Professional Documents
Culture Documents
Page no.
List of Figures
List of Tables
Abstract
Chapter 1:Introduction
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synthesis
2.2.1.4 Effect of pH on reducing power of the reducing agent
2.2.2 Glass frit
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References
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Bibliography
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Acknowledgement
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List of figures
Figure no.
Description
1.1
2.1
2.2
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2.3
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2.4
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contact
2.7
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3.1
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3.2
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3.3
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List of tables
Table no.
Description
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2.1
3.1
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Abstract
Dye sensitized solar cell (DSSC) is emerging technology which can be a good alternative to
conventional Si based solar cell technology due to their cost effectiveness and simple fabrication.
During up scaling of DSSCs, in parallel module, the energy efficiency gets degraded due to high
sheet resistance of large area FTO coated glass substrate. Incorporation of metal fingers, similar
to the case of silicon solar cells, would lower the ohmic losses. Silver is the most preferred
material for metal fingers due to its good conductivity. Typically, metal paste contains metal
particles, glass frit and organic vehicle. The metal paste can be screen printed on to the substrate
followed by sintering at appropriate temperature. Using silver nanoparticles along with low
melting glass frit such as Bi2O3-B2O3-ZnO glass would lower the sintering temperature of
printed silver paste. Silver paste should exhibit psuedoplastic behavior with minimum slumping
in order to get desired dimensions of metal fingers on the substrate. Silver paste is to be
characterized for rheology (Rheometer), conductivity (four probe method) and FE-SEM for
connectivity with substrate after sintering. The goal is to screen print silver paste with desired
properties on the glass substrate to achieve the metal fingers of desired dimensions.
Chapter 1: Introduction
In todays world, energy is an important factor for maintaining economic, environmental and
political stability. Non renewable sources of energy such as fossil fuels are depleting fast. It
urges the need to use the cost effective solar energy. Conventional solar cell modules have an
efficiency of 15%, but it requires ultra pure material, high temperature processing which makes
this technology expensive [1]. Dye sensitized solar cell (DSSC) is emerging technology which
can be a good alternative conventional Si based solar cell technology due to their cost
effectiveness and simple fabrication. Laboratory scale DSSC (using of nano size titanium
dioxide (TiO2)) provided reasonable energy conversion efficiency of about 11% [1]. This caused
increased interest in the possible large-scale application of DSSCs. Even though the performance
of DSSCs is inferior to that of conventional solar cells in terms of efficiency, a simple production
method at relatively low temperature makes them a good alternative. So, industrial researchers
are trying to scale up the DSSC technology from laboratory level to stand alone power
generators. In general, scaling up DSSCs is possible in two ways: series monolithic or
interconnect modules and parallel grid module. Series interconnect modules are prepared by
connecting individual small cells in series. Since each unit cell is prepared under ideal
conditions, it is to be expected that the performance will be the same as that of the unit cell. On
the other hand, parallel grid modules are prepared on large TCO glass substrates. A device with
an active area of a few square centimeters prepared on a fluorine-doped tin oxide (FTO) glass
substrate showed an energy conversion efficiency of only 0.3% because of ohmic losses
associated with the large substrate [2]. One way to decrease ohmic losses and thereby increase
the overall efficiency is to use current collecting metal fingers on FTO coated glass substrate.
Metal fingers are used for the same purpose in silicon based solar cells. Among many conductive
metals, silver is studied most extensively due to its low electrical resistivity (15.87 n-m at
20C). But, silver gets corroded by I-/I3- redox electrolyte. Thus, it has to be protected from
electrolyte. Many researchers tried to protect it with surlyn, overcoat of glass frit [3] etc.
The main components of conductive silver paste are silver powder for conductivity, glass frit to
bind silver particles together and organic compounds are used as a vehicle to transport the
suspended silver and glass particle. Silver inks with PbO based glass frit have been extensively
6
used for making electrical contacts in solar cells and other electronic devices due to its excellent
electrical properties [4]. Recently, PbO-based glass in silver thick films has been restricted as it
is dangerous to health and environment. This has been the motivation behind replacement of Pb
based glass frit. Generally, the firing temperature of Pb-free frit is higher than that of PbO glass
frit. [4] Thus, it is difficult to sinter silver paste at lower temperatures using Pb-free frit.
