadily, and are projected to drop even more [7].
In the long term, the IEO2017 Reference case projects increased world consumption of
marketed energy from all fuel sources except coal, where demand is essentially flat through
2040. Renewables are the world’s fastest-growing energy source, with consumption increasing
by an average 2.3% per year between 2015 and 2040. The world’s second fastest-growing
source of energy is the nuclear power, with consumption increasing by 1.5% per year over that
period.
Although consumption of nonfossil fuels is expected to grow faster than fossil fuels, fossil fuels
still account for 77% of energy use in 2040. Natural gas is the fastest-growing fossil fuel in the
2
projections. Global natural gas consumption increases by 1.4% per year [3]. World energy
consumption by energy source is shown in Figure 1.2.
Figure 1.2: World energy consumption by energy source [3].
Abundant natural gas resources and rising production-including supplies of tight gas, shale gas,
and coalbed methane-contribute to the strong competitive position of natural gas. Liquid fuels-
mostly petroleum based remain the largest source of world energy consumption. However, the
liquids share of world marketed energy consumption falls from 33% in 2015 to 31% in 2040,
as oil prices rise steadily, leading many energy users to adopt more energy-efficient
technologies and to switch away from liquid fuels when feasible [3].
With a population of 160 million, Bangladesh is one of the world's most populated countries.
Electricity is a pre-requisite for the technological and economic growth of Bangladesh. The
maximum power demand of this country has always been increasing and the rate has increased
over the past couple of years. About one-third of the total population still do not have access
to electricity [8]. The quality of power cannot be maintained because of the shortage of
generation and insufficient capacity and low quality of transmission and distribution networks.
In 1974-75, the installed electricity generation capacity was 667 MW [9] whereas in August
2016 it was 12780 MW including the 600 MW power import from India [10].
Figure 1.3 shows the increase in installed power generation capacity from 1990- 91 to 2015-
16 in Bangladesh.
3
Figure 1.3: Installed power generation capacity in Bangladesh [11].
It is evident from the Figure that the capacity has grown rapidly over the last few years.
Favorable Government policies have attracted private investment and Independent Power
Producers (IPP). They are now producing 46% of total power in Bangladesh [11]. The growth
in maximum power demand from 1994-95 to 2014 -15 in Bangladesh is shown in Figure 1.4.
Figure 1.4: Maximum power demand in Bangladesh [11].
It is clear from the figure that the demand increased rapidly after 2010. This is due to the fact
that this demand actually represents the demand of connected loads of the grid. The installed
capacity also has the similar trend in terms of increase. However, 79 % percent of the connected
consumers suffer from load-shedding, and 60% of the consumers face low voltage supply [12].
Existing power plants of Bangladesh are mostly gas and oil-fired types. Required oil has been
imported from outside countries. Gas has been taken from internal resources. At this moment,
it is no longer possible to feed further Gas-fired power plants with the available gas. Apart from
this, the Government understanding is to reduce dependency on these two primary fuels and to
go for alternative fuels [8].
4
Bangladesh Government has given a strong drive to boost renewable electrical energy
production. The government has established Sustainable and Renewable Energy Development
Authority (SREDA) to promote renewable energy and energy efficiency in 2014. To strengthen
international cooperation, Bangladesh became one of the initial members of the International
Renewable Energy Agency (IRENA), the only inter-governmental agency working exclusively
on renewable energy. Currently, renewable energy sources have a very low share of the total
generation (< 2%) [8]. The government of Bangladesh is trying to encourage the use of
renewable energy sources and formulated a renewable energy policy. One of the main focuses
of this policy is to scale up contributions of renewable energy to electricity production. The
initial goal was to generate 5% power from renewable energy sources by 2015 and 10% by
2020 [13].
Bangladesh is situated between 20.30 and 26.38 degrees north latitude and 88.04 and 92.44
degrees east which is an ideal location for solar energy utilization [14]. A state-owned
development financial institution dedicated to promote or finance infrastructure and renewable
energy projects in Bangladesh named “Infrastructure Development Company Limited
(IDCOL)” has started the solar home system (SHS) program in 2003 to ensure access to clean
electricity for the electricity-starved off-grid rural areas of Bangladesh. The program
supplements the Government’s vision of ensuring “Access to Electricity for All” by 2021.
About 4 million SHSs have already been installed under the program in the off-grid rural areas
of Bangladesh. As a result, almost 18 million beneficiaries are getting solar electricity which
is around 11% of the total population of Bangladesh. Solar PV based mini-grid projects are
installed in remote areas of the country where the possibility of grid expansion is remote in
near future. These projects provide grid quality electricity to households and small commercial
users and thereby encourage commercial activities in the project areas. So far, IDCOL has
approved 16 Solar Mini-Grid Projects, among which 7 are operational while the rest are under
construction. The mini-grid project has successfully created access to low emission electricity
for almost 5000 rural households in Bangladesh. IDCOL has additional targets to install 50
solar mini-grid by 2018. IDCOL has approved 459 solar irrigation pumps of which 324 are
already in operation. Bangladesh Power Development Board (BPDB) has also been installing
solar based power plants in different areas of the country [8].
The amount of energy which Earth surface receives from the sun is around 89000 TW, while
world energy consumption converted into power is equal to 15TW [15]. Therefore, it is clear
5
that utilization of a minuscule fraction of solar power coming to the Earth is enough to meet
our global energy demands. This fact shows what enormous potential sun energy would have
for our energy balance if it could be efficiently collected. The energy conversion of solar energy
largely depends on what types of solar cell used. There are many types of solar cell available
to generate electricity. The most common types are crystalline, thin film, dye-sensitized,
quantum dot and perovskite solar cells etc. But crystalline silicon cells are used in the largest
quantity of all types of solar cells on the market, representing about 90% of the world total
solar cell production in 2008 [16]. Silicon is safe for the environment and one of the most
abundant resources on earth, representing 26% of the crustal material. The abundance and
safety of silicon as a resource grants, the silicon solar cell is a prominent position among all
the various kinds of solar cells in the solar cell industry. World annual solar cell production of
100 GWp (Gigwatt peak) is expected to be achieved by around 2020 and the silicon solar cell
is the most viable candidate to meet this demand from the point of view of suitability for large
volume production. Among the crystalline silicon solar cells, monocrystalline silicon technique
is used as a promising method for solar cell fabrication due to its high efficiency [17]. For
monocrystalline silicon solar cell fabrication, phosphorous diffusion technique is the most
widely used technique for photovoltaic industry [18].
For the first time in Bangladesh, Bangladesh Atomic Energy Commission (BAEC) has
established a solar cell fabrication laboratory where monocrystalline silicon solar cells are
fabricated using phosphorus diffusion technique. No systematic study was conducted to
measure the contact resistance of solar cells by varying diffusion time i.e. doping density. The
present attempt has therefore been taken to determine the contact resistance with the variation
of doping concentration using Transmission Line Method (TLM). Finally, an optimum value
of contact resistance was investigated with corresponding diffusion time.
6
Chapter 2: Literature Review
2.1 Introduction
There are a variety of different semiconductor materials used in solar cells. Silicon is, by far,
the most common material used in solar cells, representing approximately 90% of the solar cell
sold today. It is also the second most abundant material on Earth (after oxygen). Crystalline
silicon cells are made of silicon atoms connected to one another to form a crystal lattice. This
lattice provides an organized structure that makes the conversion of light into electricity more
efficiently. Solar cells made out of silicon currently provide a combination of high efficiency,
low cost, and long lifetime [19].
2.2 Silicon
An atom of silicon has 14 electrons arranged in three general electron shells. The first two
shells closest to the nucleus are full. The outer shell has four electrons and is only half-
full. However, silicon will and can share electrons with its neighbors. In the case of crystalline
silicon, there are other silicon atoms that will provide electrons for sharing. Pure crystalline
silicon is a poor conductor as there are no extra electrons free to move about. Because of this,
a solar cell is constructed with silicon mixed with impurities; this is called doping the
silicon. For example, phosphorus atoms could be mixed with the silicon. Phosphorus has five
electrons in its outer shell. It still bonds with the silicon atoms but now there is an extra electron.
When energy is added to the crystal, this extra electron can break free of bond and this leaves
a hole. Throughout the lattice, a series of extra electrons moving freely of their bonds; these
electrons are called free carriers. When silicon is doped with phosphorus, it is called an N-type
crystal as it has extra electrons (N for negative). Part of a common photovoltaic cell is created
as an N-type crystal. However, it is also possible to make P-type (positive) silicon. Instead of
using phosphorus, Boron can be used. Boron has three valence or outer electrons. It,
consequently, has more holes available for the free electrons created when the N-type silicon
is energized. A hole can be thought of as an absence of an electron or a positive charge. The
holes can appear to move just like free electrons. Both electrons and holes can be called charge
carriers [20]. Figure 2.1 shows N-type and P-type silicon.
7
Negative Free-Carriers (electrons) Positive Free-Carriers (holes)
(a) N-Type Silicon (b) P-Type Silicon
Figure 2.1: (a) N-type silicon and (b) P-type silicon.
2.3 Solar Cell

A solar cell is a device that converts photons from the sun (solar light) into electricity [21]. It
is a form of photoelectric cell, defined as a device whose electrical characteristics, such as
current, voltage or resistance vary when exposed to light. Solar cells are the building blocks of
photovoltaic modules, otherwise known as solar panels. Fundamentally, the device needs to
fulfill only two functions: photogeneration of charge carriers (electrons and holes) in a light-
absorbing material and separation of the charge carriers to a conductive contact that will
transmit the electricity.
2.4 Crystalline Silicon (c-Si) solar cells
Conventional solar cells, made from silicon are flat plated and rigid and generally have the
highest efficiencies. Crystalline silicon (c-Si) is the most widely used and most efficient
material expended in the production of solar cells with commercial efficiencies sometimes
reaching 20%. It is estimated that about 80% of all solar panels are created with crystalline
silicon and this material is especially useful because it has shown both long-term performance
and reliability. Crystalline silicon cells are made from silicon wafers that can be either mono-
crystalline or multi-crystalline structures, depending on what is available or what is needed for
that particular process. All structures using pure silicon will face shortages, especially since the
material is used in other semiconductor industries as well as in solar cell. Silicon is a plentiful
element in the Earth’s crust. But most of it occurs in compounds that would be costly to extract
the pure silicon from them. Crystalline silicon is the material to make efficient solar panels.
However, because of shortages and the general high costs of silicon, other options have been
developed with other materials or smaller amounts of silicon [21].
8
2.5 Solar cell structure
The structure of a c-Si solar cell is shown in Figure 2.2. Crystalline silicon solar cell is
composed of two basic layers, the emitter which is n-doped and the base which is p-doped
semiconductor.
Figure 2.2: Structure of a crystalline silicon solar cell. Reproduced from [22].
The front contact has to be designed in a way that prevents shading of the front surface. Because
the bulk of the electron-hole pairs are generated near the surface, the position of the p-n junction
is also near the surface. This prevents recombination of charge carriers before they reach the
junction where they are separated by the electric field.
2.6 Photovoltaic Energy conversion
Photovoltaic energy conversion is the direct production of electrical energy in the form of
current and voltage from electromagnetic (i.e., light, including infrared, visible, and ultraviolet)
energy. The basic four steps needed for photovoltaic energy conversion are [23]:
1. A light absorption process which causes a transition in a material (the absorber) from a
ground state to an excited state.
2. The conversion of the excited state into (at least) a free negative and a free positive-charge
carrier pair and
3. A discriminating transport mechanism which causes the resulting free negative-charge
carriers to move in one direction (to a contact that we will call the cathode) and the resulting
free positive charge carriers to move in another direction (to a contact that we will call the
anode). The energetic, photogenerated negative-charge carriers arriving at the cathode result in
9
electrons which travel through an external path (an electric circuit). While traveling this path,
they lose their energy doing something useful at an electrical “load” and finally they return to
the anode of the cell. At the anode, every one of the returning electrons completes the fourth
step of photovoltaic energy conversion which is closing the circle by.
4. Combining with an arriving positive-charge carrier thereby returning the absorber to the
ground state. In some materials, the excited state may be a photogenerated free electron-free
hole pair. In such a situation, step 1 and step 2 coalesce. In some materials, the excited state
may be an exciton, in which case steps 1 and 2 are distinct.
2.7 Principle of solar cell operation
Solar cells are made of materials called semiconductors which have weakly bonded electrons
occupying a band of energy called the valence band. When energy exceeding a certain
threshold called the band gap energy, is applied to a valence electron, the bonds are broken and
the electron is somewhat “free” to move around in a new energy band called the conduction
band where it can “conduct” electricity through the material. Thus, the free electrons in the
conduction band are separated from the valence band by the band gap (measured in units of
electron volts or eV). This energy needed to free the electron can be supplied by photons which
are particles of light. Figure 2.3 shows the idealized relationship between energy (vertical axis)
and the spatial boundaries (horizontal axis). When the solar cell is exposed to sunlight, photons
hit valence electrons, breaking the bonds and pumping them to the conduction band. There, a
specially made selective contact that collects conduction-band electrons drives such electrons
to the external circuit. The electrons lose their energy by doing work in the external circuit such
as pumping water, spinning a fan, powering a sewing machine motor, a light bulb, or a
computer. They are restored to the solar cell by the return loop of the circuit via a second
selective contact which returns them to the valence band with the same energy that they started
with. The movement of these electrons in the external circuit and contacts is called the electric
current. The potential at which the electrons are delivered to the external world is slightly less
than the threshold energy that excited the electrons; that is, the band gap. Thus, in a material
with a 1 eV band gap, electrons excited by a 2 eV photon or by a 3 eV photon will both still
have a potential of slightly less than 1 V (i.e. the electrons are delivered with an energy of 1
eV). The electric power produced is the product of the current times the voltage; that is, power
is the number of free electrons times their potential.
10
Figure 2.3: Schematic of a solar cell. Electrons are pumped by photons from the valence
band to the conduction band.
Sunlight is a spectrum of photons distributed over a range of energy. Photons whose energy is
greater than the band gap energy (the threshold energy) can excite electrons from the valence
to conduction band where they can exit the device and generate electrical power. Photons with
energy less than the energy gap fail to excite free electrons. Instead, that energy travels through
the solar cell and is absorbed in the rear as heat. Solar cells in direct sunlight can be somewhat
(20–30° C) warmer than the ambient air temperature. Thus, PV cells can produce electricity
without operating at high temperature and without mobile parts. These are the salient
characteristics of photovoltaic that explain safe, simple and reliable operation [24].
At the heart of any solar cell is the p-n junction. Modeling and understanding is very much
simplified by using the p-n junction concept. This p-n junction results from the “doping” that
produces conduction-band or valence-band selective contacts with one becoming the n-side
(lots of negative charges), the other the p-side (lots of positive charges).
2.8 The p-n junction

