Nanotechnologies for Photovoltaic Solar Electricity

Generation

Design Group 36

Michael King, ME
Yen-Cheng Lin, ME
Serdar Marcan, CS
Arpit Mehta, ME

Faculty Advisor: Alok Rastogi

May 8th, 2009

Submitted in fulfillment of the requirements of ME494/EECE488 in the Spring Semester of

2009.

Thomas J. Watson School of Engineering and Applied Science

State University of New York at Binghamton
Abstract

The need for inexpensive, clean renewable energy is a serious problem requiring complex
solutions. A way to provide the necessary energy in a less expensive solar cell is demonstrated in
the dye-sensitized solar cell (DSSC). Provided is a detailed method of constructing these cells
complete with a bill of materials and explanation of the use of each material. DSSC currently
cannot compare with the traditional silicon based photovoltaic solar cells, however with an ease
of manufacturability at a fraction of the cost makes this product an interesting alternative for
developing countries. Research was an essential portion of the project, providing techniques for
developing the titanium dioxide deposition and dye selection. Many prototypes were created in
an effort to perfect the mechanical techniques used when fabricating these cells by hand.
Advanced testing was crucial to provide the feedback necessary to hone those skills and enhance
the efficiency of the cells.
Table of Contents

1. Introduction 1

2. Theory 3

3. Prototyping 5
3.1 Bill of Materials 5
3.2 Purpose of Each Material 5
3.3 procedure for Dye-Sensitized Solar Cell 6

4. Research 11
4.1 Discovering laboratory techniques 11
4.2 Titanium Dioxide Deposition & Sintering 11
4.3 Small Glass to Larger Glass 12
4.4 Natural Dye to Synthetic Dye 13
4.5 Natural Dye in DSSC 14
4.6 Research in dyes 14

5. Analysis 15
5.1 Natural Dyes 15
5.2 Synthetic Dyes 20
5.3 Ruthenium Bipyridal Dye 20
5.4 Changing Sealants 22
5.5 Resistance Variable 22
5.6 Testing Voltage versus Current 23
5.7 Calculating Efficiency 25

6. Conclusion 30

- Appendix A: Requirement Matrix A-1

- Appendix B: Block Diagram A-3

- Appendix C: Budget A-4

- Appendix D: Schedule A-5

- Appendix E: Laboratory Pictures A-6

List of Figures

Figure Page
Number Name Number
1 Electron Flow in Titanium Dioxide Dye-Sensitized Solar Cell 3
2 Completed Sintering process 2 inches by 2 inches plate 7
3 Completed Sintering process 1 cm by 1 cm plate 7
4 Soaking dye with sintered TiO2 Cell 8
5 Tin Oxide coating glass with liquid graphite layer 8
6 Assemble the two glass plates 9
7 Clamp the plates together 9
8 Cell, Electrolyte liquid and needle 10
9 Insert the electrolyte solution. 10
Sealing off each edge to protect the electrolyte solution from the
10 atmosphere. 10
11 Nitrogen tube furnace 13
Current (micro-Amperes) versus Time (seconds) for Blackberry Solar
12 Cell with Pencil Backing 15
Voltage (mV) versus Time (seconds) for Blackberry Solar Cell with
13 Pencil Backing 15
Current (micro-Amperes) versus Time (seconds) for Blackberry Solar
14 Cell with Graphite Backing 17
Voltage (mV) versus Time (seconds) for Blackberry Solar Cell with
15 Graphite Backing 17
Current (micro-Amperes) versus Time (seconds) for Pomegranate Solar
16 Cell with Graphite Backing 18
Current (micro-Amperes) versus Time (seconds) for Beet Solar Cel l
17 with Graphite Backing 18
Voltage (mV) versus Time (seconds) for Pomegranate Solar Cell with
18 Graphite Backing 19
Voltage (mV) versus Time (seconds) for Beet Solar Cell with Graphite
19 Backing 19
Current (Amperes) versus Voltage (Volts) for Blackberry Solar Cell
20 Without Illumination 21
Current (Amperes) versus Voltage (Volts) for Blackberry Solar Cell
21 Under Tungsten-Halogen Lamp 23
Current (Amperes) versus Voltage (Volts) for Blackberry Solar Cell
22 Under Tungsten-Halogen Lamp 24
23 Current (Amperes) versus Voltage (Volts) for Blackberry Solar Cell 25
24 Ideal Curve 28
25 Cell with Shunt Resistance 29
26 Cell with Series Resistance 29
27 I-V Characteristic for Current Photovoltaic Solar Cells 30
List of Tables