Densification of silver paste after printing is important to achieve good conductivity. Nano-sized
particles can help the substance to sinter at lower temperatures due to their higher surface energy
[4]. Therefore, it is possible to prepare Pb-free silver paste at lower firing temperatures by adding
silver nanoparticles.
Fig 1.1 - Schematic cross-section view of grid type DSSC module [5]
An electrolyte usually solution with a dissolved iodide/triiodide (I-/I3-) ion redox couple
in the space between the two electrodes
In a dye sensitized solar cell a large band-gap material namely nanocrystalline TiO2 serves as
charge transport medium. A monolayer of dye is chemically adsorbed on this material. When
light falls on dye, it causes injection of electrons into the conduction band of TiO2. The electrons
then diffuse towards a transparent conducting oxide (TCO) substrate. The dye is regenerated
through receiving electrons from an iodide/triiodide (I/I3) redox couple dissolved in the
electrolyte. After passing through a desired load, the electrons enter the cell through a counter
electrode to reduce the triiodide ions and thus complete the circuit.
(d) Electrolytes
Electrolyte is used to transfer electron from counter-electrode to the oxidized dye. This process
completes the circuit and also regenerates the dye. The electrolyte must reduce the dye cation
before the dye cation recombines with an electron in the photo-electrode. The electrolyte should
not allow its oxidized form to intercept an electron from the photo-electrode. Generally I3-/Icouple is used as electrolyte in most of the DSSC modules. There are few problems associated
with liquid electrolytes such as sealing and stability of cells. Thus, research is going on to replace
liquid electrolytes with solid or gel electrolyte. The main substitutes are gel electrolytes and
polymer electrolytes.
(e) Sealants
In order to make DSSC suitable for indoor and outdoor applications long term stability of
the module is required. By having a sealant, evaporation of electrolyte and intrusion of foreign
material from outside atmosphere in DSSC modules is avoided. Sealing can be done in many
ways. Polymer sealing can be done by surlyn, Bynel, etc. Also, glass frit and waterproofed
plastic can also be used to seal the module [6].
2.1.2 Parallel module for DSSC
ohmic losses associated with the large glass substrate. Thus, in this module, current collecting
metal fingers (shown in figure) are used same as that in silicon solar cells. The materials tried for
these fingers are Ag, Au, Cu, Al, etc. But, silver is the most researched metal due to its low
electrical resistivity (15.87 n-m at 20C), low dark current. Silver paste is having constituents
like silver powder, glass frit and organic vehicle is used for contact formation.
High conductivity and low contact resistance for minimizing series losses
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The polyol method can be used for preparation of metal nano particles. In this method, the liquid
polyol (ethylene glycol, propylene glycol, diethylene glycol) acts both, as the solvent of the
metal precursor and as the reducing agent [9].
2.2.1.2 Stabilization of metal nano particles against aggregation
Metal nano particles in colloidal dispersions approach each other and collide due to Brownian
motion. This may result in their aggregation followed by irreversible coagulation and
sedimentation, as the density of metal is very high compared to the density of typical liquids. The
best way to avoid this problem is to prevent aggregation of metal nanoparticles at the early stages
of their formation, while synthesizing the metal ink precursor. Thus, selection of stabilizer, liquid
vehicle, and stabilization procedure are of great importance as it decides the shelf life and
performance of the metal paste.
Stabilization can be done in two ways:
(a)Electrostatic stabilization: It is a result of electrostatic repulsion between electrical double
layers surrounding interacting particles. Stability of dispersions increases with increase in the
value of the electric potential of the NPs. Zeta potential () is used as a measure of the electrical
potential of a particle. But, the electrostatic mechanism is not effective in organic vehicles, and
that requires an additional or different stabilization mechanism.
(b)Steric stabilization: To overcome the problem, steric stabilization is frequently used as an
alternative. Steric stabilization is achieved by surrounding the particle with an adsorbed layer of
sterically bulky molecules, such as polymers, mostly nonionic.