A line dividing n-type from p-type silicon establishes the position of a potential barrier essential
to the operation of a solar cell. Figure 2.4 shows the Formation of the p-n junction. In the p-
type material, there are excess holes; in the n-type material, excess electrons which is shown
in Figure 2.4(a). When the n and p materials are in contact, free electrons in the n-type material
11
adjacent to the many holes in the p-type material at the junction will jump into the p- side,
which is equivalent to a hole moving over into the n-type material. This charge transference
process happens rapidly along the dividing line (junction), sending huge numbers of electrons
to ‘the p-type side and holes to the n-type side as shown in Figure 2.4(b). This causes an
immediate imbalance of charge: more negative charges (extra electrons) along the p-type side
of the interface, more positive charges (ions) along the n-type side which is shown in Figure
2.4(c). When electrons move over into the p-type material during junction formation, they find
holes in the silicon bonds and drop into them.
In like manner, holes that transfer to the n-type side are quickly filled by the n-type side’s
numerous extra electrons. Consequently, carriers that form the junction lose their freedom of
movement. Thus, although a charge imbalance exists at the junction, there are very few free
electrons on the p-type silicon side to be pulled back to the n-type side, and very few free holes
on the n-type side to be transferred back to the p-type material. So, the charge imbalance stays
fixed in place.
The process of charges moving across the junction to create a charge imbalance in the above
described manner does not continue indefinitely. Charged carriers that have already crossed
the junction set up an electric force (field) that acts as a barrier opposing the further flow of
free carriers. As more carriers cross the junction, the barrier enlarges, making it increasingly
difficult for other carriers to cross. Eventually, an equilibrium is established where no more
electrons or holes switch sides. This creates a fixed potential barrier at the junction with the n-
type side adjacent to the junction being positively charged and the p-type side adjacent to the
junction being negatively charged. Movement of electrons into the p-type silicon and holes into
the n-type silicon builds up a fixed potential barrier at the junction opposing the further
movement of free carriers and creating a state of equilibrium. The “height” (that is, the strength
of the electric force) of the barrier, it should be noted, depends upon the amount of dopant in
the silicon-the more the dopant, the more charge imbalance induced and the greater the barrier’s
ability to separate charges.
12
Figure 2.4: Formation of p-n junction.
Some qualities of the barrier oppose the crossing of majority charge carriers which is shown in
Figure 2.4(d). That is, electrons in the n-type material would have to climb the barrier against
the built-in field to enter the p-type material. Similarly, holes in the p-type region are held back
13
from entering the n-type region. Here minority carriers are not hindered by the barrier. In fact,
free electrons on the p-type side, of which there are very few, being the minority carrier there
are driven by the junction field to the opposite, n-type side.
The same is true of holes driven from the n-type side. But normally (under no illumination)
there are so few minority carriers on their respective sides that their movement is nil, and there
is balanced by the few majority carriers that randomly assume enough energy to cross the
barrier. This selective barrier at the junction is the means of separating charges during electron-
hole generation under illumination. It is the key to the production of a photovoltaic electric
current [25].
2.9 Analysis of p-n junction
As it is known that an electric field spontaneously occurs at the interface between p and n-type
semiconductors, in so-called space charge region (SCR). The built-in potential difference
across the p-n junction, is [26-27],
= ……………………………..… (2.1)
where Nd and Na stand for the density of donor and acceptor atoms. Q is the absolute value of
the charge of an electron. The width of the space charge region is given by [27-28],
=√ + ……………………………… (2.2)
Where εs is the local permittivity of the semiconductor. It is chosen that the origin of the
longitudinal axis at the interface between differently doped semiconductors. According to
equations 2.1 and 2.2, the built-in potential difference increases with increasing doping, while
the width of the SCR decreases. In solar cells both high potential difference and wide SCR are
needed for effective drift of charge carriers towards the right direction, so a compromise must
be made when choosing the doping level. The SCR is highly resistant part of p-n junction while
the bulk of the junction has very low resistance for electric current. Any applied bias would
have the highest drop in the SCR.
14
A hole current flows from the n to the p- side of the junction known as hole generation current.
It is minority carrier current because it results from the eneration of holes when electrons are
thermally excited from valence to conduction band on the n-side. A hole must be generated
within a diffusion length from SCR and when it reaches the SCR, it is immediately driven to
the p-side by strong electric field. Similarly, there flows an electron generation current from
the p to the n-side of the junction. Another hole current flows from the p-side to the n-side of
the junction known as hole recombination current. It results from the holes that reach the SCR
with sufficient energy to surmount the potential barrier of the SCR. The number of such holes
is proportional to and thus depends strongly on the potential step ΔV across the
junction. If a forward (positive) bias is applied, such that it raises the potential of the p-side
with respect to the n-side, the potential barrier is lowered and the recombination current is
stronger. In that case, the electric current flows with little resistance through the p-n junction
dominated by majority carrier current. On the contrary, if a negative bias is applied, the
potential barrier is increased and only little current flows through the device. This is known as
the rectifying action of a diode.
In equilibrium, when no external bias is applied, the net electric current is zero. When a forward
bias V is applied, the net charge current density, flowing in the direction of recombination
currents, is given by [27]
= + 1 ……………………… (2.3)
Where and are hole and electron generation current densities. The situation is
considerably altered when a p-n junction within a photovoltaic material is illuminated. The
generation currents resulting from photogenerated minority charge carriers are increased. The
so-called photocurrent becomes the dominant electric current, flowing in the opposite direction
as recombination current. It is taken that the potential drop across the junction to be the
difference between the built-in bias Vbi and the applied bias V, Vj = Vbi V. Now, it is necessary
to find a solution for electric current density flowing through a photovoltaic device under
illumination and applied bias. In general, the problem consists of solving a set of coupled
differential equations for the hole density, the electron density, and the electrostatic potential,
given specified forms for the photogeneration, the recombination and the hole and electron
currents [26]. It is a complex problem but analytic solutions can be found by using two
15
approximations which allow the hole and electron currents to be decoupled. The first one is so-
called depletion approximation which assumes there are no free charge carriers in the space
charge region around the junction. The electric field vanishes at fixed distances from the
junction. Within the neutral regions away from the junction, majority carrier densities have
their equilibrium value and variations in minority carrier densities determine the current. In
neutral regions, there is no electric field and currents of minority carriers are only diffusive.
The depletion approximation allows the solutions in neutral p and n-regions to be decoupled.
In the second approximation, it is assumed that the recombination process to be linear in the
minority carrier density. It is sometimes called superposition approximation [26] because the
effect of bias and illumination are decoupled so the solution to the current is the sum of both.
Some important steps are discussed now in solving the problem of electric current density.
When a device is illuminated with light with energy W, the rate of charge generation, g is given
by [26]
( , )= 1 ( ) ( ) ( ) ( )
…………………….... (2.4)
Where R is the reflectance of the material, bs (W) is the incident photon flux and α (W) is the
absorption coefficient which is given by the matrix element calculated with use of the Fermi
golden rule [29]. Integrating over photon energies, it is obtained the integrated charge
generation rate G. In the presence of both the electric field E and charge carrier density gradient,
the carrier current density can be written as the sum of a term proportional to the density
gradient diffusion current and a term proportional to the field – the drift current [26-27]:
( )= ∇ + μ and ( )= ∇ + μ …….. (2.5)
Here, Jp denotes charge current density as a consequence of the motion of holes and Jn denotes
charge current density as a consequence of the motion of electrons. Μp and μn are mobilities
while Dp and Dn are the corresponding diffusion constants of holes and electrons respectively.
If we combine equations (2.5) with the steady state continuity equations, take the current
generated by a spectrum containing a single wavelength and reduce the problem to one
dimension, x, then the transport equations in the case of zero electric field in the neutral p and
n- regions simplify to [30]:
16
( , ) …………………………..… (2.6)
+ = 0, =
for holes in the n-region
( , ) …………………………….….. (2.7)
+ = 0, =
for electrons in the p-region. Lp and Ln stand for diffusion lengths of holes and electrons,
depending on the charge carrier lifetime τ,
=√ , = √( )………………………………. (2.8)
At the boundary with the SCR, the condition for density of holes is given by [28]
= ( 1), = …………………………………….. (2.9)
The boundary condition at the outer surface is determined by the surface recombination rate
Sp,
= ( ) ………………………………….. ………………….. (2.10)
It follows that the hole current in the n-region and the electron current in the p-region, which
we obtain in a similar way, can be written as [26],
( , )= , ( , )= ,…………….…… (2.11)
The current in the space charge region can be determined from carrier continuity. It can be
written as integral of difference between charge recombination rate U and charge generation
rate G over the SCR: [31],
= ∫ ( ) ………………………………………………….... (2.12)
This is equal to electrons and holes within the space charge region. The net current is given by
the sum of hole and electron currents at any point and is constant through the device in steady
state. A general solution for p can be obtained analytically by solving equation (2.6). From
(2.12) and after integrating over energy, general solution for Jp is obtained and similarly
solution for Jn. There are two separate contributions to the net current density. The first one is
17
proportional to the incident spectral photon flux density and the second one is proportional to
1 as a consequence of applied bias. With solutions for current densities, dark current
J dark can be calculated, the case where there is no contribution from illumination, and the
short-circuit current Jsc, the case where V = 0. The J is illustrated in Figure 2.5 as a function of
applied bias V. By adding short-circuit current and dark current, current-voltage characteristics
of a solar cell is constructed:
( )= J ( )=J J , 1 ……………… (2.13)
m,0 is material-dependent constant and m is ideality factor that describes the deviation from
ideal diode behavior with m = 1. The last term in expression (2.13) is indeed the same one
obtained by general analysis of p-n junctions [28]. The additional current density Jsc is a
consequence of light illumination. The sign of the currents is chosen so that photocurrent is
positive. With increasing V, the flux emitted from a solar cell increases and the net current
decreases. The expression provides the open-circuit voltage – the voltage, at which the current
is zero,
= ln + 1 …………………………………………… (2.14)
,
If the V is increased above the Voc, the cell begins to act like a light emitting device. Voc must
always be less than Eg/q, where Eg is the band gap of the semiconductor used.
Figure 2.5: Current-voltage (black) and power-voltage (grey) characteristics of an ideal diode
(ideal photovoltaic device). Vm and Jm denote voltage and current density at maximum power
point. Reproduced from [26].
18
2.10 Fabrication of monocrystalline silicon solar cell
Monocrystalline type silicon solar cell fabrication deals with a set of basic materials, chemicals
components and equipment’s and machineries. The basic materials [32] used for solar cell
fabrication are monocrystalline type silicon wafers that are p-type doped initially. Fabrication
of monocrystalline silicon solar cell from p-type silicon wafer requires several numbers of
process steps which are described here.
2.10.1 Cleaning and texturing of wafers
Wire sawing is used to cut silicon ingots into wafers. This process induces small cracks
penetrating around 10 μm deep into the wafer surface. Saw damage has to be removed from
the wafer surface because it reduces the mechanical strength of the wafer and increases
recombination in the surface region. Alkaline or acidic solutions can be used for saw damage
removal [33]. In addition, this process step is normally used to form a surface texture that
reduces the total reflection of the wafer. The wafer is cleaned to remove metal and organic
contaminants that would cause an increase of surface and bulk recombination during the
following high-temperature process steps. A solution of sodium hydroxide NaOH or potassium
hydroxide KOH and water is normally used for alkaline saw damage removal on multi- or
monocrystalline silicon wafers. Alkaline etching has different etch rates for different
crystallographic orientations. This anisotropy results in small pyramids with a square base
randomly distributed over the wafer surface for monocrystalline silicon wafers with a (100)
surface orientation. To improve the lateral uniformity and the anisotropy of the etching process,
isopropyl alcohol (IPA) is added to the etching solution. Applying this texture the total
reflection of a polish-etched planar, silicon wafer can be reduced from 35% to 12% [34]. After
texturing, the wafers are rinsed in deionized (DI) water, cleaned in hydrochloric acid (HCl),
rinsed in DI water, cleaned in hydrofluoric acid (HF), rinsed in DI water, and finally dried in
hot air. HCl removes metal impurities from the wafer surface. HF etches the native silicon
dioxide off, removes metals from this surface, and forms a hydrophobic surface. Alkaline saw
damage removal, texture, and cleaning are performed in batch processes.
2.10.1.1 Saw damage removal process
Saw damage results from the wire sawing process used to slice silicon ingots into wafers. As a
result of this mechanical process, cracks of about 1-10 μm deep are introduced into the surfaces
of the wafer. Removing the saw damage from the wafer surface improves the mechanical
19
strength of these thin wafers and increases the recombination at the surface region [35]. Saw
damage removal is done using NaOH and De-Ionized (DI) water solution at 70°C temperature
which also removes the organic contaminants, a thin oxide layer and metal particles from the
surface of the wafers. The overall chemical reaction generally accepted are summarized in
equation 2.15- 2.18 [36]. The etching rate of silicon depends on the product of hydroxide ions
([OH]-) and free water concentration ([H2O]) [37].
NaOH + H2O → Na+ + OH-…................................. (2.15)

Si + 4OH- → Si(OH)4 …..........................................(2.16)
Si(OH)4 + 2OH- → SiO2(OH)-- + 2H2O….................(2.17)
4H2O + 4e- → 4OH- + 2H2…..................................... (2.18)
2.10.1.2 Hydrophobic process
The hydrophobic process is done to remove the native oxide [38]. A solution of the ratio of HF
(Hydrofluoric Acid): H2O (DI-water) = 1 ml: 50 ml is prepared for hydrophobic process. The
wafers passed the saw damage removal process are dipped into this HF solution for few minutes
and then they are removed from the HF solution and dipped for few minutes in DI-water.
2.10.1.3 Texturing process
The solar cell efficiency is connected with device fabrication processes, such as silicon surface
texturing, which increases the surface absorption area of incident radiation on the cell and,
consequently, reduces the substrate reflectance and increase the efficiency [39]. At high -
temperature, the chemical reaction between silicon and alkali occurs as follows:
Si+2OH-+H2O=SiO32-+2H2↑…………………. (2.19)
So hot alkaline solution is usually used to corrode the silicon. For different crystalline faces
and crystalline directions, the atoms are arranged differently, so the strength between the atoms
is different. According to principles of electrochemical corrosion, their corrosion rate will be
different. For {100} planes, the spacing of the adjacent two planes is maximum and the density
of covalent bonds is the minimum, so the adjacent layer along the {100} atomic planes are
most prone to breakage. On the other hand, atoms within the {111} planes have the minimum
distance, and the surface density of covalent bonds is the maximum, which results in that the
corrosion rate is the minimum along the <111> direction. Therefore, the corrosion faces
20
revealed by preferential etching solution are (111) planes. After single crystalline silicon
material with <100> orientation was corroded preferentially, the pyramids on the surface of
mono-crystalline silicon come from the intersection of (111) planes. The "pyramid" structure
is shown in Figure 2. 6 [40].
Figure. 2.6: Light trapping by “pyramid” covered at the textured surface.
2.10.2 SEM analysis of textured wafer
The scanning electron microscope (SEM) uses a focused beam of high-energy electrons which
interact with the sample and generate a variety of signals at the surface of solid specimens.
These signals reveal information about the sample including external morphology (texture),
chemical composition and crystalline structure and orientation of materials making up the
sample [41]. Scanning electron microscope was invented by Manfred von Ardenne in 1937.
The scanning electron microscope (SEM) is a microscope that uses electrons instead of photons
to form an image [42]. This microscope, basically, consists of an electron gun and a set of
electromagnetic fields to guide the electron beam toward the sample surface. Then, the beam
scans the sample thanks to scanning coils. Finally, backscattered and secondary electrons
received from the surface are collected by detectors and converted in a signal to produce the
final image. Nowadays, the surface morphology of a solid sample can be studied by the SEM,
because it has much higher resolution and has a large depth in field than a traditional
microscope. On the other hand, in addition to the backscattered and secondary electrons from
the sample surface, there are others types or signals produced during this process (Auger
electrons, X-ray fluorescence photons and others photons with various energies) that could be
used in chemical analysis [43]. Figure 2.7 shows the Schematic diagram of the Scanning
electron microscope measurement system.
21
Figure 2.7: Schematic diagram of the Scanning Electron Microscope measurement system.
2.10.3 Surface Reflection (SR)
Reflection of light (and other forms of electromagnetic radiation) occurs when the waves
encounter a surface or other boundary that does not absorb the energy of the radiation and
bounces the waves away from the surface. For high-efficiency solar cells, lowest possible
spectral reflection is needed. This is due to the fact that reflected light is unable to generate
electron-hole pairs. Since the white light is composed of spectral content varying from visible
to near infrared, the solar cell must also be characterized for the same wavelength range.
Spectral solar cell reflection response is measured by collecting reflected light from the surface
as a function of wavelength. A simple spectral reflection Measurement (SRM) system has been
used to measure the reflection of Si wafers. A computer-controlled monochromator illuminates
the wafer under test over a broad (400-1200 nm) spectral range. Reflected light from the surface
is focused onto a photodetector connected to a lock-in amplifier to provide detection capability
over extremely large (μV to V) scale. A Lab VIEW-based computer interface is used to acquire
SRM as a function of wavelength.
2.10.4 Diffusion
Diffusion is the process to introduce a controlled amount of dopants into the semiconductor to
alter the conductivity type of that semiconductor [44]. In the diffusion process, the dopant
22
atoms are introduced from the gas phase by using doped-oxide sources. The doping
concentration decreases monotonically from the surface, and the in-depth distribution of the
dopant is determined mainly by the temperature and diffusion time. Boron is the most common
p-type impurity in silicon, whereas arsenic and phosphorus are used extensively as n-type
dopants. These three elements are highly soluble in silicon with solubilities exceeding 5 x 1020
atoms/cm3 in the diffusion temperature range (between 800oC and 1200oC). These dopants can
be introduced via several means, including solid sources (As2O3 for As, and P2O5 for P), liquid
sources (BBr3, AsCl3, and POCl3), and gaseous sources (B2H6, AsH3, and PH3). Usually, the
gaseous source is transported to the semiconductor surface by an inert gas (e.g. N2).
2.10.4.1 Atomic mechanism of diffusion