Table Page
Table Name
Number Number
1 Current and Voltages of Synthetic Dyes 20
1. Introduction

Energy is one of the greatest problems facing current and future generations. Population growth
combined with development in foreign countries has caused the world demand for energy to
increase greatly. According to the Energy Information Administration [1], world demand for
energy will increase by fifty percent from 2005 to 2030, from 462 to 695 quadrillion (1015)
British Thermal Units (BTUs). Much of this growth comes from developing countries such as
India and China.

Unfortunately, the majority of this energy will come from unclean sources such as gas and coal.
As described by the Kuznets curve, when a country initially develops it will take on
environmentally unsound practices while it grows. Countries that have already developed can
afford to enact laws protecting the environment and restrict the amount of pollution coming from
energy production. Natural gas and coal are both the fastest growing forms of energy production
both of which rely on tapping a limited natural resource and pollute the environment when
burned.

The sun provides a potentially unlimited source of energy, at least for the next five billion years.
Humans consume 4.1 x 1020 Joules of electricity per year, while the sun provides 4.3 x 1020
Joules of energy to the Earth in one hour [2]. Not all this energy is harvestable, since most fall on
areas where it cannot be captured and no device will have 100% efficiency, but it shows that the
sun provides an incredible amount of energy. Only a small portion of this energy need be
captured to power humanity’s needs.

Solar electricity’s primary advantage is that it is based on an unlimited, clean resource. Unlike
the energy utilized from coal, solar energy does not output any harmful byproducts when it is
utilized. It does not emit carbon dioxide or greenhouse gases to produce electricity. It is also an
unlimited resource since the sun will continue to provide light to the earth for the next five
billion years. Unlike other resources used for energy, such as petroleum, the sun also is not
controlled by a nation or organization. The sun is a completely independent resource.
The main impediment to the large scale use of solar electricity is economics. Traditional solar
cells, made of silicon, are not cost effective. High purity silicon is the foundation of most
computers and processor products and is naturally a very scarce resource, resulting in a more
costly product. Silicon based cells do not perform well in diffused light, meaning that installation
must be on a roof or an area with an unobstructed view of the sun. Commercial silicon cells are
also quite large. This may become a problem for installation on private residences where the
overall load of the cell combined with the housing component might be too large for the
structural capabilities of the roof. This comes at an added cost to the consumer. The cost of solar
cells must be decreased by at least 25 times in order to compete with fossil fuels. Novel
approaches to solar technology must be considered in order to create a cell that is suitable for
wide-scale use.

The major technical advantage with such nanocrystalline solar cells is the fact that the surface
area of grain boundaries is very high, significantly increasing the density of recombination. The
nanostructure of the titanium dioxide (TiO2) layers acts as a semiconductor “sponge”, absorbing
hundreds of dye monolayers to receive photons from light and release electrons to the titanium
dioxide [3].

These structures also have potential for high absorption due to a higher density at the band edge.
Nano-sized surfaces will have a very close contact area, significantly decreasing the band gap
and increasing efficiency. The larger the band gap the more energy is required to move the
electrons from one end of the junction to the other. Nanowires provide a more direct path for
charge transport to the contacts; whereas dendritic nanowire structures also allow for enhance
light harvesting [4].

The efficiency is increased with decreasing titanium particle size and increasing titanium layer
thickness. Smaller particle size creates larger surface areas for the sensitizing dye to adhere to,
while allowing for greater sun penetration depth. The thicker layers create more electron flow
over the exposed surface area, theoretically creating more current.
Theory

In traditional solar cells silicon performs two primary functions. First, the silicon must accept the
photon from light. Then it must create an electric field to separate the charge particles and create
the flow of electricity. Dye-sensitized solar cells (DSSC) divide the functions into separate
components of the solar cell, as shown in Figure 1.