The most frequently used stabilizing agent is poly (N-vinyl-2-pyrrolidone) (PVP) of various
molecular weights. It exhibits a highly effective protective function in both organic and aqueous
media. PVP has been shown to be an effective stabilizer of aqueous dispersions of Ag
nanoparticles as for organic solvents as well as in polyol synthesis [9]
2.2.1.3 Chemical reduction method for silver nano particle synthesis
For chemical reduction method, choice of reducing agent is of prime importance. The precursor
used in most cases is silver nitrate. Reducing agents like formaldehyde (HCHO) [10], hydrazine
monohydrate (N2H4) [11], [4], glucose [12], ammonium formate (HCOONH4) [12], sodium
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borohydrate (NaBH4) [12] can be used. The reducing ability will determine the formation
kinetics and thus the reaction temperature. The reaction can be carried out in aqueous or organic
solvents in the presence of suitable protective agent such as PVP, PVA, etc. [10].
2.2.1.4 Effect of pH on reducing power of the reducing agent
Solution alkalinity plays important role in deciding the reducing power of the reducing agent.
Suitable amount of base such as NaOH, Na2CO3, and NH3.H2O can be added in order to
maintain the pH during the reduction reaction of silver nitrate.
During reduction of silver nitrate with formaldehyde, two reaction mechanisms are proposed in
[11,10].
2Ag+ + HCHO + 3OH = 2Ag + HCOO + 2H2O
2Ag+ + HCHO + OH = Ag + HCOOH + H2
They studied the effect of solution pH during formation of silver nanoparticles. The ratio of
formaldehyde to silver nitrate is maintained at 4 (after trying ratio from 1 to 120) so that
sufficient formaldehyde should be present to reduce silver nitrate. Using only formaldehyde gave
very slow reduction rates at room temperature due decrease in pH of the solution as the reaction
proceeds. Thus, pH is maintained at 7 by using Na2CO3 (Na2CO3/AgNO3=1) which favored the
reduction process. Although higher pH favors the reduction process, it affects the particle size
adversely. Use of powerful base such as NaOH caused adverse effect on particle size. This
prompted them to use Na2CO3 to replace NaOH. Also, addition of too much of Na2CO3 caused
the particles to grow as shown in figure. This is because, PVP (protective agent) molecules are
capable of combining with hydroxyl ions. This reduces the effective quantity of PVP to protect
silver colloids. Thus, maintaining pH to the optimum level is important to get good reduction
rate and particle size.
14
(a)
(b)
Fig 5 (a) Solution pH as a function of time with different additions of [Na2CO3]/[AgNO3] = (a)
0; (b) 1; (c) 2: [AgNO3]D0.005 M, [HCHO]/[AgNO3] = 4, [NaOH]/[AgNO3] = 1, PVP/AgNO3 =
9.27) (b) Effect of [Na2CO3]/[AgNO3] ratio on silver average size and its standard deviation
(other conditions (other conditions same as that in fig (a)) [10]
2.2.2 Glass frit
Glass frits are metal oxides that play an important role in the formation of the contact. It acts as a
permanent binder and also helps during sintering of metal particles.
PbO based paste were extensively used for contact formation in solar cells. The toxic nature of
PbO based paste has been the motivation behind its replacement with lead free paste. Generally,
the firing temperature of Pb-free frit is higher than that of PbO glass frit [4]. So, it is difficult to
sinter silver paste at lower temperatures using Pb-free frit. Thus, many researchers have studied
the low melting lead free glass systems. One of the low melting lead free glass systems is Bi2 O3B2O3-ZnO ternary system which can be considered as an alternative to lead oxide glasses
because the bismate glasses have unique thermal and optical properties [13]. The thermal
properties (Tg, Tm) and crystal phase information for Bi2O3-B2O3-ZnO glass with different
compositions is shown in the table.
15
Table 2.1 - The compositions (in mol %), thermal properties and crystal phase of Bi2O3-B2O3ZnO glass samples [13]
2.2.2.1 Effect of glass content on different properties of silver paste
In general, the sheet resistance increases with increase in glass content of silver paste. The sheet
resistance of substrate for the case where silver paste (with different glass content) was prepared
using different shaped micron size silver particles is shown in figure [14].