[
Impurity atoms may occupy either substitutional or interstitial positions in the Silicon lattice.
Figure 2.8 shows Substitutional and interstitial impurities in silicon. Impurity atoms utilized as
dopants such as boron (B), phosphorus (P) and arsenic (As) occupy substitutional positions
where the dopant atoms can contribute free electrons or holes to the silicon lattice (dopant
atoms introduced to silicon by ion implantation may not occupy substitutional positions until
the dopant is activated). During high-temperature processing impurity profiles are redistributed
through a process known as diffusion. The redistribution of impurities may be intentional as in
a “drive-in” step or unintentional as a result of high-temperature oxidation, deposition or
annealing processes.
Figure 2.8: (a) Substitutional and (b) Interstitial impurities in silicon.
The movement of a substance due to diffusion is driven by the slope of the concentration
profile. Impurity atom diffusion may be vacancy, interstitial or a combination mechanism
known as interstitialcy. Figure 2.9 shows the vacancy, interstitial and interstitialcy diffusion
mechanisms.
23
Figure 2.9: Vacancy, interstitial and interstitialcy diffusion mechanisms.
Vacancy diffusion occurs when a substitutional atom exchanges lattice positions with a
vacancy, requires the presence of a vacancy. Interstitial diffusion occurs when an interstitial
atom jumps to another interstitial position. Interstitialcy diffusion results from silicon self-
interstitials displacing substitutional impurities to an interstitial position requires the presence
of silicon self-interstitials, the impurity interstitial may then knock a silicon lattice atom into
a self-interstitial position. It is important to observe here that since dopant atoms such as
phosphorus, arsenic and boron occupancy substitutional positions once activated, dopant
diffusion is closely linked to and controlled by the presence of vacancy and interstitial point
defects. Whether an impurity atom occupies a substitutional or interstitial position in single
crystal silicon, the atom is trapped in a periodic potential defined by the lattice. Figure 2.10
shows the impurity atom diffusing along a periodic potential. The probability of an atom
jumping from one position to the next increases exponentially with increasing temperature.
Figure 2.10: Impurity atom diffusing along a periodic potential.
Impurity profile spreading due to random thermal motion is illustrated in Figure 2.11.If random
thermal motion causes 20% of the atoms in each position to jump to a new position in each unit
of time, 10% of the atoms would be expected to jump to the left and 10% of the atoms would
be expected to jump to the right at time = 1. The areas of higher concentration would have
more atoms jump out of the area than jump in. Over time the net result of the random thermal
motion would be a gradual spreading of the profile, time = 0, time = 4. At infinite time the
impurity distribution would be uniform throughout the background medium [45].
24
Figure 2.11: Impurity profile spreading due to random thermal motion - diffusion.
2.10.4.2 Fick’s first law of diffusion

[[
From Figure 2.12, considering two equal thickness slices of a solid where slice 1 and slice 2
have different impurity concentrations, C1 and C2 given by
= …………………………….… (2.20)
and
= ………………………………. (2.21)
and, N1 and N2 are the number of impurity atoms in slice 1 and slice 2 respectively, A is the
cross-sectional area of the slices and h is the thickness of the slices.
Atoms throughout the solid are constantly vibrating from thermal energy. At a given
temperature each atom in the slice has a frequency of jumps to the adjacent slice, v, with equal
probability of jumping in either direction, therefore the frequency of jumps from one slice to
the next in a particular direction is v/2. For the plane separating slice 1 from slice 2, the flow
of atoms across the boundary is
= ………………………. (2.22)
and
25
= ………………………….. (2.23)
where t is time, left to right is the positive direction and right to left is the negative direction of motion.
Figure 2.12: Diffusion from a concentration gradient.

[[ [
Combining equations 2.22 and 2.23 yields the net flow across the boundary
[
= ( ) …………………... (2.24)
[[
and substituting concentration from equations 2.20 and 2.21 into equation 2.24, gives
( )
= ……………………….. (2.25)
Since the concentration gradient is given by
= ……………………………… (2.26)
equation 2.25 and 2.26 can be combined to give
= ……………………..…… (2.27)
By now introducing flux, j, defined as the number of units passing through a boundary area per
unit time, dividing equation 2.27 by area, the expression for flux may be found as
= = …………....……… (2.28)
26
The diffusion constant D, is now introduced and defined as
≡ ……………………………... (2.29)
[
Combining equations 2.28 and 2.29 results in
= ……………………..…….. (2.30)
which in partial differential terms is known as Fick’s first law
= …………..……………….. (2.31)
Fick’s first law relates the flux of atoms across a boundary to the concentration gradient and
from Fick’s law, it can be seen that regions with a large concentration gradient diffuse more
rapidly than regions with a small concentration gradient [45].
2.10.4.3 Fick’s second law of diffusion

Fick’s first law allows the diffusive flux as a function of the concentration gradient to be
calculated, Fick’s second law allows the concentration function, C(x), to be calculated as a
function of time.
Since matter is conserved the time change in concentration in slice 2 must be the sum of the
fluxes across the slice 1 to slice 2 boundary and the slice 2 to slice 3 boundary. Which results
in
= ……………………………… (2.32)
and
= ……………………………….. (2.33)
Therefore
= ……………………………….. (2.34)
In differential terms, equation 2.34 is the transport equation
27
= ……………………..……. (2.35)
Substituting Fick’s first law - equation 2.31 into equation 2.35 gives Fick’s second law
= ………………………….. (2.36)
Fick’s second law as derived in the preceding sections is identical in form to the equation for
heat conduction differing only in the constant D, and therefore the large body of work on heat
flow can be applied to the problems of impurity atom diffusion in silicon.
2.10.4.4 Single step diffusion

[
Early in the development of integrated circuit fabrication technology, semiconductor doping

was accomplished by exposing semiconductor substrates to a high concentration of the desired
impurity. In order to maintain good process control, the concentration of the impurity dopant
was maintained at a level in excess of the level required to achieve solid solubility of the dopant
at the semiconductor surface (solid solubility is the maximum doping level that is soluble in
silicon at a given temperature). The high concentration of dopant reduced the process control
requirements to time and temperature. The doping source may be a gas containing the dopant
of interest such as arsine, AsH3, an arsenic source, or a glass layer such as P2O5 as a phosphorus
source. The dopant in these cases may be considered an infinite impurity source in contact with
a semi-infinite medium (the semiconductor substrate thickness is orders of magnitude greater
than the diffusion depth of the dopant for most instances of practical interest).
The surface concentration of the semiconductor will be Cs set by the solid solubility at any
time during the diffusion process and the dopant concentration in the gas CG is > CS. To solve
for the impurity profile in the silicon versus time, Fick's second law equation 2.36, must be
solved for the boundary and initial conditions, where the boundary conditions are given by
= , = 0, > 0……………… (2.37)

and the initial conditions are
= 0, > 0, = 0 ………………....... (2.38)
Figure 2.13 shows the single step diffusion at initial conditions.
28
Figure 2.13: Single step diffusion at initial conditions.
The solution to Fick’s law for single step diffusion that will be derived here will apply Laplace
transforms [46]. There are several alternate methods that can also be utilized to reach the same result.
The Laplace transform for a known function of t, for t > 0, is
̅( ) = ∫ ( ) ………………….………………..…… (2.39)
Laplace transforms of common functions may be constructed by integrating equation 2.39.
Starting with Fick’s law - equation 2.36, multiplying both sides by e-pt and integrating with
respect to t from zero to infinity results in
∫ ∫ = 0……………….……... (2.40)
Assuming that the orders of differentiation and integration can be interchanged (this
can be justified for the functions of interest [42]), then
̅
∫ = ∫ = ………..………….... (2.41)
Integrating by parts
[
∫ =[ ] + ∫ = ̅ ………. (2.42)
Since the term in the square brackets vanishes at t = 0 for the initial conditions, equation 2.38
and at t = infinity through the exponential factor, equation 2.36 reduces to
29
̅
= ̅ ……………………………….……… (2.43)
By treating the boundary conditions equation 2.37 in the same way
̅=∫ = , = 0……………. (2.44)
Thus the Laplace transform reduces from the partial differential equation 2.36 to an ordinary
differential equation 2.43. The solution of equation 2.43 that satisfies equation 2.44 and for
which C bar remains finite as x approaches infinity is
̅= ………………………...............………. (2.45)
where, b2 = p/D. The Laplace transform for equation 2.45 is
( , )= ………………………….…. (2.46)
√
where, erfc is the complementary error function, one of the most important functions in
2
diffusion theory. The total number of impurity atoms Q which enter a 1 cm section of silicon
is defined by
( )≡∫ ( , ) ……………………..……… (2.47)
Integrating equation 2.47 results in
( )= √ ………………………………….….. (2.48)
√
If a single step diffusion as outlined above is used to introduce impurities into silicon as
dopants, equation 2.48 can be utilized to calculate the total number of dopant atoms introduced.
Q will also be used later to calculate profiles resulting from two-step diffusion processes. The
gradient or slope of the impurity profile can be calculated by
⁄
= …………………….……… (2.49)
√
30
Figure 2.14 showns Complementary error function profile evolution versus time [47].
Figure 2.14: Complementary error function profile evolution versus time.
Using the asymptotic approximation for the complementary error function equation 2.50 results
that is valid for most practical situations [47].
( , )……………………………… (2.50)
2.10.4.5 Double step diffusion
Figure 2.15 shows the Pre-deposition and drive-in process of diffusion.
Figure 2.15: Pre-deposition and drive-in process.

31
Following the pre-deposition step the impurity distribution can be determined by solving the
diffusion equation which satisfies the boundary conditions
= 0……………………………………… (2.51)
and
(∞, ) = 0…………………………..……. (2.52)
The solution must also provide for a constant Q to be maintained in the semiconductor. The
initial condition is given by equation 1.27 using the Dt for the pre-deposition step. Solving
equation 1.27 with the boundary condition given by equation 2.51 and equation 2.52 is a
difficult problem. In practice, the Dt from the drive-in step is much greater than the Dt for the
pre- deposition step. A practical approximation is to assume that the total dopant Q is located
in a sheet at the interface.
By differentiation, it may be shown that
⁄
= ………………………… (2.53)
√
is a solution to equation 2.46 where A is an arbitrary constant. Equation 2.53 is symmetric

about x, tends to zero as x approaches infinity positively or negatively for t>0, and at t=0
vanishes everywhere but x=0, where it becomes infinite.
The total amount of impurities Q, diffusing in a cylinder of infinite length and unit
cross section is given by
=∫ ………………………………. (2.54)
If the concentration distribution is given by equation 2.53, then
⁄4 = , = 2√ ……. (2.55)
and
=2 √ ∫ =2 √ ……….. (2.56)
Equation 1.37 shows that amount of impurity diffusing remains a constant and is equal to the
32
amount in the interface sheet at x = 0. Therefore, substituting for A from equation 2.56 into
equation 2.53 results in
( , )= ⁄
……………..……….. (2.57)
√
In the actual pre-deposition - drive-in case being considered the gas-silicon interface truncates
one side of the distribution, (equation 2.54 assumes the distribution is continuous in both
directions). Equation 2.57 becomes
( , )= ⁄
……………………… (2.58)
√
Which is the drive-in concentration following pre-deposition. Equation 2.58is the well-known
gaussian distribution. The top of Figure 2.16 illustrates the progression of the impurity profile
with time as a linear plot and the bottom of Figure 2.16 illustrates a log plot.
Figure 2.16: Gaussian distribution normalized concentration versus distance for successive
times [47].
33
Since Q is fixed, as the impurities diffuse into the silicon the surface concentration Cs must
decrease, this is in contrast to the single step diffusion case where Cs is a constant. From
equation 2.58, the surface concentration may be calculated by
( )= ……………………..…....…. (2.59)
√
Thus the concentration distribution can also be represented by
( , )= ( ) ⁄
………………..….. (2.60)
The gradient of the concentration distribution can be obtained by differentiating equation

2.60 and is given by
= ( , )…………………..……… (2.61)
Figure 2.17 presents some values of the error function and Gaussian function versus z where
= …………………………….…….…. (2.62)
√
Figure 2.17: Gaussian and error function values versus z.
34
2.10.4.6 Diffusivity
In order for an impurity to diffuse through silicon, the impurity must either move around silicon
atoms or displace silicon atoms. During interstitial diffusion, the diffusing atom jumps from
one interstitial position to another interstitial position, with relatively low barrier energy and a
relatively high number of interstitial sites. Substitutional atoms require the presence of a
vacancy or an interstitial to diffuse and must break lattice bonds. Vacancy and interstitial
formation are relatively high-energy processes and so are relatively rare in equilibrium.
Breaking bonds to the lattice is also a relatively high-energy process and substitutional atoms
tend to diffuse at a much lower rate than interstitial atoms.
The diffusion process can be characterized by a barrier with activation energy Ea, where Ea is
the energy required to jump from one site to the next site. The probability of an atom jumping
to another site is given by the product of two terms. The first term is the frequency with
which the atom collides with the barrier v0 (the frequency of atomic oscillation in silicon is
13 14
approximately 10 to 10 per second). The second term is the probability the atom will
surmount the barrier during a collision (given by the Boltzmann factor exp(-Ea/kT)) where k
is Boltzmann’s constant and T is the temperature in degrees Kelvin. The rate at which atoms
jump to a new position is given by
⁄
= ………………..……. (2.63)
[
Each atom can move to any adjacent site, so equation 2.63 should be multiplied by the number
of adjacent sites which is four for silicon for both the interstitial and substitutional case. For the
interstitial case equation 2.63 becomes
⁄
=4 ……..………..... (2.64)
For substitutional atoms an additional term must be added to account for the probability of a
vacancy or interstitial existing in the adjacent site (vacancies for vacancy diffusion and
interstitials for interstitialcy diffusion). If Ed is the energy for point defect formation, the
resulting expression is
( )⁄
=4 ………... (2.65)
35
Experimentally determined activation energies for interstitial atoms are approximately 0.5eV
and for substitutional atoms are approximately 3eV (including defect formation) [48]. It is now
possible to rewrite the diffusion constant equation 2.29 in terms of the physical properties of
the materials. Substituting equation 2.64 into equation 2.29 and taking into account that the
spacing between atoms h is d divided by the square root of 3 for a diamond structure, interstitial
diffusivity is given by
⁄
= …………..…………. (2.66)
Substituting equation 2.65 into equation 2.29 and taking into account account that the spacing
[
between atoms is d divided by the square root of 3 for a diamond structure, interstitial
diffusivity is given by
( )⁄
= …………….…... (2.67)
Equations 2.66 and 2.67 imply that the diffusivity for all interstitial atoms will be the same and
the diffusivity for all substitutional atoms will be the same, this is not the case. Electric fields,
impurity - lattice size mis-match induced strain and multiple diffusion mechanisms complicate
actual diffusivity values.
Ion implantation generates interstitial-vacancy pairs by knocking lattice atoms from their lattice
position, oxidation is a partially complete reaction and injects interstitials into the underlying
silicon, nitridation and silicide formation inject vacancies. Silicon surfaces act as
recombination sites for point defect concentrations so that the proximity of a surface must be
taken into account. Interstitials may also cluster together to form defects which grow and shrink
depending on time, temperature and interstitial concentrations with the result that defects may
act as an interstitial sink or source. Interstitials and vacancies may also recombine in the bulk.
= + (1 ) ………………… (2.68)
where, Deff is the effective diffusivity, D* is the equilibrium diffusivity, fI is the fraction of
diffusion due to an interstitialcy mechanism, CI is the interstitial concentration, C*I is the
equilibrium interstitial concentration, Cv is the vacancy concentration and C*v is the
equilibrium vacancy concentration.
36
Equation 2.68 allows vacancy, interstitialcy or mixed vacancy-interstitialcy diffusivity in the
presence of point defects to be modeled. One of the classic experiments for determining the
effect of interstitials on diffusivity and therefore the interstitialcy component of diffusion is
illustrated in Figure 2.18. The experiment begins with the formation of a uniform doped layer.
A layer of silicon nitride (Si3N4) is then deposited and patterned to leave an opening where
oxidation is to take place - Si3N4 of sufficient thickness can block thermal oxidation. A silicon
dioxide (SiO2) layer is then grown in the Si3N4 opening. Oxidation is usually incomplete and
approximately 1 in every 1,000 silicon atoms are unreacted. The unreacted silicon atoms break
free of the interface and become silicon self-interstitials. The concentration of silicon self-
interstitials is higher under the center region where oxidation is occurring and if interstitials
increase the diffusivity of the dopant being measured then the dopant will diffuse deeper under
the center section. Conversely, if interstitials retard diffusion, for example, if interstitials
recombine with vacancies limiting the vacancy supply for vacancy diffusion, the dopant will
diffuse to a shallower depth under the center section.
Figure 2.18: Experiment to measure oxidation enhanced diffusion.
It is important to note here that the oxidation reaction is consuming silicon in the center section.
Without diffusivity enhancement, the distance between the SiO2-Si interface and diffusion
boundary under the center section would be smaller than the distance between the Si3N4-Si
37
interface and the diffusion boundary out at either side. Many researchers have investigated the
mechanisms of diffusion. Recently Grossman [49] has pointed out that experimental
measurements of the interstitialcy component of diffusion for a single species require the
solution to a single equation, equation 2.68 with three unknowns, the percent of interstitialcy
diffusion and the ratios of interstitial and vacancy concentrations to equilibrium. If however,
two different diffusing species are measured under identical conditions a system of two
equation in two unknowns can be formulated and solved without resulting to assumptions about
the vacancy and interstitial ratios. Grossman has performed this experiment for boron and
antimony and found
(860℃) ≥ 0.98 0.01…………….…… (2.69)
and
(790℃) ≤ 0.01 0.01………………..… (2.79)
Or in other words, B diffuses through an almost exclusively interstitialcy mechanism and Sb