Figure 1: Electron Flow in Titanium Dioxide Dye-Sensitized Solar Cell

The components of a DSSC are sandwiched between two conductive glass plates. The glass
plates are coated with a layer of tin oxide to allow the flow of electricity across the glass. As
shown in the figure, titanium dioxide is deposited on the top glass plate layer. The
nanocrystalline titanium dioxide layer is highly porous with large a surface area allowing
electrons to freely flow through its surface to the conductive glass layer. Titanium dioxide takes
on the function of charge separation seen in traditional silicon solar cells by allowing the
negative charges to flow through its surface.
As shown in Figure 1, a dye is deposited onto the titanium dioxide layer. The dye takes on the
function of light absorbance since titanium dioxide cannot directly absorb photons from light.
The dye absorbs the photons, which then excites an electron in the dye. The electron is passed
through the titanium dioxide onto the conductive layer of the glass plate. This essentially creates
the anode in the circuit. However, the electron lost by the dye must be replenished. As seen in
Figure 1, the cell contains a liquid electrolyte within it. This is an iodide/triiodide solution.
Iodide gives an electron to the dye, which converts it to triiodide.

Triiodide must be converted back to iodide. The lower layer of conductive plate is coated with a
backing on the conductive side, most commonly consisting of either platinum or carbon. The
backing layer makes up the counter electrode in the circuit and returns an electron to the
electrolyte solution. This makes up the cathode in the dye sensitized solar cell and completes the
circuit. Electricity is the flow of electrons. This cell allows electrons to flow from the dye and
titanium dioxide to power an object, the electrons are then returned through the carbon backing
and electrolyte solution.

The entire process is similar to artificial photosynthesis. A synthetic or organic dye takes the
place of chlorophyll in plants, though actual chlorophyll can be used. Titanium dioxide replaces
carbon dioxide as the electron acceptor in photosynthesis. The electrolyte solution and carbon
backing replaces water and oxygen as the electron donor. The process is regenerative because no
one material is entirely used up by the process [5].

The reactions found in the solar cell are:

Dye + Photon  Excited Dye

Excited Dye + Titanium Dioxide  Free Electron in Titanium Dioxide + Oxidized Dye
Oxidized Dye + 3/2 I- Dye + ½ I3-
½ I3- + e- (from carbon backing)  3/2 I-
3. Prototyping

3.1 Bill of Materials

Ethanol
Nitric/Acetic Acid
Conductive glass plates with the Tin oxide (SnO2) coating
Nanocrystalline Titanium dioxide (TiO2) Degussa P25 powder
Various Dyes- blackberry, beetroot juice or pomegranate juice, Gallium(III),
Coumarin 153, Styrl 7 and B3 (N4) Ruthenium dye
Liquid graphite – Water and Isopropyl based
Ethylene Glycol
Potassium iodide
Potassium iodine
Isopropanol alcohol
Bunsen burner
Multimeter
Convection oven (or furnace)
Binder clips
Glass rod
Mortar
Pestle
Tape
Alligator clip
Solar illumination
Hardman’s EPOXY resin based two part sealant
Voltage current provider
Computing efficiency software program

3.2 Purpose of Each Material

Titanium dioxide (Nanocrystalline TiO2 Degussa P25 powder)

• Covered with sensitized dye

• Dye donates electrons to TiO2

• TiO2 passes electrons to silicon dioxide and then to the external circuit

Conductive glass plates (Tin oxide or SnO2 coating)

• Two glass plates hold the solar cell, top glass having layer of TiO2 and
graphite layer is on the bottom glass

• Glass allows light (photons) to pass through to dye

• Conductive coating of Tin oxide (SnO2) on glass receives electrons from

TiO2, passes it to electrical circuit
 Sensitized Dye
• Coats TiO2

• Receives photons and releases electrons through TiO2 to conductive glass

• Absorbs light radiation

Electrolyte (Potassium iodide and iodine (Iodide/electrolyte solution))

• Surrounds TiO2 in solar cell

• Creates voltage potential between itself and TiO2

• Allows flow of electrons by voltage potential

• Restores electrons to dye to maintain circuit

Backing (which is graphite or platinum layer, is on the bottom glass)

• Completes electric circuit by providing counter-electrode

• Provides electron to triiodide to convert it back to iodide

Sealant
• The electrolyte solution is very sensitive to light and the water or even
moisture from the air, therefore seal off the cell to prevent cell interaction
with air.