However, the adhesive strength and Vickers hardness increases with increase in glass content in
silver paste. Thus, it is important to optimize the glass content in silver paste to get a good
balance between sheet resistance and adhesive strength.
(a)
(b)
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(c)
Fig. 2.5 (a) Dependence of sheet resistance of fired film samples on the glass weight percentage
(b) Dependence of adhesion strength of fired film samples on the glass weight percentage
(c) Dependence of Vickers hardness of fired film samples on the glass weight percentage [14]
2.2.3 Organic compounds
Organic compounds are used as a vehicle to transport the suspended silver and glass particles.
The organic compound plays an important role in deciding the desired rheological properties to
the paste. During sintering, the organic compounds get evaporated leaving a dense mixture of
silver particles and glass frit. Organic vehicle used in silver paste is a mixture of ethyl cellulose
and terpineol.
substrate through mesh openings. Screen printing is one of the worlds oldest methods of
printing words and images. Screen printing first appeared in a recognizable form in China long
back in 960 AD. But, this technology was first introduced in photovoltaic industry only few
decades back in 1970s. In 1976, Spectrolab, Inc. combined screen-printing with a laminated
module design to print metal contacts on the surface of solar cell [15].
Screen printed contact technology is very rapid and cost effective metallization process. The
screen printing equipment is robust, simple, and inexpensive and can be easily automated. It also
produces less chemical waste and thus does not affect the environment very much. Thus, screen
printing is very effective in mass production of solar cells. Most solar cell manufactures use the
basic screen printing technique for metallization. In fact, over 90% of all crystalline silicon
modules are manufactured using screen printing and about 60% of flexible thin film modules use
screen printing in the manufacturing process [16]. Other methods of printing are pad printing,
photolithography, ink-jet printing. But, screen printing stands out as the most popular printing
methods due to its advantages.
2.4.1 Main components of the screen printing process
(a) A screen with desired mesh size
(b) A squeegee
(c) The metal paste of desired composition
(a) Screen
Usually nylon mesh is used for screen printing metal paste on glass substrate. The size of the
mesh in the screen determines the minimum width of the fingers. In case of fine line printing on
the substrate, the mesh with small opening is required. The mesh with fine mesh size experiences
higher tension. Thus, stainless steel mesh is used which provides higher strength.
(b)Squeegee
A squeegee is used to provide shear stress which causes the viscosity of the paste to decrease
which ensures free flow of the paste through the mesh openings. The pressure applied by the
squeegee affects the final efficiency of solar cell [17].
18
(c)Metal Pastes
The metal paste which is used should have desired properties such as viscosity for getting a good
print on the substrate.
2.4.2 General procedure for contact formation by screen printing
The screen printing process consists of three steps. In the first step, the screen is covered with
paste by moving a squeegee over the surface of the screen-printing mask in the filling phase.
Secondly, the squeegee moves over the screen, again applying an additional vertical force that
presses the screen on the wafer and the paste through the meshes of the mask. In the last step the
mask is lifted, creating distance to the solar cells surface, which is known as the snap-off
distance. Emulsion over mesh (EOM) is used to increase the theoretical height of the printed
contacts, thus, increasing the aspect ratio. The screen printing process is summarized in figure 1.
Fig 2.6 - Printing cycle steps, main parts of screen-printing machine are detailed along with the
process sequence followed to define the contact [17].
19
Squeegee pressure
The pressure applied also plays an important role in the deposition of the paste. When
very high pressure is applied, excessive paste from the screen could be deposited which
can break the wafer. On the contrary, when too little pressure is applied, the paste might
not get released from the screen at all.
Squeegee speed
The speed of the squeegee movement also determines the print quality. If the speed is too
high, the paste can miss many holes and lead to a non-uniform deposition.