diffuses through an almost exclusively vacancy mechanism. Grossman further suggests that
any substitutional dopant in silicon should diffuse through either a pure vacancy or a pure
interstitialcy mechanism.
A complete diffusion model needs to account for point defect interactions with the diffusing
species and also formations of defect clusters. For example, a complete set of interactions for
boron would need to account for the following eight interactions [50]:
A neutral interstitial interacts with a cluster to either grow or shrink the cluster
+ ↔ 0………………………………….. (2.80)
An interstitial and vacancy either annihilate each other or are generated as a Frenkel pair
+ ↔ 0……………………………….…. (2.81)
An interstitial and a hole interact to create a positively charged interstitial from a neutral
interstitial or a positively charged interstitial releases a hole and becomes neutral.
+ ↔ ………………………………… (2.82)
A negatively charged boron atom combines with a neutral interstitial to form a neutral boron
38
interstitial pair and release an electron or a neutral boron - interstitial pair captures an electron
and breaks up into a negatively charged boron atom and a neutral interstitial.
+ ↔ + ………………………… (2.83)
A negatively charged boron atom combines with a neutral interstitial and a hole to form a
neutral boron-interstitial pair or a natural boron-interstitial pair releases a hole and breaks up
into a negatively charged boron atom and a neutral interstitial.
+ + ↔ …………….……... (2.84)
A neutral boron - interstitial pair combine with a vacancy annihilating the vacancy - interstitial
pair and releasing a negatively charged boron atom and a hole or a hole and a negatively
charged boron atom combine and generate a neutral boron - interstitial pair and release a
vacancy.
+ ↔ + ………………..….….. (2.85)
A positively charged boron - interstitial pair combine with a vacancy annihilating the vacancy
interstitial pair and releasing a negatively charged boron atom and two holes or two holes and
a negatively charged boron atom combine and generate a positively charged boron interstitial
pair and release a vacancy.
+ ↔ +2 ………………….…. (2.86)
A negatively charged boron atom and a positively charged boron - interstitial pair combine to
form a neutral boron cluster or a neutral boron cluster breaks apart into a negatively charged
boron atom and a positively charged boron - interstitial pair.
+ ↔ ………………………….... (2.87)
The equation set can be implemented through a set of reaction diffusion equations of the form
[48]:
= . + + + …. (2.88)
This system of equation contains a large number of parameters that must be known in order to
39
evaluate the model predictions. Recently general purpose differential equation solvers have
become available which allows systems like this to be evaluated. The intrinsic model is given
by
= + + + + for n or p≪ ……(2.89)
0 +
where: Di is the intrinsic diffusivity, D is the neutral vacancy - impurity diffusion, D is the
positively charged vacancy - impurity diffusion, D- is the negatively charged vacancy -

=
impurity diffusion and D is the doubly negatively charged vacancy - impurity diffusivity and
ni is the intrinsic carrier concentration. For extrinsic silicon,
= + + + + for n or p ≫ …………(2. 90)
where, Dx is the extrinsic diffusivity. For specific impurities not all vacancy charge state
impurity combinations will participate in the diffusivity.
2.10.4.7 Phosphorous diffusion
Phosphorous (P) diffusion is currently the primary method for emitter fabrication in silicon (Si)
solar cell processing [51]. The thermal diffusion of phosphorus is necessary to create an n-type
emitter to the p-type wafer [52]. The diffusion depends on various factors of which temperature
and gaseous environment are most important [53]. P-type silicon wafers are widely used in
solar industries and therefore diffusion technologies have been developed to deposit n-type
doping elements to create the p-n junction. Along with nitrogen (N2) and oxygen (O2) gases,
phosphorus oxychloride (POCl3), a liquid source of phosphorus is also widely used in the
standard diffusion process of solar cells [54-55]. Due to its low boiling temperature (105.8 ˚C)
[56], at temperatures between 850-900˚C in the diffusion chamber, POCl3 is decomposed into
simple phosphorus compounds like P4, P8, P2O5, etc. In oxygen environment and at 850°C
temperature, the diffusion coefficient (D) can be approximated as D~0.0013μm2/hr.
The phosphorus diffusion fabrication of crystalline silicon solar cell with emitter diffusion,
surface passivation and screen printing of electrode leads to the formation of n+ type emitter
at the top surface of the wafer. Phosphorus oxychloride (POCl3) is a liquid source which
vaporizes at room temperature itself hence it should be kept in cool place. For the diffusion
40
process, the vapors are carried out by the carrier nitrogen and oxygen is passed through another
valve. The reaction takes place, the phosphorus oxychloride reacts with oxygen forms
phosphorus pentoxide and then the phosphorus pentoxide reacts with the silicon to give the
silicon dioxide and the phosphorus. Generally, the phosphorous diffusion process is performed
in two steps. The first step is called predisposition that involves the formation of phosphorous-
rich oxide films on the silicon substrate. The second step is called drive-in [56-59] which the
phosphorous-rich oxide film acts as an infinite source for phosphorous diffusion into the Si
substrate. During pre-deposition, phosphorus pentoxide (P2O5) forms on the surface of the
wafers by the reaction of phosphorous with oxygen.
The P2O5 immediately reacts with the silicon, by resulting in diffusion of phosphorus and
formation of the phosphosilicate glass (PSG) [SiO2: (P2O5) x] layer on the Si surface [60]. The
phosphorus atoms formed at the PSG-Si interface penetrate through the silicon wafer [61] and
can be simplified with the following reaction equations:
POCl3 (liquid) + N2 (bubble) → POCl3 (vapor) (pre-deposition)....... (2.91)

4POCl3 + 3O2 →2P2O5 + 6Cl2............................................................ (2.92)
2P2O5 + 5Si →4P + SiO2 (drive-in)................................................... (2.93)
P + 3Si → n-type doped Si................................................................. (2.94)
The POCl3 gas distribution system located at the furnace backside. It is made out of Teflon
materials which protect the distribution system from chemical attack. The glass flask is filled
with POCl3 liquids which act as a source of phosphorus diffusion. For more details, the
schematic diagram of the POCl3 gas distribution system is shown in Figure 2.19. As described
in the diagram, phosphorous trichloride (POCl3) in vapour form is carried out by the carrier
nitrogen and oxygen gases through appropriate valves to the diffusion tube. The diffusion
process takes place inside the quartz tube.
41
Figure 2.19: Schematic diagram of the gas distribution system of POCl3 furnace.
2.10.5 Front and back surface metallization (Screen Printing)
Metallization creates electrodes on p-type and n-type layers of the cell. Different metallization
methods and materials are applicable for the c-Si solar cell fabrication. The most used
technology in the industry is screen printing. Screen-printing (SP) is cost-effective, robust,
simple, inexpensive and fast method of metallization of the solar cells [62-63]. This technique
has been widely used for solar cell fabrication since the early 1970s. A screen consists of a
mesh made of stainless steel and coated wiht an emulsion. The technology is based on the use
of thick metal pastes deposited by applying a squeegee force which allows that the pastes flow
through the openings of the screen. The pastes contain an organic binder and a solvent, glass
frit, silver (Ag particles) to contact n-type material and aluminum (Al particles) to contact p-
type material. The paste components need to ensure both: a necessary low viscosity to print
over the wafer surface and a higher viscosity after the printing step. Following diffusion, screen
printed metallic contacts are formed to form electrical contacts to n and p doped regions. A
thick and viscous metal solution or paste is forced through stainless screen grid onto the wafer
in selected lithographically defined open regions in the screen. The metal lines on the front
surface (n-type) are made of silver and on the back surface (p-type) are made of aluminum.
Aluminum contact on the wafer backside also serves to form a heavily diffused p++ layer that
reduces contact resistance and enhances back surface reflectance. Appropriately-designed
screens are used for this process and screen printers are used to form Ag and Al contacts to
42
front and back solar cell surfaces. The printing process begins as a silicon wafer is placed onto
the printing table. A very fine-mesh print screen mount within a frame is placed over the wader;
the screen blocks off certain areas and leaves other areas open where the paste can go through.
Screens used for front side printing typically have a much finer mesh size than do backside
screens due to the finer metal lines required on the front side. After a measured amount of paste
is dispensed onto the screen, a squeegee distributes the paste over the screen to uniformly fill
the screen openings. As the squeegee moves across the screen, it pushes the paste through the
screen openings and onto the wafer surface. This process must be tightly controlled for
temperature, pressure, speed, and many other variables. After each printing step, the wafer goes
to a drying furnace to solidify the paste. Each solar cell has conductive lines on both front and
back sides that are printed using screen masks and which have different functions.
2.10.6 Drying
After screen printing, the silicon wafers are required to go through drying at relatively low
temperature (around 120°C) for certain period. The wafers are placed in a preheated oven at
120- 200°C for 10 minutes after each time of edge isolation, back and front side printing so
that the paste gets attached well to the wafer surface.
2.10.7 Rapid Thermal Annealing (RTA)
Following screen printing, high-temperature process is used to cure the solar cells contacts in
order to form ohmic contacts. The rapid thermal annealing furnace is used to cure or fire screen
printed contacts on silicon solar cells. In order to establish an ohmic contact (low resistive
contacts), contact firing is recommended in silicon solar cell processing. Conventionally, any
RTA process is capable to do the process. In this case, a belt conveyer system integrated RTA
processing unit is used for a continuous processing of contact firing. A conveyor belt furnace
capable of reaching 1000 °C temperature is used for this step. Rapid thermal annealing furnace
uses infrared heating.
In the furnace, radiant heating from IR (Infrared) lamps provides heat directly to objects
without first heating the surrounding air. IR waves excite molecules within a substance
(product) thus generating heat but pass generally undisturbed through the surrounding
atmosphere. Other substances such as glass, ceramics and some organic materials are also
transparent to IR waves. Objects suspended in these media can, therefore, be heated directly
43
by IR waves without directly heating the supporting media. Not all heating in the furnaces
occurs via direct IR radiation. The belt and air inside the furnace are heated via the IR lamps.
The amount of direct heating via IR radiation is determined by three factors: (1) The level of
IR radiation emitted from the heat lamps (2) The amount of IR absorbed by a product (3) The
level of edge heat introduced into the furnace. The heating chamber technology allows for rapid
heat-up and cool-down times. Radiant heating allows for rapid startups and profile changes and
system stabilization. The heating chambers consist of an outer metallic shell fabricated from
either aluminum or stainless steel, lined with a refractory-ceramic-fiber (RCF) insulation.
Controlled atmosphere heated sections allow process gas to pass through the RCF insulation.
The wafers are passed through a moving belt which goes inside the RTA machine. Rapid
Thermal Annealing is important because it provides proper contact between the conductor and
the semiconductor. After RTA fabrication of solar cell is completed.
2.11 Metal – semiconductor contacts
The metal-semiconductor contact has been a topic of research for more than 100 years and goes
back to the early work of Braun (1874), who discovered the asymmetric nature of electrical
conduction between metal contacts and semiconductors [64]. This phenomenon was explained
decades later by Schottky, who introduced a kind of barrier height which is formed as soon as
a metal and a semiconductor are in a close contact [65-66]. In honor of his work, metal-
semiconductor contacts are often called Schottky-contacts and the bending in the band diagram
the Schottky-barrier. In the 1950s and 1960s, the research into ms-contacts was driven by their
technical importance in semiconductor technology and later microelectronics. The theoretical
understanding of ms-contacts was further increased by the work of Bardeen, Crowell, and Sze
[67-70]. A summary of the physics of metal-semiconductor contacts is given by Rhoderick and
Williams [71].
For solar cell applications, the ms-contact plays an important role: the metallic contact should
be as small as possible and the voltage drop over the barrier should be negligible compared to
the voltage drop over the total device. The contact should not degrade device performance to
any significant extent, it should not inject minority carriers into the device and the contacts
should be made in a reproducible manner. A summary of the contact requirements and a review
of the contact theory, especially for contacts on solar cells, is given by Schroder and Meier
[72]. Figure 2.20 shows the energy band diagram of a ms-contact on an n-type semiconductor
before and after an intimate contact is formed.
44
Figure 2.20: Energy band diagram of a ms-contact on a n-type semiconductor before and
after an intimate contact is formed.
2.11.1 Schottky contacts and barrier height
If a metal and a semiconductor are in direct contact a constant electrochemical potential is