3.3 Procedure for Dye-Sensitized Solar Cell [6]

1. Lab coat and gloves are advised when working in chemistry labs.

2. Identify the conducting side with the tin oxide coated glass piece by using a
multimeter to measure resistance. The conductive side will have a resistance
of 20-30 ohms with 2 inches by 2 inches area of glass.

3. Tape the glass with 3~4 mm wide tape on the one side edge at conducting side
up for electrical contact, then wipe off any contaminants or oils by using
tissue wet with Acetone.

4. Dilute Acetic acid to a pH level of 3, slowly pour the acid into the water,
down the side of the container - never pour the water into the acid.
5. Grind about 1 gram of nanocrystalline titanium dioxide (TiO2) Degussa P25
powder in a mortar and pestle while gradually adding 1.66 ml diluted Acetic
acid until obtain a colloidal suspension with a smooth consistency, somewhat
like latex paint.

6. Replace some of the TiO2 suspension (paint) and quickly apply on the
conductive side of glass plate evenly with a glass rod. Proper spacer thickness
is recommended to be 7~10 micrometers of TiO2. (The TiO2 layer may
propagate large cracks and peel off easily if the TiO2 layer is too thick)
Quickly move the glass plate to pre-heated convection oven with 100~150
degree Celsius to dry.

7. Carefully remove the tape without scratching the TiO2 layer.

8. The sintering process in the convection oven or furnace occurs at 450 degrees
Fahrenheit for approximately thirty minutes. It has completed once the surface
turns to a light green color while heating. The titanium dioxide changes back
to white once the sample has returned to a lower temperature, as shown in the
following Figures 2 and 3.

Figure 2. Completed sintering process for 2 inches by 2 inches plate

 Figure 3. Completed sintering process for 1 cm by 1 cm plate

9. After cooling off, soak with the dye of your choice until the titanium dioxide
has become completely immersed in the dye. This could take anywhere to 48
hours to a full week. A uniform color on the back of the glass side is a key
indicator to when the cell is ready, shown in Figure 4 Below.

Figure 4. - Soaking dye with sintered TiO2 Cell

10. Rinse gently with water and then with ethanol (the ethanol serves to remove
water from the porous TiO2)
 11. The second tin oxide glass plate is coated with a liquid graphite layer on the
conductive side as shown in Figure 5. Allow the sample to air dry. Step 3
should be performed prior to the liquid carbon application.

Figure 5. Tin oxide coated glass with liquid graphite layer

12. Place the fully dried carbon coated glass into the convection of and bake at
150 degrees Fahrenheit for approximately twenty minutes. After removing
from the oven and cooling, test the surface of the carbon with a multimeter.
Should the resistance of the carbon still be out of the desired range of one to
three hundred ohms, place back into the oven for another ten minutes and
retest with multimeter after cooling.

13. Assemble the two glass plates with dyed TiO2 and liquid carbon layers
touching each other, but offset so that uncoated glass extends beyond the
sandwich for electrical contact as shown in Figure 6. Do not rub or slide the
plates. Clamp the plates together as shown in Figure 7.

Figure 6. Assemble the two glass plates Figure 7. Clamp the plates together
14. The electrolyte solution is made with the ratio of 10ml of Ethylene Glycol
with 0.127g of I2 and 0.83g KI. The electrolyte solution is very sensitive to
light and the water, even moisture from the air could damage the solution.
Close the bottle tightly and avoid exposure to light, as shown in Figure 8.