Fig 2.7 - Evolution of viscosity and shear rate during printing [18]
Rheological changes in the paste during printing are time and shear dependent and specifically
the actions during and just after the print stroke are framed in milli-seconds. Figure 2.7 shows the
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changes in viscosity and shear rate prior to, during and after screen printing. If stirring is applied
prior to printing, the viscosity of the paste is reduced. Further reduction in viscosity is caused by
the squeegee action when the paste is pushed by squeegee over the screen surface. The steep
change in viscosity and shear rate is observed when the paste is forced through the screen
openings. After the paste is released from the screen opening, the shear rate returns to original
proportions and the viscosity increases. Thus the paste recovers its original structure. The speed
of the recovery of the paste structure determines the slumping character of the paste. In case of
using a snap-off the screen is lifted directly behind the squeegee. Thus, the paste has very little
time to recover the structure. If no snap-off is used, the paste has little more time to regain its
structure, but it will be disturbed again when the screen is lifted.
The paste flow behavior during the squeegee movement is not understood in detail and is
dependent on different assumptions. As indicated in figure 2.7, when the screen openings are
filled, the shear rate has a maximum value, which is supposed to be more than 1000 reciprocal
seconds. In general commercially available pastes can be printed fairly easily, but show
extensive slumping actions, broadening the printed lines by over 50% [18]. If, on the other hand,
a paste is produced for less slumping, then it is extremely difficult or impossible to print and to
keep the printing quality under control in mass production. This often leads to blockages in the
screen (clogging) or interruptions in the printed lines. Thus, a paste with optimum slumping
character is recommended.
22
23
The process developed by [10] was followed. Silver nitrate solution of 0.01M prepared from
silver nitrate powder. Formaldehyde solution (37% by wt. or 10.05M) was used to make 2M
formaldehyde solution. As described in [10], the quantities of formaldehyde, PVP and sodium
carbonate were taken in the ratio:
solution
solution
AgNO3
0.43gm
0.85gm
HCHO
28.33ml (2M)
56.66ml(2M)
Na2CO3
0.425gm
0.85gm
PVP
3.94gm
7.88gm
Compound
Table 3.1 - Amounts of different raw materials required when 250ml and 500ml of 0.01M
AgNO3 solution are used respectively
The procedure for making silver nano particle is explained in a flow chart. Due to small size of
silver particles, colloid is quite difficult to separate from the solution. In the last step, acetone of
the same volume as that of the solution has to be added [10] and then the colloid is separated
from the solution through centrifuge and filtration. Due to low solubility of PVP in acetone, PVP
protected silver colloids agglomerate and can be separated easily. If the precipitate is kept wet, it
can be re-dispersed by de-ionized water. Only the size of the silver nanoparticles might increase
marginally during the re-dispersion process [10].
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Characterize nano particles with particle size analyzer to get average particle size and
particle size distribution
Characterize morphology of nano particles with FE-SEM and X ray diffraction for
crystallinity
Glass frit
Prepare low melting Bi2O3-B2O3-ZnO glass by conventional melt quench technique and
frit it with the help of three roll mill
Silver Paste
Prepare silver paste by adding silver nanoparticles, glass frit, and organic vehicle in
proper proportions
Characterize the paste for rheology using a rheometer with cone and plate geometry
Screen print the paste with desired dimensions on FTO coated glass
Drying and sintering the paste at different temperatures (depending on Tg of glass frit and
size of nano particles) after screen printing
Characterize sintered paste for sheet resistance with four probe method and FEG-SEM