formed within both materials; in steady-state conditions the Fermi energies in both materials
are at the same level, thus the conduction band and valence band of the semiconductor
are bended to balance in the difference between the metal work function and the semiconductor
electron affinity. The formed Schottky barrier can be described as the difference in metal
work function and semiconductors electron affinity ,
, = - , n-type , = -( ), p-type……………. (2.95)
where q is the potential necessary to excite an electron from the Fermi level to the vacuum
level, and is the potential defined by the difference between the conduction band and
vacuum level. For a metal-semiconductor junction, the different combinations are possible.
Figure 2.21 shows the contact barriers for semiconductor of different types and work functions.
The metal can be in contact with an n-type or a p-type semiconductor, where the metal work
function is either larger or smaller than the electron affinity. Therefore two kinds of contacts
can be distinguished, a rectifying contact shown as Figure. 2.21a) and d) and an ohmic contact
shown as Figure 2.21b) and c). The difference is visible in the IV-characteristic, which is linear
for ohmic contacts, where the current can flow in either direction with a negligible small
45
voltage drop, and nonlinear for rectifying contacts, where the current can flow easily only in
one direction.
For the contact to an n-type semiconductor as shown in Figure. 2.21b), where is greater than
the electron can flow from the semiconductor into the metal without any barrier and
becomes zero or negative. A negative or neutral barrier can also be formed on p-type silicon
when is larger than . In general, as long as the majority charge carriers are accumulated
at the contacts, the contact obtains an ohmic behavior. However, Fig. 2.21b) and c) are very
uncommon in practice, and the majority of metal-semiconductor contacts are of rectifying
nature and the IV-characteristic is not linear. In fact, for a real contact the direct proportionality
between the potential barrier and metal work function, and for n-type silicon, could never be
measured. Even if a relation between barrier height and metal work function was found
experimentally, it was less strong than expected. The influence of the metal work function
seems to be less important. Surface states at the interface layer, acting as donors or receptors,
play an important role for contact formation as first proposed by Bardeen [68]. It is also
assumed by Tove that the formation of a dipole determines the measured barrier height [71,
73-74]. Similar results are found by Cowly and Sze where the role of the dipole is played by
an insulating interface layer [69]. With common metals, an ohmic contact to n-type emitters
seems not to be possible, as common metals like Al, Ag, Au, Pt or Ni form rather high barriers
(0.6-0.9 eV). Even if the height of the Schottky barrier is reduced due to image force lowering,
which should be less than 0.2 eV for ND <1020 cm-3, relatively high (> 0.5 eV) barriers exist on
heavily doped silicon. Therefore, these contacts are ohmic in a different way. A current flow is
possible, and according to the definition of an ohmic contact given by Meier and Schroder,
“the contact should supply any current that the device requires in its normal mode of operation”,
therefore rectifying contacts can appear ohmic.
46
Figure 2.21: Contact barriers for semiconductor of different types and work functions.
2.11.2 Current transport mechanism and contact resistance of a Schottky barrier
For the transport of charge carriers in the metal-semiconductor junction, three mechanisms can
be distinguished: (i) the thermionic emission (TE), which describes the thermal activation of
charge carriers over the barrier and is valid for low doping concentrations ND <1×1017 cm-3, (ii)
the field emission (FE), which describes the tunnelling of charge carriers through the barrier
and is valid for high doping concentrations ND >1×1020 cm-³, and (iii) the thermionic field
emission (TFE), which is a combination of both and is valid for doping concentrations in
between [70, 75-76]. For silicon solar cells in general, with typical emitter doping
concentrations of 1×1018cm-3 <ND <5 ×1021 cm-³, the dominant transport mechanism for the
charge carriers are the TFE and the FE; for industrially fabricated solar cells in particular, where
the surface doping concentration is generally far above 1x1020 cm-3, the dominant mechanism
is the tunnelling process (FE). Both theories predict mainly a dependence on the doping
concentration (ND) and the barrier height ( ) of the metal-silicon or silicide-silicon junction.
The higher the doping concentration and the lower the barrier height, the better the electrical
contact. A simulation of the contact resistance as a function of ND corresponding to different
theories for silver as a contact metal with a barrier height of 0.78 eV [70] is shown in Figure.
2.22.
47
Figure 2.22: Current flow mechanism in a metal semiconductor junction – a) thermionic
emission, b) thermionic field emission, c) field emission.
For the different current transport mechanisms a current density, dependent on the applied
voltage and the barrier height, can be given and the specific contact resistance can be
subsequently calculated [76]. In all given equations the lowering in the barrier height due to
image forces is considered.
= …………………………………………... (2.96)
→
2.11.2.1 Thermionic emission (TE)
The current transport in a ms-contact on a lowly doped silicon with moderate barrier height is
dominated by the thermionic emission, which means the thermal activation of the charge
carriers over the barrier and only electrons from the n-type emitter with energy larger than the
barrier can contribute to the current transport. If the Schottky barrier is too high, the contact
changes its behavior from ohmic to rectifying. The current density can be given by [70]:
( )
= exp 1 …………….. (2.97)
With A*≈ (m*/ )·120 Am-2K-2 being the effective Richardson constant, m* the effective
electron mass and m0 the free electron mass.
Using Equation 2.96 the resistivity can then be calculated as:
( )
( )= exp ………………………..…….. (2.98)
48
2.11.2.2 Thermionic field emission (TFE)
When the doping concentration is high, the depletion region width becomes smaller. Therefore,
electrons can tunnel through the barrier, in addition to the thermionic emission process.
Electrons with sufficient energy are activated over the barrier and electrons with less thermal
energy are then able to tunnel through the thinner barrier. The TFE, therefore, is a combination
of the field emission and the thermionic emission [76-78] and the current density can be
expressed as:
( )
= exp ћ
1 ………… (2.99)
And the specific contact resistance is:
( )
(TFE)= exp ……………………………………..… (2.100)
With
= ( )
exp ………………….… (2.101)
and the characteristic energy :
ћ
= ……………………………………………..…… (2.102)
E00 represents a characteristic energy which is related to the tunnelling probability and depends
on the doping concentration. The increase in E00 with ND reflects the barrier becoming thinner
at higher doping levels, leading to increased carrier tunnelling.
2.11.2.3 Field emission (FE)
The tunnelling of charge carriers through the barrier is described by the field emission, which
is the case either for very high doping concentrations or very low temperatures. The tunnelling
49
is now possible without any thermal activation, as the barrier is thin enough and the current
can be given by:
∝ exp 1 …………..(2.103)
( )
and the resistivity for the field emission is equal to
( )
(FE) = exp …………………..…………. (2.104)
With
= exp …….….….. (2.105)
The ratio kT/ , used in C1 and C2, is a measure of the relative importance of the thermionic
process in relation to the tunnelling process [76]:
- For kT/E00 >> 1 the thermionic emission (TE) dominates the current transport on a barrier
(ND < 1017 cm-3)
- For highly doped semiconductors or very low temperatures, kT/E00 << 1 the current transport
can be described by the field emission (FE), which is the main transport mechanism (for ND ≥
1020 cm-3).
- In the case that the thermionic and tunnelling processes are comparable, kT/E00 ≈ 1 the current
transport on a Schottky barrier is described by the thermionic field emission (TFE) (1017 cm-
3<N <1020 cm-3).
D
50
Figure 2.23: Simulation of the theoretical resistivity ρc as a function of doping concentration
(ND) for silver as a contact metal.
The areas for the different current transport mechanism are marked and the region for contact
resistivities for printed and fired contacts on silicon solar cells is illustrated. The contact
resistivities for all three current transport mechanisms are summarized as a function of doping
concentration in Figure 2.23. All are dependent on ND and the different areas where they are
valid are marked. The resistivity is strongly reduced for higher doping concentrations (ND >1018
cm-3), which is the doping level of n-type silicon emitters. As the resistivity of industrially
produced silver contacts – printed and fired, is reduced due to a reduced contact area, the doping
level has to be very high (ND >1020 cm-3) to guarantee an ohmic contact behavior. In general,
the experimentally determined values for the resistivity fit very well to the theory. In Figure
2.6 ρc is plotted over ND for Al-n-Si contacts, measured at RT additionally to the theoretically
expected values for =0.7 eV and =0.6 eV [76].
51
Figure 2.24: Resistivity as a function of the doping concentration for different barrier heights
(left) and in combination with experimentally determined values for Al contacts on n-doped
silicon (right) [76].
The influence of the barrier height on the resistivity is shown in Fig. 2.6. Here ρc is plotted as
a function of ND for different barrier heights. For common materials, the barrier height varies
from 0.5 eV <ϕB < 0.8 eV. The reported barrier heights are widely scattered e.g. for Ni between
0.55 eV and 0.74 eV, depending on the experiment. Half of the data are around 0.6 eV,
therefore, the given values are average values [79]. The results for silver vary between 0.62 eV
and 0.78 eV and are only slightly higher than for nickel. The contact formation using metals
which form silicides is supposed to be preferred. However, the difference in barrier height
between metal-silicon or silicide-silicon contacts is negligible; sometimes higher, sometimes
lower and rarely exceeding 0.05 eV [73, 79]. The formation of silicide has therefore only a
minor impact on the electrical contact parameter. The advantage of silicide is more a
mechanical aspect, as the metal, if it forms a silicide, is chemically connected with the
semiconductor and the adhesion is increased. That is also the reason why silver contacts
evaporated on silicon do not adhere, as silver does not form silicides in this case. Additionally,
it should be mentioned that the barrier height on p-type silicon is, in general, lower than on n-
type. Table 2.1 shows the barrier heights for selected metals which are used for the
metallization of semiconductors. Metals, commonly used for the metallization of silicon solar
cells are highlighted [79].
52
Table 2.1: Barrier heights for selected metals which are used for the metallization of
semiconductors [79].
2.11.3 Recombination of charge carriers in Solar Cells

]
The recombination process of charge carriers is defined as the reverse process of their
generation. The thermal-equilibrium condition of a semiconductor (in the dark) can be
disturbed by illuminating the device, increasing the charge carrier concentration by generation
of electron-hole pairs [80]. After generation, the carriers tend to return to their original state of
equilibrium through the event of recombination. Thus, the two mechanisms to disturb the
equilibrium-condition are [81]: the recombination process of the electron-hole pairs
(undesirable) and the thermal generation through photon illumination (required). Both
mechanisms must fulfill the principle of conservation of energy. In solar cells, the
recombination leads to an undesirable reduction of solar cell efficiency due to the losses of
generated carriers. The generation increases by optimizing the absorption of photons from the
incident light on the solar cell device. The event of generation is the most important process in
a solar cell, for converting the incident sunlight into electrical energy. In semiconductors, there
are three fundamental recombination possibilities [80, 82] which are the band-to-band radiative
recombination, the band-to-band Auger recombination (non-phononic mechanism), and the
recombination through defect levels or traps (phononic mechanism). The last two events
dominate in Si solar cells.
2.11.3.1 Band-to-band Radiative Recombination
The radiative recombination is the reverse of the absorption and occurs when an electron jump
from the conduction band, EC, into the valence band, EV, and this event is, therefore, faster in a
direct-bandgap (Eg ) semiconductors than in an indirect one. Direct-bandgap semiconductors
(as GaAs) have the minimum of EC and the maximum of EV at the same wave vector, k [83].
An electron with the necessary energy to jump from the valence band into the conduction band
becomes free to move in the crystal. By the transition of the electron to the conduction band, a
53
hole is created, which is as well free to move in the valence band [83]. An electron, however,
can also lose energy and fall back into the valence band, recombining with a free hole [83].
The energy by this recombination event is released in the form of a photon. Hence, this is a 3-
particle process [80]. Their energy is near to the visible range and therefore this process is
exploited in devices such as light-emitting diodes (LEDs). Due to the indirect bandgap in most
group IV-semiconductors (Si, Ge), the radiative recombination is unlikely to occur and is
normally negligible.
2.11.3.2 Auger Recombination

The Auger recombination is defined as band-to-band recombination. In the band-to-band
Auger process, an electron at EC falls back to the EV by transferring its original energy to an
electron in EC, which is excited to a higher level in the Brillouin zone. The separation of the
wave vector, k, in indirect-semiconductors assist the occurrence of an Auger event with
minimal activation energy. The Auger mechanism dominates the recombination in heavily
doped silicon or when silicon is in high-injection levels [84]. The Auger recombination is the
direct recombination between an electron and a hole and, in solar cells, occurs when holes are
injected into the heavily doped n+-region (emitter) [81]. Efficiency is affected by the minority
carrier lifetime in the heavily doped regions [82]. Good quality bulk materials are
predominantly affected by Auger recombination [82, 85]. Furthermore, the quantum efficiency
and the emitter saturation current of highly doped emitter layers are affected at low injection
conditions [86]. This recombination process is quantified via the Auger coefficients [87].
2.11.3.3 Recombination through Defect Levels, Shockley-Read-Hall
Impurities, incorporated in the bulk material during crystal growth, doping, processing, and so
forth, can act as recombination centers located within the band gap [83]. The resulting
Shockley-Read-Hall (SRH) [88, 89] recombination process is the predominant recombination
process in Si bulk devices [84]. Electrons within non-pure materials and in transition between
bands are affected by the energy states created within the band gap (impurity in the lattice).
Recombination in semiconductors is shown in Figure 2.25.
54
Figure 2.25: Recombination in semiconductors [90].
2.12 Contact resistance
Contact resistance refers to the resistance associated with the metal-semiconductor barrier at
the interface between the semiconductor and the metal contact [91]. In a solar cell, for example,
current traveling laterally in the emitter toward a grid line must pass through this interface
before traveling in the contact grid. The magnitude of this contact resistance depends on the
semiconductor material (silicon, gallium arsenide) and dopant type (p or n), and on the contact
material (titanium, silver, nickel silicide), but it depends most strongly on the doping
concentration near the semiconductor surface. A metal-semiconductor junction results in an
Ohmic contact (i.e. a contact with voltage independent resistance) if the Schottky barrier
height, fB, is zero or negative. In such case, the carriers are free to flow in or out of the
semiconductor so that there is a minimal resistance across the contact. For an n-type
semiconductor, this means that the work function of the metal must be close to or smaller than
the electron affinity of the semiconductor. For a p-type semiconductor, it requires that the work
function of the metal must be close to or larger than the sum of the electron affinity and the
band gap energy. In transistors and other electronic devices, the contacts are a necessary part
of the device, and it is useful to determine the contact resistance so that we can have some idea
of how it might affect device performance [92].
55
2.13 Transmission Line Method (TLM) measurement system
Transmission Line Method (TLM) is used in semiconductor physics and engineering to

determine the contact resistance between a metal and a semiconductor. The technique involves
making a series of metal-semiconductor contacts separated by various distances [93]. This
model gains its name from transmission lines that are used in power transmission [94]. A
typical arrangement for a TLM test pattern is shown in Figure 2.26. There is a single rectangular
region (blue in the figure) that has the same doping (i.e. same sheet resistance) as the contact
areas of the devices. An array of contacts (darker gray in the figure), with various spacings, is
formed over the doped region [95].
Figure 2.26: A typical arrangement for a TLM test pattern.
The measured total resistance consists of several components:

=2 +2 + ……………………….. (2.106)
Where the resistance due to the contact metal, is is the contact resistance associated with
the metal/semiconductor interface, and is the usual semiconductor resistance. The
resistance of a single contact would be + . However, in most situations, the resistivity
of the metal in the contact is so low that >> , and so can be ignored.
The semiconductor resistance is
= ……………………………………….. (2.107)
So equation 2.105 becomes
= +2 …………………………………. (2.108)
56
If resistors of several different lengths are constructed, keeping all other details the same, the
total resistances of each can measured and plotted as shown in Figure 2.27.
Figure 2.27: TLM-measurement, where the measured resistance RTLM is plotted as a function
of the spacings between the contact pads.
In the limit of a zero-length resistor, the residual resistance would be just twice the contact
resistance. The can be found from the graph by extrapolating back to L = 0.
Now equation 2.107 becomes,
=2 ……………………. (2.108)
Finally we get the contact resistance
= …………………….… (2.109)
2.14 Conclusion
The efficiency of the solar cell can be impacted by various means. One of the major factors
that affect the performance of the solar cell, is the resistance between the metal and
semiconductor i.e. contact resistance.
57
Chapter 3: Experimental Procedure
3.1 Introduction
Fabrication of silicon solar cell from the silicon wafer is a tedious process which requires good
handling of wafers preventing them from contamination. Hence clean environment has to be
ensured and the entire process is carried out in a clean room, proper laboratory safety rules and
regulation like wearing proper suites, gloves, head cover, mask, safety goggles and other safety
issues has to be maintained to ensure proper safety. In this research, monocrystalline silicon
solar cells are fabricated by varying diffusion time i.e. doping concentration. Then the contact
resistances of both sides of solar cells are determined by using Transmission Line Method
(TLM) measurement system. Fabrication and investigation of contact resistance of the solar
cell are done at Solar Cell Fabrication and Research Division (SFRD) of Bangladesh Atomic
Energy Commission (BAEC).