15. Insert few drops of electrolyte solution between the glass plates as seen in
Figure 8 and connect to a multimeter with alligator clip to each plate’s
electrical contact area to test the current and voltage produced by solar
illumination.

16. Clamp the two glass plates together and quickly seal the top, left and right
edges of the cell as illustrated in figure 9. Be sure to hold the cell upright
allowing the electrolyte to flow out of the bottom.

Figure 8. Insert the electrolyte solution.

 Figure 9. Sealing off each edge to protect the electrolyte solution from the atmosphere.

Figure 10. Sealing off each edge to protect the electrolyte solution from the atmosphere.

17. Once the three sealed sides has had time to properly set, approximately five to
ten minutes. Inject approximately 0.5 ml of the KI electrolyte solution.

18. The hope is to retain as much of the electrolyte solution in the cell before
being completely sealed. Once the cell no longer absorbs any of the
electrolyte, dry properly and seal with the resin based epoxy

19. Once the final edge has seal properly use a small amount of acetone and water
to clean the surfaces of the cell of any dirt or excess sealant. It may be
necessary to use a small razor to scrape and unwanted sealant away.

20. Using voltage as an input through the cell, a computer program captures
current versus voltage data. This data can be used to calculate the efficiency of
the cell.

4. Research

4.1 Discovering laboratory techniques for creating solar cell

All initial laboratory techniques were provided by Professor Alok Rastogi in the research paper
Titanium Dioxide Dye Sensitized Solar Cells [7]. No publication or author name was attached,
but the article did provide information on the newly researched cell. Adequate details into the
chemical structure of the electrolyte solution as well as the titanium dioxide layers were given.
The author suggested that similar cells have reached efficiencies of ten percent at fifty watts per
square meter (50W/m2). These are very exciting results with large scale possibilities given the
easy manufacturability of this product.

Through extensive research from peer reviewed publications, the process of creating these solar
cells was simplified. The Binghamton University Library’s electronic catalog of scientific and
technical journals was the foundation of our research in cell construction and dye selection. The
initial unnamed paper suggested using a ruthenium bipyridal dye, which is still currently used in
commercial applications. This dye is expensive and difficult to synthesize so to cut the overall
cost of this product, less expensive chemical dyes were purchased.

The co-creator of this brand of photovoltaic cells, Michael Grätzel has numerous publications
which were very important to our design process. Confirming the quoted results from the
mystery paper with information from a reputable author and source was necessary to justify our
design method. The paper Demonstrating Electron Transfer and Nanotechnology: A Natural
Dye-Sensitized Nanocrystalline Energy Converter [8] explained in much greater detail how
titanium dioxide cells have the capability of creating a current with either sophisticated
chemicals or natural dyes.

4.2 TiO2 Deposition and Sintering

The application of the titanium dioxide is of particular importance to ensure the success of
creating a highly efficient cell. The titanium dioxide is prepared in a solution of acetic acid and
water. The application of the titanium dioxide to the conductive glass can be done on a variety of
ways when in a solution form. A centrifuge can be used to ensure an even coating, but a large
amount of material is lost in the process. Spray and brush methods posed the potential of
contamination. The method chosen was a small diameter glass rod where the titanium dioxide is
rolled on in even layers. An even layer is ideal for dye absorption and to ensure that light can
transmit through the cell.
Discovering techniques for consistently developing these cells took time and many prototypes.
Mastering the application of the titanium dioxide is so important because cracks easily
propagate. This is particularly troubling because of the potential of short circuiting the cell
should the electrolyte solution make contact with tin oxide conductive backing. Only by
fabricating many titanium dioxide samples would it be possible to determine what exactly makes
a stable sample.

To combat this problem an optical microscope was used to observe which sintering method was
the most consistent with required specifications. The air flow and temperature conditions prior to
sintering were tested for a hot air gun, hot plate with steady state airflow conditions and free air
flow. Examining the size and pattern of cracks, the hot plate at 100 degrees Celsius had the best
results after several trials.