for connectivity with substrate
Optimize properties of the paste by try different proportions of the above components
27
References
[1] Won Jae Lee, Easwaramoorthi Ramasamy, Dong Yoon Lee, Jae Sung Song, Dye-sensitized
solar cells: Scale up and currentvoltage characterization, Solar Energy Materials & Solar Cells
91 (2007) 16761680
[2] Easwaramoorthi Ramasamy, Won Jae Lee, Dong Yoon Lee, Jae Sung Song, Portable,
parallel grid dye-sensitized solar cell module prepared by screen printing, Journal of Power
Sources 165 (2007) 446449
[3] Won Jae Lee, Easwaramoorthi Ramasamy, Dong Yoon Lee, Jae Sung Song, Glass frit
overcoated silver grid lines for nano-crystalline dye sensitized solar cells, Journal of
Photochemistry and Photobiology A: Chemistry 183 (2006) 133137
[4] Sunghyun Park, Dongseok Seo, Jongkook Lee, Preparation of Pb-free silver paste
containing nanoparticles, Colloids and Surfaces A: Physicochem. Eng. Aspects 313314 (2008)
197201
[5] Won Jae Lee, Easwaramoorthi Ramasamy, Dong Yoon Lee, Jae Sung Song, Grid type dyesensitized solar cell module with carbon counter electrode, Journal of Photochemistry and
Photobiology A: Chemistry 194 (2008) 2730
[6] H. Aguilar Ribeiro, P. M. Sommeling, J. M. Kroon, A. Mendes, C. A. V. Costa, Dye
sensitized Solar Cells: Novel Concepts, Materials, and State-of-the-Art Performances,
International Journal of Green Energy, Vol 6: 3 (2009), 245 256
[7] Lei Wang, Xiaoming Fang, Zhengguo Zhang, Design methods for large scale dye-sensitized
solar modules and the progress of stability research, Renewable and Sustainable Energy
Reviews 14 (2010) 31783184
[8] Matthias Hrteis, Fine-Line Printed Contacts on Crystalline Silicon Solar Cells, PhD Thesis
[9] Alexander Kamyshny, Joachim Steinke and Shlomo Magdassi, Metal-based Inkjet Inks for
Printed Electronics, The Open Applied Physics Journal, 2011, 4, 19-36
[10] Kan-Sen Chou, Chiang-Yuh Ren, Synthesis of nanosized silver particles by chemical
reduction method, Materials Chemistry and Physics 64 (2000) 241246
[11] Keunju Park, Dongseok Seo, Jongkook Lee, Conductivity of silver paste prepared from
nanoparticles, Colloids and Surfaces A: Physicochem. Eng. Aspects 313314 (2008) 351354
28
[12] Qian Peng, Yuelin Zhu, Three reductions used in preparation of the silver nano-particle for
crystalline silicon solar cell and its characterization, Advanced Materials Research Vols. 399401 (2012) pp 1524-1527
[13] Yu-Jin Kim, Seong-Jin Hwang and Hyung-Sun Kim, Thermal Properties of Bi2O3-B2O3ZnO Glass System, Materials Science Forum Vols. 510-511 (2006) pp 578-581
[14] Luo Shiyong, Wang Ning, Xu Wencai, Lv Yong, Preparation and rheological behavior of
lead free silver conducting paste, Materials Chemistry and Physics 111 (2008) 2023
[15] Guoxiao Yao, High efficiency metal stencil printed silicon solar cells, PhD thesis, page 2223
[16] Tina E. Rardin, Renmei Xu, Printing Processes Used to Manufacture Photovoltaic Solar
Cells, The Journal of Technology Study, Volume 37, number 2, Fall 2007
[17] Dr. Luis Jaime Caballero, Solar Energy, edited by Radu D Rugescu, Chapter 16 Contact
Definition in Industrial Silicon Solar Cells
[18] Jaap Hoornstra, Arthur W. Weeber, Hugo H.C. de Moor, Wim C. Sinke, The importance of
paste rheology in improving fine line, thick film screen printing of front side metallization, 14th
European photovoltaic solar energy conference and exhibition, 30 June - 4 July, 1997, Barcelona
Bibliography
[1] Screen-printed solar cells,http://pveducation.org/pvcdrom/manufacturing/screen-printed
solar-cells. (Accessed on 10/9/2011)
29
Acknowledgement
I would like to take this opportunity to express a deep sense of gratitude to my guide, Prof. Parag
Bhargava, Department of Metallurgical Engineering and Materials Science, Indian Institute of
Technology, Bombay. His continuous encouragement and competent guidance motivated me and
instilled a sense of confidence in me. I would like to thank Prof. Rajiv Dusane, HOD,
Department of Metallurgical Engineering & Materials Science, IIT Bombay. I would also like to
thank all the faculty & students from our department for their help & support.
30