Monocrystalline silicon solar cell fabrication deals with a set of basic materials, chemicals,
components, equipment, and types of machinery. The basic materials used for solar cell
fabrication are P-type monocrystalline silicon wafers which are collected from abroad.
Fabrication of crystalline silicon solar cell starts with square shape of 127×127 mm2 in size
and 200 μm in thickness, (100) oriented Czochralski Si (or Cz-Si) wafer. Fabrication of
monocrystalline silicon solar cell from wafer requires several numbers of process steps to get
the final solar cell output. Figure 3.1 shows the sequence of the solar cell fabrication process
steps and Figure 3.2 shows the starting p-type monocrystalline silicon wafers for solar cell
fabrication used in this experiment. Each step of solar cell fabrication is described.
58
Cleaning and Texturing of wafer
SEM analysis of textured wafer
Surface Reflection Measurement
Phosphorous Diffusion
Front Surface Metallization (TLM pattern)
Back Surface Metallization (TLM pattern)
Drying
Rapid Thermal Annealing
Figure 3.1: Sequence of the solar cell fabrication process steps.
59
Figure 3.2: Starting p-type monocrystalline silicon wafer.
3.2.1 Cleaning and texturing of wafer
Cleaning and texturing of the raw wafer is done for the removal of saw damage results from
the wire sawing process, organic contaminants, thin oxide layer and metal particles from the
surface of the wafer and for the formation of random, sub-wavelength pyramid features on the
wafer surface to reduce reflection and enhance light absorption. This cleaning and texturing
process of monocrystalline silicon wafers is done in the wet-chemical bench which is shown
in Figure 3.3. DI (De-ionized) water supplied to the wet-chemical bench by DI water plant is
shown in Figure 3.4.
Figure 3.3: Wet-chemical bench.
60
Figure 3.4: DI-water plant.
In this research, six sample wafers are taken for the cleaning and texturing purpose and each
sample contains more than one wafer. Cleaning and texturing of samples is done by three steps
which are described here.
Step 1: Saw damage removal process
In saw damage removal process, at first, a tray containing the wafers is washed using DI water.
A beaker is properly cleaned using detergent and DI water. 6.5 liters DI water is taken in this
cleaned beaker and then the beaker is placed on the heating system in the wet chemical bench.
When the temperature of water reached 35° C, 650 grams of sodium hydroxide (NaOH) pellet
is added to make 10 % NaOH solution in the beaker. Then the tray containing raw wafers is
transferred to that beaker and dipped in that solution for 10 minutes. After 10 minutes the tray
containing wafers is removed from the beaker and dipped in DI water for 1 minute. Now the
wafers are ready for the next step.
Step 2: Hydrophobic process
The hydrophobic process is done to remove the native oxide from the wafers. In this process a
solution of the ratio of HF (Hydrofluoric Acid): H2O (DI-water) = 1ml: 50ml is prepared in a
beaker. The wafers are dipped into this HF solution for 30 seconds and then they are removed
from the HF solution and dipped for 1 minute in DI-water.
61
Step 3: Texturing process
A solution of the ratio of KOH: IPA: H2O (DI-water) = 1 gram: 5 ml: 125 ml is prepared for
the texturing process. Initially, the beaker is washed with DI-water and then 6 liters of DI-water
containing beaker is placed on an electronic heater. Then 48 gram of potassium hydroxide
(KOH) pellet is added to the beaker. When the temperature of the beaker is reached 70° C, the
boat containing the wafers is placed into the beaker and then 240 ml of Isopropyl Alcohol (IPA)
is added to the beaker. The wafers are kept in that solution for 10 minutes. After that, the tray
containing wafers is removed from the beaker and then dipped for 1 minute in DI-water. Then
the hydrophobic process is repeated and finally, the wafers are dried using the compressed air
and that concludes the texturing process. Figure 3.5 shows the drying of the textured wafer
using compressed air.
Figure 3.5: Drying of textured wafer using compressed air.
62
The morphological analysis of the textured wafer is studied by using a Field Emission Scanning
Electron Microscope (FESEM), model: JSM-7600F.SEM analysis is done in glass and
ceramics Engineering department of BUET.
3.2.3 Surface Reflection Measurement (SRM)
Surface reflection measurement system is used to measure the reflectance of wafers surface.
Figure 3.6 shows the detailed system schematic of the surface reflection measurement system.
Figures 3.7-3.9 show the pictures of the complete system. Light from a tungsten-halogen lamp
is focused onto the entrance slit of the monochromator using a condenser lens (Figures 3.6 and
3.7). The output from the monochromator is directed to the wafer with a simple folding mirror
(Figure 3.8). A large convex lens close to the surface is used to collect reflected and scattered
light and focus onto a Si photodiode is shown in Figure 3.7 (b). The zero order (white light)
and red light from the monochromator is shown in Figure 3.8. Figure 3.9 (a) shows a working
system inside a cabinet for the protection against external light. Reflected light from Si wafer
focused onto the photodetector is shown in Figure 3.9 (b). The signal from the photodetector
is connected to lock-in amplifier for measurement through the LabVIEW interface.
Figure 3.6: Schematic diagram of the surface reflection measurement system.
63
Figure 3.7: The surface reflection measurement system showing (a) folding mirror for
directing light at near normal incidence to the wafer and (b) large convex lens to collect
reflected and scattered light.
Figure 3.8: The output from the monochromator with (a) zero order and (b) red color.
64
Figure 3.9: Working SRM system (a) inside a cabinet to block external light and (b) focused
light spot reflected from Si surface on the detector plane.
In this experiment, all of these six samples are cleaned and textured by using the same process.
Therefore only one textured wafer is taken to measure the surface reflectance of the wafer. This
measurement is done by using surface reflectance measurement (SRM) system. Surface
reflectance data is given in APPENDIX A.
3.2.4 Phosphorous diffusion

[
The cleaned and textured wafers are subjected to phosphorous diffusion to form p-n junctions.
Generally, the phosphorous diffusion process is performed in two steps. The first step is called
pre-deposition that involves the formation of phosphorous-rich oxide films on the silicon
substrate. The second step is called drive-in which the phosphorous-rich oxide film acts as an
infinite source for phosphorous diffusion into the Si substrate. During pre-deposition,
phosphorus pentoxide (P2O5) forms on the surface of the wafers by the reaction of phosphorous
with oxygen. In this experiment, six samples of wafer, indicated as sample 1, sample 2, sample
3, sample 4, sample 5, and sample 6 are diffused by varying diffusion time. At first, the POCl3
(Phosphorus oxychloride) diffusion furnace is turned on and the centre zone temperature is set
to 600° C. Once the temperature reached to 600°C, sample 1 is transferred to the diffusion
65
chamber. After keeping this sample inside, the container mouth of the furnace is closed
properly. Nitrogen gas supply is turned on for 10 minutes and then increases the temperature
at the furnace to 875° C. At 875° C, nitrogen gas supply is turned off and oxygen and POCl3
supply are turned on simultaneously. After 5 minutes, oxygen and POCl3 gas supply are turned
off simultaneously and then nitrogen gas supply is again turned on. After 10 minutes, nitrogen
gas supply is turned off and only oxygen gas supply is turned on for the next 10 minutes. After
that oxygen gas supply is turned off and nitrogen gas is allowed to flow. Finally, the
temperature of the chamber is reduced to 600° C from 875° C and during this stage nitrogen
gas supply is kept turned on. Once the temperature of the chamber dropped to 600° C, the
nitrogen gas supply is turned off and the sample is taken out. Once the sample 1 is cooled
naturally to room temperature, it is ready for the next stage. Similarly, sample 2 to sample 6
are diffused by varying diffusion time and drive-in time. Table 3.1 shows the phosphorous
diffusion parameters of sample 1 to sample 6.
Table 3.1 Phosphorous diffusion parameters of sample 1 to sample 6.
Sample name Diffusion time (min.) Drive-in time (min.)
Sample 1 5 10
Sample 2 10 15
Sample 3 15 20
Sample 4 20 25
Sample 5 25 30
Sample 6 30 35
66
Figure 3.10 shows POCl3 diffusion furnace used in solar cell fabrication and Figure 3.11 shows
the POCl3 gas distribution system located at the furnace backside.
Figure 3.10: POCl3 diffusion furnace used in solar cell fabrication.
Figure 3.11: POCl3 gas distribution system located at furnace back (left), N2 and O2 gas
cylinder (right).
67
3.2.5 Front and back surface metallization (TLM pattern)
[[[[ [[[[
Following diffusion, screen printed metallic contacts are formed to form electrical contacts to
n and p doped regions. A thick and viscous metal solution or paste is forced through stainless
screen grid onto the wafer in selected lithographically defined open regions in the screen. The
metal pads on the back surface (p-type) are made of aluminum and on the front surface (n-type)
are made of silver. Appropriately designed screens are used for Transmission Line Method
measurement system. Figure 3.12 and Figure 3.13 show the screen printer and contact screen
respectively.
Figure 3.12: Screen printer.
Figure 3.13: Contact screen.
68
3.2.6 Drying
After screen printing, solar cells are required to go through drying process at relatively low
temperature (around 150°C) for certain period. In this experiment, printed solar cell is placed
in a preheated oven at 150°C for 10 minutes after each time of back and front side printing so
that the paste gets attached well to the wafer surface. Figure 3.14 shows the electrical dryer.
Figure 3.14: Electrical Dryer.
The rapid thermal annealing furnace is used to cure or fire screen printed contacts on silicon
solar cells. In this experiment, RTA of screen-printed solar cells is done at a temperature of
500°, 600°, and 820° C respectively. The solar cell is passed through a moving belt which goes
inside the RTA machine. Rapid thermal annealing is important because it provides proper
contact between the conductor and the semiconductor. Within this step fabrication of solar cell,
is successfully completed. These solar cells are now ready to measure the contact resistance.
Figure 3.15 shows the rapid thermal annealing furnace with exhaust system connected.
69
Figure 3.15: Rapid Thermal Annealing Furnace with exhaust system connected.
3.3 Measurement of contact resistance by TLM measurement system
Transmission Line Method (TLM) is used for the measurement of contact resistance between
metal and semiconductor of a solar cell. In this experiment, a different screen is used for the
front and back contact based on TLM pattern which has six pattern areas. Figure 3.16 shows
the schematic diagram of the TLM pattern used in this system.
Figure 3.16: Different test location for contact resistance measurement.
70
Figure 3.17 schematically describes the method in which resistance is measured between
adjacent pads while their separation is systematically increased.
Figure 3.17: 4 mm x 10 mm paste pads with the distance of 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm,
0.5 mm, 0.6 mm, and 0.7 mm for TLM pattern.
A total of six patterns are screen-printed using silver paste for the front side and aluminum
paste for back side on the test wafer respectively. Each pattern has 8 identical contact pads of
dimensions 4x10 mm2 with separation varying from 0.1 mm to 0.7 mm with an increment of
0.1 mm between each consecutive pad. The instrumental setup of contact resistance
measurement is shown in Figure 3.18.
Figure 3.18: Instrumental setup of contact resistance measurement system.
In order to measure resistance from all six patterns, a system of two rotary pole switches is
used. Figure 3.19 shows the diagram of the switches used. Switch # (a) is used to select a
71
pattern on the wafer i.e. its position varied from # 1 to # 6 and Switch # (b) varied from positions
1 through 7 in order to measure the resistance among all eight contact pads.
(a) (b)
Figure 3.19: Rotary pole switches for (a) pattern selection (b) resistance measurement between
neighboring contact pads.
The measured resistances for front side and back side are plotted as a function of distance
(between two adjacent contact pads) and the linear regression analysis is used to calculate the
intercepts of plotted curves. Then the contact resistances are calculated dividing the number of
pads. After this, the contact resistance versus diffusion time graphs are illustrated for six
samples.
3.4 Conclusion
Six monocrystalline silicon solar cells are fabricated successfully following different steps. The
surface reflectance of the textured wafer is measured by using Surface Reflectance
Measurement (SRM) system. The diffusion time is varied for the six solar cells and the contact
resistances of these fabricated solar cells are investigated by using the Transmission Line
Method (TLM) measurement system.
72
Chapter 4: Result and Discussion
4.1 Introduction
In this research, six monocrystalline silicon solar cells are fabricated by the variation of doping
concentration. During solar cell fabrication, various process steps are followed. After
fabrication, Transmission Line Method (TLM) is used for the determination of contact
resistance for the different doping concentration. Fabrication of solar cell and investigation of
contact resistance results are discussed.

Monocrystalline silicon solar cells are fabricated by following various steps. The results of
each process steps during solar cell fabrication are discussed
4.2.1 Cleaning and texturing of wafer
In the present work, all of the six samples are cleaned and textured using the same chemical
recipe. This step is completed by following three processes such as saw damage removal
process, hydrophobic process, and texturing process. The chemical ratio, temperature and time
are the same for all samples. Finally, the wafers are dried using the compressed air and that
concludes this process. The goal for cleaning the samples is to eliminate surface contaminants
that arise from the processing of crystalline substrate material or unintentionally added to the
manufacturing environment. The texturing modifies the silicon surface by providing an
optically rough surface that traps light incident to this surface.

SEM analysis of wafer is carried out at low and high magnification and images are shown in
Figure 4.1. After texturing, the wafer surface is fully covered with pyramids. On the wafer
surface, some large and small pyramids with some foreign particles and micro pores are also
observed. The foreign particles and micro pores on the wafer surface have an effect on the
reflectance but the uniformity of the pyramids leads to a lower surface reflectance.
73
(a)
(b)
Figure 4.1: SEM image (a) at low and (b) at high magnification showing the surface of
textured wafer.
74
4.2.3 Surface Reflection Measurement
In this experiment, surface reflectance of the textured wafer is measured using collecting
reflected light from the surface as a function of wavelength by the surface reflectance
measurement system. The primary reflectance data of wafer are given in APPENDIX A.1. The
normalized data are obtained by dividing all the primary data obtained from the mirror
reflectance data. The normalized reflectance data are given in APPENDIX A.2. Then the
percentage reflectance data are calculated by dividing the normalized data by 100. The
percentage reflectance data are given in APPENDIX A.3. The graphical representation of
percentage reflectance data for the wafer is shown in Figure 4.2.
80
Raw wafer
70
Textured wafer
60
% of Reflection
50
40
30
20
10
0
400
425
450
475
500
525
550
575
600
625
650
675
700
725
750
775
800
825
850
875
900
925
950
975
1000
1025
1050
1075
1100
1125
1150
1175
1200
Wavelength (nm)
Figure 4.2: Reflectance versus wavelength curve of wafer.
Figure 4.2 shows that the percentage of reflectance decreases with increasing wavelength up
to 500 nm and gets almost steady value in the range of wavelength 500 to 1000 nm. Further
increase of wavelength the percentage of reflectance increases. It is found that in the visible
75
range (450-1000 nm), the reflectance decreases and the minimum reflectance is 15.08 %. The
percentage of reflectance values of the raw wafer and textured wafer are shown in Figure 4.3.
40.00%
36.22%
35.00%
30.00%
25.00%
20.00%
15.08%
15.00%
10.00%
5.00%
0.00%
raw wafer textured wafer
Figure 4.3: Percentage of reflectance values of raw wafer and textured wafer.
4.2.4 Phosphorous diffusion
Phosphorous atoms are diffused into the p-type silicon wafers using phosphorous oxychloride
by a diffusion furnace to form the p-n junction. In this experiment, six samples are doped by
varying the diffusion time. The doping concentration is changed with doping time. P-type Si
wafers before and after phosphorous diffusion are shown in Figure 4.4.
76
(a) (b)
Figure 4.4: P-type Si wafers (a) before and (b) after Phosphorous diffusion.
4.2.5 Front and back surface metallization (TLM pattern)
In this experiment, following diffusion, screen printed metallic contacts are formed to form
electrical contacts to n and p doped regions. The front surface (n-type) is made of silver and
the back surface (p-type) are made of aluminum. Aluminum contact on the wafer backside also
serves to form a heavily doped p++ layer that reduces contact resistance and enhances back
surface reflectance. Appropriately designed screens are used for TLM process. The solar cell
before and after screen printing is shown in Figure 4.5.
(a) (b)
Figure 4.5: Solar cell (a) before and (b) after screen printing.
77
4.2.6 Drying
In this experiment, solar cells are placed in a preheated oven at 150° C for 10 minutes each
time after the back and front side metallization so that the paste gets attached well to the wafer
surface.