4.3 Movement from small glass plates to large glass plates

Professor Rastogi provided a small sampling of conductive glass to be used in the beginning
trials of the titanium application. Four inch square conductive glass plates were obtained to be
used in combination with synthetic dyes to produce larger current outputs. Larger glass plates
introduced new difficulties in creating a uniform layer of titanium dioxide. Another concern was
that samples could no longer fit into the nitrogen tube furnace which had since been used to
sinter all titanium dioxide shown in Figure 11. It was decided to purchase a convection oven
from a local retail store to replace the furnace.
 Figure 11. Nitrogen tube furnace

Commercial convection ovens are coated inside and out with several varnishes for scratch
resistance and aesthetic look. The particulates from these varnishes contaminated the titanium
cells during the sintering process, turning the samples a red-brown color. To resolve this issue the
convection oven was left on for approximately one half hour to effectively burn off the interior
sealants. Also small aluminum protective coverings were assembled for the conductive glass
while inside the convection oven. Leaving the oven door during sintering helped to prevent
contamination. This was to promote even heating throughout the cell.

The overall goal has remained to create a cell which will operate with an efficiency between
three and five percent. Larger conductive glass pieces would allow for ease of creating a small
panel to be analyzed in direct and diffused light conditions.

4.4 New Methods for Sintering

Previously a tube furnace was used to heat the titanium dioxide layer on the conductive glass
plate. However, the larger glass plates would no longer fit in the tube furnace. In order to heat the
titanium dioxide layer to 450 degrees Celsius, a Bunsen burner was originally used. The Bunsen
burner was able to heat the glass plate to the requisite 450 degrees. It turned the titanium dioxide
to the yellow-green color that shows the sintering is finished. However, upon removal from the
Bunsen burner, the titanium dioxide would appear singed and brown at the edges.

A hot plate on the highest setting was used to heat the glass plate. The hot plate was able to sinter
the layer more quickly than the Bunsen burner and was able to heat more than one
simultaneously. The hot plate was then used over the Bunsen burner to heat he titanium dioxide
layer. The only problem with the hot plate was that if the glass plate was removed too quickly,
then the glass plate was cracked. It also could crack if left on the plate too long. This problem
was mitigated by heating the glass plates on top of a steel sheet placed on the hot plate.

4.5 Movement from natural dyes to synthetic dyes

It was suggested in multiple research papers that natural dyes could replace the chemical dyes at
the cost of the desired efficiency levels. This is possible because the requirements for an effective
dye are to darken the titanium, enhancing sunlight absorption and to create electrons through a
process similar to artificial photosynthesis. Pomegranate seeds, blackberries, and beet root were
used in place of the expensive chemical dyes. Natural dyes performed well but as expected not
up to the desired three to five percent because of the impurity of the solution. To gain a larger
output current from the given area, chemical dyes were necessary.

4.6 Research various types of dye used in DSSC

Michael Grätzel’s Conversion of sunlight to electric power by Nanocrystalline dye sensitized

solar cells is where an ideal dye sensitizer is described. The majority of the study in the dye is
the delicate balance between the energy producing requirements in the natural sunlight while
remaining stable in the photo-electrochemical environment. Ruthenium bipyridyl or N3 dyes
were suggested again as the most effective sensitizer quoting that “has been unmatched for eight
years by virtually hundreds of other complexes” [9]. Seeking a less costly alternative, organic
coumarin dyes showed efficiency results of approximately eight percent. Coumarin 343 is known
to excite electron movement in titanium dioxide at a much higher rate than most competitive
dyes, however the wavelength at which the coumarine absorbs the dye is lower than desired and
the range is limited.