RTA of screen-printed cells is done at a temperature of 500°, 600°, and 820° C respectively.
The solar cells are passed through a moving belt which goes inside the RTA machine. Rapid
thermal annealing is important because it provides proper contact between the conductor and
the semiconductor. The fabrication process steps are now finished with RTA and
monocrystalline silicon solar cells fabrication is now successfully completed.
4.3 Investigation of contact resistance

The contact resistance depends on the semiconductor material (silicon, gallium arsenide) and
dopant type (p or n), and the contact material (titanium, silver, aluminum, nickel silicide), but
strongly dependent on the doping concentration near the semiconductor surface. Low values
of contact resistance are associated with heavy doping and vice versa [96]. Contact resistance
losses occur at the interface between the silicon solar cell and the metal contact. To keep top
contact losses low, the top N+ layer must be as heavily doped as possible. However, a high
doping level creates other problems. If a high level of phosphorus is diffused into silicon, the
excess phosphorus lies at the surface of the cell, creating a "dead layer", where light generated
carriers have little chance of being collected.
4.3.1 Determination of contact resistance for front side of solar cell
The front contact resistances of six monocrystalline silicon solar cells are measured by using
Transmission Line Method. The contact resistance data for front side of sample 1 to sample 6,
with the diffusion time variation are given in APPENDIX B. The plot of resistance versus
distance (between two adjacent contact pads) for the front side TLM pattern area 1~6 of six
samples are shown in Figure 4.6 ~ 4.11 and the linear regression analysis curve for the front
side of six samples are shown in Figure 4.12~ 4.17.
78
95
Sample 1
90 area 1
area 2
area 3
85
area 4
area 5
Resistance (Ω)
80 area 6
75
70
65
60
55
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
Figure 4.6: Resistance data from the TLM measurement system for front side of sample 1.
80
Sample 2
75 area 1
area 2
70 area 3
area 4
Resistance (Ω)
area 5
65 area 6
60
55
50
45
40
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
79
65 Sample 3
60 area 1
area 2
55 area 3
area 4
area 5
50
Resistance (Ω)
area 6
45
40
35
30
25
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
50 Sample 4
45 area 1
area 2
area 3
40 area 4
Resistance (Ω)
area 5
35 area 6
30
25
20
15
10
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
80
17 Sample 5
15 area 1
area 2
13 area 3
area 4
Resistance (Ω)
area 5
11
area 6
1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
105 Sample 6
area 1
100 area 2
area 3
95 area 4
area 5
Resistance (Ω)
90 area 6
85
80
75
70
65
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
81
95 Sample 1
90 Linear (area 1) y = 47.371x + 56.656
Linear (area 2) y = 52.061x + 55.306
Linear (area 3) y = 48.021x + 56.52
85 Linear (area 4) y = 51.082x + 54.949
Linear (area 5) y = 51.886x + 55.03
Resistance (Ω)
80 Linear (area 6) y = 53.079x + 55.017
75
70
65
60
55
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
Figure 4.12: Linear regression analysis curve for the front side of sample 1.
80 Sample 2
75 Linear (area 1) y = 48.679x + 40.884
Linear (area 2) y = 48.4x + 41.74
Linear (area 3) y = 49.679x + 40.47
70
Linear (area 4) y = 49.114x + 41.95
Resistance (Ω)
Linear (area 5) y = 49.839x + 41.157

65 Linear (area 6) y = 49.968x + 41.856
60
55
50
45
40
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
82
65 Sample 3
60 Linear (area 1) y = 49.864x + 25.689

Linear (area 2) y = 50.918x + 25.643
55 Linear (area 3) y = 51.982x + 25.85
Linear (area 4) y = 50.75x + 26.401
Linear (area 5) y = 48.679x + 26.274
Resistance (Ω)
50 Linear (area 6) y = 47.175x + 28.024
45
40
35
30
25
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
50 Sample 4
45 Linear (area 1) y = 49.829x + 10.637

Linear (area 2) y = 51.243x + 10.301
40 Linear (area 3) y = 53.279x + 9.5443
Linear (area 4) y = 52.279x + 11.263
y = 53.564x + 9.7771
Resistance (Ω)
Linear (area 5)
35 Linear (area 6) y = 50.257x + 10.383
30
25
20
15
10
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
83
17 Sample 5
15 Linear (area 1) y = 19.064x + 2.5043
Linear (area 2) y = 18.6x + 2.5129
Linear (area 3) y = 18.014x + 2.3386
13 Linear (area 4) y = 17.768x + 2.73
Linear (area 5) y = 19.886x + 1.5329
11 Linear (area 6) y = 20.546x + 1.6414
Resistance (Ω)
1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
105
Sample 6
100 Linear (area 1) y = 49.818x + 66.077
Linear (area 2) y = 50.804x + 65.569
Linear (area 3) y = 49.993x + 65.913
95 Linear (area 4) y = 49.361x + 66.82
Linear (area 5) y = 52.711x + 64.806
Linear (area 6) y = 52.196x + 65.743
90
Resistance (Ω)
85
80
75
70
65
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
84
Using linear regression analysis, the intercept of Figure 4.12 for area 1 of sample 1 is
calculated. Then the contact resistance is calculated dividing the intercept by the number of
pads. It is found that the intercept is 56.656 and the number of pads is 2. Using the contact
resistance formula, it is found that the front contact resistance for the TLM pattern area 1 of
sample 1 is 28.328 Ω. In a similar way, contact resistances for the TLM pattern area 2, 3, 4, 5,
and 6 become 27.653 Ω, 28.260 Ω, 27.475 Ω, 27.515 Ω, and 27.506 Ω respectively. The
average front contact resistance of sample 1 is 27.789 Ω. Following the similar way, the front
contact resistances of sample 2, sample 3, sample 4, sample 5, and sample 6 are calculated. The
summary of the front contact resistances of TLM patterns of six samples is shown in Table 4.1.
Table 4.1: Summary of the front contact resistances of TLM pattern for six samples.
Contact resistance of front side
Sample Area 1 Area 2 Area 3 Area 4 Area 5 Area 6 Average

name (Ω) (Ω) (Ω) (Ω) (Ω) (Ω) (Ω)
Sample 1 28.328 27.653 28.260 27.475 27.515 27.506 27.789
Sample 2 20.442 20.87 20.235 20.975 20.579 20.928 20.672
Sample 3 12.845 12.822 12.925 13.201 13.137 14.012 13.157
Sample 4 5.319 5.151 4.772 5.632 4.889 5.192 5.159
Sample 5 1.252 1.256 1.169 1.365 0.767 0.821 1.105
Sample 6 33.039 32.785 32.957 33.41 32.403 32.872 32.911
In this research, six samples are doped with phosphorous atoms with the time variation of 5
minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, and 30 minutes and the
corresponding front contact resistances are found 27.789 Ω, 20.672 Ω, 13.157 Ω, 5.159 Ω,
1.105 Ω, and 32.911 Ω respectively. The change in front contact resistance with diffusion time
is shown in Figure 4.18. From the Figure 4.18, it is seen that contact resistance decreases with
phosphorous doping time i.e. doping concentration increases.
85
35 Contact resistance with diffusion time variation
30
Contact resistance (Ω) 25
20
15
10
0
5 10 15 20 25 30 35
Diffusion time (min)
Figure 4.18: Contact resistance versus diffusion time curve for front side of solar cells.
The contact resistance is affected by three main factors like semiconductor materials, doping
concentration and type of conductor materials. There are others factors those affected the
contact resistance like metallization materials quality, firing recipe and air quality of the
laboratory. However, the doping concentration is the significant factor which controls the
contact resistance. Higher doping density reduces the contact resistance significantly but over
doping produces “dead layer” on the semiconductor surface. The dead layer is formed when
phosphorous atoms exceed the solid solubility of silicon and make the silicon electrically
inactive [97]. The dead layer also acts as a recombination center which increases auger
recombination and thus saturation current density.
In this research, front contact resistance started to decrease when doping time is 5 minutes and
continue until 25 minutes where the contact resistance is the least. After this time, silicon wafer
formed a dead layer on its surface. From the Table 4.1 and Figure 4.18 it is found that at 25
minutes doping time, the minimum contact resistance is found and at 30 minutes of doping
time, a dead layer is formed and it is considered as electrically isolated. So from this
experiment, it can be said that, for the optimum diffusion time 25 minutes, the minimum front
contact resistance becomes 1.105 Ω which is compatible with the high-efficiency solar cells.
86
4.3.2 Determination of contact resistance for back side of solar cell
The back contact resistances of six monocrystalline silicon solar cells are measured by using
Transmission Line Method. The contact resistances data for back side of sample 1 to sample 6,
with the diffusion time variation are given in APPENDIX C. The plot of resistance versus
distance (between two adjacent contact pads) for the back side TLM pattern area 1~6 of six
samples are shown in Figure 4.19 ~ 4.24 and the linear regression analysis curve for the back
side of six samples are shown in Figure 4.25~ 4.30.
5.6
Sample 1
5.4 area 1
area 2
5.2 area 3
area 4
5 area 5
Resistance (Ω)
area 6
4.8
4.6
4.4
4.2
3.8
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
Figure 4.19: Resistance data from the TLM measurement system for back side of sample 1.
87
7.8 Sample 2
7.6 area 1
area 2
7.4 area 3
area 4
7.2
Resistance (Ω)
area 5
area 6
7
6.8
6.6
6.4
6.2
6
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
Sample 3
8.4
8.2 area 1
area 2
8 area 3
area 4
Resistance (Ω)
7.8 area 5
area 6
7.6
7.4
7.2
6.8
6.6
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
88
10
Sample 4
9.8 area 1
area 2
9.6 area 3
area 4
Resistance (Ω)
9.4 area 5
area 6
9.2
8.8
8.6
8.4
8.2
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
10.8 Sample 5
10.6 area 1
area 2
10.4 area 3
area 4
Resistance (Ω)
10.2 area 5
area 6
10
9.8
9.6
9.4
9.2
9
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
89
100 Sample 6
95 area 1
area 2
90 area 3
area 4
Resistance (Ω)
85 area 5
area 6
80
75
70
65
60
55
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
5.6
Sample 1
5.4 Linear (area 1) y = 2.1286x + 3.8986
Linear (area 2) y = 2.0071x + 3.8714
5.2 Linear (area 3) y = 2.1929x + 3.8243
Linear (area 4) y = 2.1179x + 3.87
5 Linear (area 5) y = 2.2143x + 3.8143
Linear (area 6) y = 1.9607x + 3.9171
Resistance (Ω)
4.8
4.6
4.4
4.2
3.8
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
Figure 4.25: Linear regression analysis curve for the back side of sample 1.
90
Sample 2
7.8
7.6 Linear (area 1) y = 1.9643x + 6.1657

Linear (area 2) y = 2.0429x + 6.1429
7.4 Linear (area 3) y = 2.0571x + 6.0857
Linear (area 4) y = 2.0429x + 6.17
Resistance (Ω)
7.2 Linear (area 5) y = 2.1464x + 6.0714

Linear (area 6) y = 2.125x + 6.0943
7
6.8
6.6
6.4
6.2
6
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
8.4 Sample 3
8.2 Linear (area 1) y = 2.0714x + 6.7357
Linear (area 2) y = 1.8857x + 6.8243
8 Linear (area 3) y = 2.0357x + 6.7657
Linear (area 4) y = 1.9536x + 6.8043
Linear (area 5) y = 2.0357x + 6.7871
7.8 Linear (area 6) y = 1.9893x + 6.7143
Resistance (Ω)
7.6
7.4
7.2
6.8
6.6
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
91
10
Sample 4
9.8 Linear (area 1) y = 2.025x + 8.33
Linear (area 2) y = 2.0357x + 8.2814
Linear (area 3) y = 1.9393x + 8.3871
9.6
Linear (area 4) y = 2.1036x + 8.3229
Linear (area 5) y = 2.0071x + 8.3986
9.4 Linear (area 6) y = 2.0607x + 8.3214
Resistance (Ω)
9.2
8.8
8.6
8.4
8.2
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
10.8
Sample 5
10.6 Linear (area 1) y = 2.0893x + 9.11
Linear (area 2) y = 2.0929x + 9.0757
10.4 Linear (area 3) y = 2.1357x + 9.1071
Linear (area 4) y = 2.0857x + 9.1329
Linear (area 5) y = 2.1036x + 9.1243
Resistance (Ω)
10.2 Linear (area 6) y = 2.1036x + 9.17
10
9.8
9.6
9.4
9.2
9
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
92
100
Sample 6
95 Linear (area 1) y = 51.129x + 55.094
Linear (area 2) y = 49.371x + 57.124
90 Linear (area 3) y = 50.85x + 56.45
Linear (area 4) y = 53.204x + 55.041
Linear (area 5) y = 50.636x + 54.991
85
Linear (area 6) y = 50.443x + 55.927
Resistance (Ω)
80
75
70
65
60
55
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Distance (mm)
Using linear regression analysis, the intercept of Figure 4.25 for area 1 of sample 1 is
calculated. Then the contact resistance is calculated dividing the intercept by the number of
pads. It is found that the intercept is 3.8986 and the number of pads is 2. Using the contact
resistance formula, it is found that the back contact resistance for the TLM pattern area 1 of
sample 1 is 1.949 Ω. In a similar way, contact resistance for the TLM pattern area 2, 3, 4, 5
and 6 becomes 1.936 Ω, 1.912 Ω, 1.935 Ω, 1.907 Ω, and 1.959 Ω respectively. The average
back contact resistance of sample 1 is 1.933 Ω. Following the similar way, the back contact
resistances of sample 2, sample 3, sample 4, sample 5, and sample 6 are calculated. The
summary of the back contact resistance of TLM patterns for six samples is shown in Table 4.2.
93
Table 4.2: Summary of the back contact resistance of TLM pattern of six samples
Contact resistance of back side
Sample Area 1 Area 2 Area 3 Area 4 Area 5 Area 6 Average

name (Ω) (Ω) (Ω) (Ω) (Ω) (Ω) (Ω)
Sample 1 1.949 1.936 1.912 1.935 1.907 1.959 1.933
Sample 2 3.083 3.071 3.043 3.085 3.036 3.047 3.061
Sample 3 3.368 3.412 3.383 3.402 3.394 3.357 3.386
Sample 4 4.165 4.141 4.194 4.161 4.199 4.161 4.170
Sample 5 4.555 4.538 4.554 4.566 4.562 4.585 4.560
Sample 6 27.547 28.562 28.225 27.521 27.496 27.964 27.886
For the back contact of the solar cells, contact resistances for the six samples are found 1.933
Ω, 3.061 Ω, 3.386 Ω, 4.170 Ω, 4.560 Ω, and 27.886 Ω for their corresponding time variation.
Figure 4.29 shows the variation of back contact resistance with their corresponding time
variation.
94
30
Contact resistance with diffusion time variation

25
20
Contact resistance (Ω)
15
10
0
5 10 15 20 25 30 35
Diffusion time(min.)
Figure 4.31: Contact resistance versus diffusion time curve for backside of solar cells.
From Figure 4.29, it is seen that back contact resistance increases with the increase of doping
time. During the increment of doping time, a time is reached i.e. 25 minutes time, when the
contact resistance becomes maximum. After 25 minutes of doping time, back contact resistance
starts to rise sharply. This may be due to the phosphorous atoms exceeds the solid solubility of
silicon. That is why at 30 minutes of doping time, back contact resistance reached the peak
value.
From the Table 4.2 and Figure 4.29 it is found that at 5 minutes doping time, the minimum
contact resistance is found and at 30 minutes of doping time a dead layer is formed and it is
considered as electrically isolated. So from this experiment, it can be said that, for the optimum
diffusion time 25 minutes, the back contact resistance becomes 4.560 Ω which is compatible
with the high-efficiency solar cells.
In case of front contact resistance, it is seen that contact resistance decreases with the increase
of doping time or doping concentration but back contact resistance increases with the increases
of doping time or doping concentration. The possible reason is that after diffusion the structure
of the wafer becomes n+-p-n+, but for making a solar cell, the back side n+ layer must be made
the p+ layer. In order to make the p+ layer on the back side, the aluminum paste is used for over
95
doping the n+ layer by rapid thermal annealing furnace at 820° C temperature. When doping
concentration is increased, the aluminum paste remains fixed. Since doping concentration
increased with time but aluminum concentration remains fixed that is why back contact
resistance increased with doping concentration.
4.4 Conclusion
Six monocrystalline solar cells are fabricated with the variation of diffusion time. During
fabrication, same fabrication process steps are followed. Then metal-semiconductor contact
resistances are measured by using Transmission Line Method. From this study, it is found that
for higher doping concentration, the contact resistance is decreased for the front side of the
solar cell and is increased for the back side of the solar cell until the dead layer of phosphorus
is formed.
96
Chapter 5: Conclusion
The energy conversion efficiency of a solar cell can be significantly increased with the
improvement of cell parameters. One of the important parameters is the contact resistance
which plays a significant role to improve the cell efficiency. Contact resistance losses occur at
the interface between the semiconductor and the conductor. To keep the contact losses low, the
top n+ layer must be as heavily doped as possible. However, over doping creates other
problems. If an excess level of phosphorus is diffused into silicon, the excess phosphorus lies
at the surface of the cell creates a dead layer. Therefore the region under the contacts should
be heavily doped, while the doping is controlled by the diffusion time. The aim of this thesis
was to investigate the contact resistance of both sides of the solar cell. In the present study,
monocrystalline silicon solar cells are fabricated by the variation of diffusion time i.e. doping
concentration and corresponding front and back contact resistances are then measurement by
Transmission Line Method (TLM) measurement system. Following conclusions are drawn
from the research work:
1. All the samples are cleaned and textured using chemical solution of NaOH: H2O (DI) = 1
gram: 10 ml, HF: H2O (DI) = 1 ml: 50 ml, and KOH: IPA: H2O (DI) = 1 gram: 5 ml: 125 ml at
70° C temperature and from the Scanning Electron Microscope (SEM) analysis result, it is
observed that all the textured samples are covered with almost uniformly distributed pyramid
structure.
2. From the Surface Reflection Measurement (SRM) results, it is seen that cleaning and
texturing made the wafers significantly lower reflective than the raw wafers. It is found that
before and after cleaning and texturing the surface reflection is about 36.22% and 15.08%
respectively.
3. Samples are doped with phosphorous atoms for 5 minutes, 10 minutes, 15 minutes, 20
minutes, 25 minutes, and 30 minutes respectively in a diffusion furnace at 875° C temperature
to form an n-type layer on the p-type substrate which constitutes the solar cell.
4. Front and back side of six samples are screen printed using silver paste and aluminum paste
respectively by a TLM pattern screen for the measurement of contact resistance.
5. Screen printed samples are placed in a preheated oven at 150° C for 10 minutes after each
time of back and front side printing so that the paste gets attached well to the wafer surface.
97
6. Rapid Thermal Annealing (RTA) of screen-printed solar cells is done at a temperature of
500° C, 600° C, and 820° C to form ohmic contacts and cure the contacts between the conductor
and the semiconductor.
7. From the TLM measurement, it is found that the contact resistance depends on diffusion
time i.e. doping concentration. The results show that increasing the diffusion time lowering the
front contact resistance of the solar cells. On the other hand, increasing diffusion time also
increases the back contact resistance of the solar cells. It is observed that in 25 minutes of
diffusion time, optimum front and back contact resistances are found which are compatible
with the high-efficiency solar cells.
98
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appendix-a
A.1. Primary reflectance data of wafer
Wavelength Mirror Raw wafer Textured wafer

(nm) (mv) (mv) (mv)
400 0.024725 0.0155215 0.0065661
425 0.040666 0.0215215 0.0098348
450 0.087673 0.0417907 0.0206389
475 0.158449 0.069762 0.0359296
500 0.292401 0.128179 0.0644254
525 0.502468 0.2175955 0.1089669
550 0.80426 0.3451945 0.1725055
575 1.181906 0.5026805 0.2510035
600 1.640238 0.689773 0.3425471
625 2.167014 0.9091605 0.4429742
650 2.708453 1.0919703 0.5464143
675 3.552594 1.411175 0.6692499
700 4.640623 1.809872 0.8590782
725 5.240974 2.0250655 0.9545136
750 5.488286 2.0919565 0.9850546
775 5.70666 2.136947 0.989206
800 5.648857 2.108702 0.965302
825 5.825751 2.16734 0.9770823
850 6.098089 2.258137 0.9988966
875 7.021928 2.5928295 1.1237427
900 7.853732 2.896797 1.2391289
925 8.521851 3.134508 1.3155632
950 9.3948919 3.434506 1.4320719
975 9.757879 3.5384425 1.4735997
1000 9.768766 3.5391465 1.4735552
1025 8.975764 3.262974 1.3877869
1050 7.011224 2.6526225 1.1329507
1075 4.810238 1.924637 0.852826
1100 3.059425 1.3565765 0.5925437
1125 1.892884 0.9413255 0.4210208
1150 1.121371 0.6171005 0.2863743
1175 0.67246 0.4257345 0.1985538
1200 0.553446 0.40884 0.203877
106
A.2. Normalized reflectance data of wafer
Wavelength Raw wafer Textured wafer

(nm)
400 0.62776542 0.265565217
425 0.529225889 0.221843309
450 0.476665564 0.195407708
475 0.440280469 0.185758137
500 0.433367174 0.181332352
525 0.431053448 0.177863362
550 0.427207595 0.175489717
575 0.423313434 0.173371796
600 0.416532264 0.171839876
625 0.411545282 0.169416861
650 0.403171201 0.167244058
675 0.397223831 0.165383446
700 0.390006256 0.163121308
725 0.38639106 0.162125231
750 0.381167545 0.161283103
775 0.374465449 0.160334238
800 0.373297111 0.159884482
825 0.372027572 0.158717827
850 0.370302401 0.157804858
875 0.36924752 0.156233356
900 0.368843373 0.154775806
925 0.36782009 0.153375288
950 0.365571671 0.152430922
975 0.362624142 0.151016394
1000 0.362292075 0.150843535
1025 0.363531617 0.154614905
1050 0.378339431 0.160591
1075 0.400112635 0.17229393
1100 0.443408974 0.183678126
1125 0.497296982 0.212422927
1150 0.550308952 0.24537828
1175 0.63310011 0.295264848
1200 0.738796558 0.368377403
107
A.3. Percentage reflectance data of wafer
Wavelength Raw wafer Textured wafer

(nm) (%) (%)
400 62.77654196 26.5565217
425 52.92258889 22.1843308
450 47.66655641 19.5407708
475 44.02804688 18.5758136
500 43.33671738 18.1332351
525 43.10534482 17.7863362
550 42.72075946 17.5489717
575 42.33134344 17.3371796
600 41.65322624 17.1839875
625 41.15452821 16.9416861
650 40.31712014 16.7244058
675 39.72238314 16.5383446
700 39.00062556 16.3121308
725 38.63910601 16.2125230
750 38.11675448 16.1283102
775 37.44654491 16.0334237
800 37.32971113 15.9884481
825 37.20275721 15.8717827
850 37.03024013 15.7804857
875 36.92475201 15.6233355
900 36.88433728 15.4775806
925 36.78200898 15.3375287
950 36.55716708 15.2430922
975 36.2624142 15.1016394
1000 36.22920746 15.0843535
1025 36.35316169 15.4614905
1050 37.83394312 16.0591000
1075 40.01126348 17.2293930
1100 44.34089739 18.3678125
1125 49.72969817 21.2422927
1150 55.0308922 24.5378728
1175 63.310011 29.5264848
1200 73.87965583 36.8377402
108
appendix-b
B.1. Resistance between adjacent contact pads of six TLM pattern areas for front side of
sample 1
Pattern Resistance between contact pads (ohm)

Area 1 and 2 2 and 3 3 and 4 4 and 5 5 and 6 6 and 7 7 and 8
1 61.43 66.52 69.71 76.28 80.4 85.39 89.50
2 60.21 65.40 70.58 77.43 81.80 86.49 91.00
3 62.19 65.35 69.70 76.03 81.63 85.80 89.40
4 59.84 64.41 71.63 75.45 80.19 85.64 90.51
5 60.58 65.07 69.48 76.53 81.47 86.91 90.45
6 61.03 64.50 70.61 76.90 82.12 86.54 92.04
sample 2

1 45.38 51.39 55.18 60.34 65.41 69.38 75.41
2 46.25 50.36 56.58 62.54 66.91 70.52 74.54
3 45.73 50.31 55.26 59.91 65.37 70.63 75.18
4 47.49 52.38 55.49 60.58 66.51 72.43 76.29
5 45.17 51.49 56.14 62.37 66.34 70.58 75.56
6 46.48 52.76 57.32 61.32 65.19 72.49 77.34
109
sample 3

1 30.61 35.43 41.37 45.26 50.61 55.41 60.75
2 30.54 36.15 40.31 46.68 51.49 55.39 61.51
3 31.48 35.59 41.74 46.29 52.49 56.31 62.60
4 32.17 36.42 40.51 46.35 52.48 57.46 61.52
5 31.81 35.36 40.79 45.19 51.13 55.71 60.23
6 32.92 36.59 42.29 47.23 52.49 56.39 60.35
sample 4

1 15.34 20.34 26.45 30.46 35.62 40.26 45.51
2 16.18 20.17 25.36 30.59 35.81 40.53 46.95
3 13.96 21.18 25.38 31.18 36.09 41.89 46.31
4 15.71 22.43 26.27 33.48 37.41 42.53 47.39
5 15.16 20.19 25.12 32.59 36.29 42.54 46.53
6 15.41 20.27 25.04 31.28 35.58 40.51 45.31
110
sample 5

1 4.53 6.05 8.27 10.14 12.37 13.68 15.87
2 4.84 5.98 7.83 9.74 11.86 13.73 15.69
3 4.04 5.83 7.99 9.89 10.99 12.99 15.08
4 4.71 6.41 7.69 9.75 11.54 13.43 15.33
5 4.07 5.46 7.18 8.98 11.26 13.65 15.81
6 4.13 5.24 7.43 10.20 12.18 13.87 15.97
sample 6

1 70.34 75.63 81.76 86.87 91.65 95.46 100.32
2 71.09 75.85 80.45 85.41 90.73 96.16 101.54
3 70.51 76.74 80.86 85.70 90.59 95.65 101.32
4 72.42 76.45 81.63 86.18 91.05 95.71 102.51
5 70.18 75.04 80.98 85.52 91.32 96.70 101.49
6 71.34 76.38 81.02 85.59 92.40 97.31 102.31
111
appendix-C
C.1. Resistance between adjacent contact pads of six TLM pattern areas for back side of
sample 1

Area
1 and 2 2 and 3 3 and 4 4 and 5 5 and 6 6 and 7 7 and 8
1 4.12 4.32 4.53 4.75 4.96 5.18 5.39
2 4.08 4.28 4.45 4.68 4.87 5.08 5.28
3 4.03 4.27 4.49 4.71 4.90 5.17 5.34
4 4.11 4.30 4.48 4.69 4.91 5.16 5.37
5 4.01 4.26 4.48 4.74 4.93 5.14 5.34
6 4.13 4.31 4.50 4.68 4.89 5.09 5.31
sample 2

1 6.36 6.57 6.75 6.93 7.17 7.34 7.54
2 6.34 6.56 6.78 6.94 7.14 7.38 7.58
3 6.28 6.50 6.69 6.92 7.15 7.32 7.50
4 6.38 6.59 6.76 6.99 7.19 7.39 7.61
5 6.27 6.49 6.73 6.96 7.15 7.35 7.56
6 6.30 6.53 6.71 6.95 7.19 7.36 7.57
112
sample 3

Area
1 6.94 7.14 7.36 7.57 7.79 7.98 8.17
2 7.01 7.21 7.39 7.58 7.75 7.96 8.15
3 6.97 7.19 7.36 7.57 7.79 7.98 8.20
4 6.99 7.21 7.39 7.58 7.79 7.96 8.18
5 6.98 7.19 7.41 7.61 7.81 8.01 8.20
6 6.88 7.12 7.34 7.53 7.70 7.91 8.09
sample 4

Area
1 8.51 8.72 8.95 9.18 9.36 9.55 9.71
2 8.48 8.69 8.89 9.11 9.29 9.51 9.70
3 8.57 8.77 8.97 9.20 9.35 9.54 9.74
4 8.53 8.73 8.96 9.18 9.38 9.59 9.78
5 8.61 8.79 9.01 9.18 9.41 9.60 9.81
6 8.52 8.73 8.96 9.14 9.34 9.58 9.75
113
sample 5

1 9.31 9.55 9.74 9.91 10.18 10.35 10.58
2 9.27 9.50 9.71 9.92 10.14 10.31 10.54
3 9.32 9.54 9.76 9.94 10.18 10.37 10.62
4 9.34 9.56 9.74 9.96 10.20 10.39 10.58
5 9.31 9.55 9.76 9.99 10.20 10.37 10.58
6 9.37 9.59 9.81 10.02 10.23 10.42 10.64
sample 6

Area
1 60.18 65.25 70.82 75.36 80.49 85.63 91.09
2 62.99 66.87 71.36 76.49 80.98 86.93 92.49
3 62.00 66.89 71.39 76.33 81.39 86.43 93.10
4 61.03 66.09 70.02 75.28 81.87 87.52 92.45
5 60.12 65.19 70.09 75.06 80.25 85.67 90.34
6 61.39 66.01 71.49 75.41 80.10 86.17 92.16
114
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Study and Investigation of The Contact Resistance of Monocrystalline Silicon Solar Cell-10-128

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Figure 2.

24: Resistivity as a function of the doping concentration for different

Figure 3.18: Instrumental setup of contact resistance measurement system…….. 71

Figure 4.2: Reflectance versus wavelength curve of wafer…………………….. 75

MDGs Millennium Development Goals

Figure 1.1: World energy consumption by country grouping [3].

Figure 1.2: World energy consumption by energy source [3].

Figure 1.4: Maximum power demand in Bangladesh [11].

Figure 2.1: (a) N-type silicon and (b) P-type silicon.

2.3 Solar Cell

2.4 Crystalline Silicon (c-Si) solar cells

2.6 Photovoltaic Energy conversion

2.7 Principle of solar cell operation

2.8 The p-n junction

2.9 Analysis of p-n junction

( )= ∇ + μ and ( )= ∇ + μ …….. (2.5)

for holes in the n-region

= ( 1), = …………………………………….. (2.9)

= ( ) ………………………………….. ………………….. (2.10)

( )= J ( )=J J , 1 ……………… (2.13)

2.10.1 Cleaning and texturing of wafers

2.10.1.1 Saw damage removal process

NaOH + H2O → Na+ + OH-…................................. (2.15)

2.10.1.2 Hydrophobic process

2.10.1.3 Texturing process

Figure. 2.6: Light trapping by “pyramid” covered at the textured surface.

2.10.2 SEM analysis of textured wafer

2.10.3 Surface Reflection (SR)

2.10.4.1 Atomic mechanism of diffusion

Figure 2.8: (a) Substitutional and (b) Interstitial impurities in silicon.

Figure 2.10: Impurity atom diffusing along a periodic potential.

2.10.4.2 Fick’s first law of diffusion

Figure 2.12: Diffusion from a concentration gradient.

Since the concentration gradient is given by

equation 2.25 and 2.26 can be combined to give

Combining equations 2.28 and 2.29 results in

which in partial differential terms is known as Fick’s first law

2.10.4.3 Fick’s second law of diffusion

In differential terms, equation 2.34 is the transport equation

2.10.4.4 Single step diffusion

Early in the development of integrated circuit fabrication technology, semiconductor doping

= , = 0, > 0……………… (2.37)

= 0, > 0, = 0 ………………....... (2.38)

Figure 2.13 shows the single step diffusion at initial conditions.

Laplace transforms of common functions may be constructed by integrating equation 2.39.

By treating the boundary conditions equation 2.37 in the same way

̅=∫ = , = 0……………. (2.44)

where, b2 = p/D. The Laplace transform for equation 2.45 is

( )≡∫ ( , ) ……………………..……… (2.47)

Integrating equation 2.47 results in

Figure 2.14: Complementary error function profile evolution versus time.

2.10.4.5 Double step diffusion

Figure 2.15 shows the Pre-deposition and drive-in process of diffusion.

Figure 2.15: Pre-deposition and drive-in process.

is a solution to equation 2.46 where A is an arbitrary constant. Equation 2.53 is symmetric

If the concentration distribution is given by equation 2.53, then

Thus the concentration distribution can also be represented by

The gradient of the concentration distribution can be obtained by differentiating equation

Figure 2.17: Gaussian and error function values versus z.

Figure 2.18: Experiment to measure oxidation enhanced diffusion.

(860℃) ≥ 0.98 0.01…………….…… (2.69)

(790℃) ≤ 0.01 0.01………………..… (2.79)