5. Analysis
5.1 Natural Dyes

Initial solar cells were created using natural dyes from certain fruits, such as blackberries,
pomegranate, and beets. The first solar cell was created using a cell soaked in blackberry juices.
Since the liquid graphite was not obtained yet, the backing was created using graphite from a
lead pencil. The current and voltage of this cell is shown below:
 Figure 12: Current (micro-Amperes) versus Time (seconds) for Blackberry Solar Cell with Pencil Backing

Figure 13: Voltage (mV) versus Time (seconds) for Blackberry Solar Cell with Pencil Backing

In both figures, the cell is initially exposed to natural sunlight. After a certain point, the sunlight
is blocked and the effects on the cell are observed. In Figure 12, the current starts off at
approximately 3 micro-amperes, but begins to decrease slowly from the initial value in sunlight.
The sunlight is blocked after 3 seconds, and the current drops precipitately. The current goes to
1.5 micro-amperes, a decrease of over half. However, there is still some current produced,
showing that the cells are able to work in diffuse light. The sunlight is blocked, but it still picks
up enough light being reflected by the surroundings to produce some current. The current for this
cell is very low compared to later natural dye solar cells.

Figure 13 shows the voltage produced by the cell. The voltage starts off at 325 millivolts and
starts to gradually increase from there. After 7 seconds, the sunlight is blocked and the voltage
begins to drop. The voltage decreases to approximately 290 mV. While the voltage does decrease
with reduced light, it does not show as large of percent decrease as the current.

Voltage measures the electrical potential between two areas. The measured voltage was as
expected, while the current was low. In a dye-sensitized solar cell, a strong voltage between the
anode and cathode implies that the cell was properly made and the components are functioning
properly. The cell is able to create a potential difference. However, the low current implies that
the electrons are not able to freely flow from the anode to cathode.

The low current is likely a result of the dye used, since fruit dyes are an impure substance.
However, greater currents were produced using fruit dyes in later experiments. In this case, the
poor current was most likely a result of the pencil backing. The pencil backing initially used
probably could not produce a full, even coating on the conductive glass plate. This would result
in a decreased current.

Solar cells were later produced using liquid graphite. Liquid graphite provided a much more
complete coating of the glass surface. Voltage and current were tested again with a blackberry
solar cell.

Figure 14: Current (micro-Amperes) versus Time (seconds) for Blackberry Solar Cell with Graphite Backing
 Figure 15: Voltage (mV) versus Time (seconds) for Blackberry Solar Cell with Graphite Backing

As shown in Figure 14, the current is much larger in the solar cell with liquid graphite coating
compared to the cell with a pencil coating. The current starts off very high, at 35 micro-Amperes
and then gradually decreases to 26 micro-Amperes on its own. After approximately 15 seconds,
the sunlight is blocked. The current gradually decreases to less than 15 micro-Amperes. As in the
case of the first solar cell, blocking sunlight decreases the current by approximately 50 percent.
The cell still produces some current in blocked sunlight, showing that the cell still functions
under diffuse light.

As shown in Figure 15, the voltage is similar to that of the original cell. In this case, the voltage
is actually somewhat lower. The voltage slowly drops, even when exposed to sunlight. At
approximately 20 seconds, the light is blocked and the voltage drops slowly. It does not drop as
much as the current does in reduced light.

The experiment was repeated for different types of fruit – pomegranate and beet. At this point,
only the liquid graphite backing was used due to superior results.
Figure 16: Current (micro-Amperes) versus Time (seconds) for Pomegranate Solar Cell with Graphite Backing

Figure 17: Current (micro-Amperes) versus Time (seconds) for Beet Solar Cel l with Graphite Backing

Figure 18: Voltage (mV) versus Time (seconds) for Pomegranate Solar Cell with Graphite Backing
 Figure 19: Voltage (mV) versus Time (seconds) for Beet Solar Cell with Graphite Backing

Figure 16 and 17 show current for the solar cells made from the dyes of pomegranate and
blackberry. Both the pomegranate and blackberry decrease in current from their initial values. In
the pomegranate, the sun is blocked at 18 seconds. While the solar cell continued to decrease in
current, it did not show the marked decrease in current as in the other cases. The beet solar cell
was removed from sunlight at approximately 20 seconds. It shows the noticeable decrease in
current. The current declines from 25 micro-Amperes to 15 micro-amperes.

Figure 18 and 19 show voltage for both solar cells. The pomegranate shows a strong voltage of
400 mV, while the beet shows a voltage more in line with the rest of the solar cells made. The
pomegranate voltage decreased slightly from its initial value of 418 mV. The sunlight was
removed at 13 seconds. The voltage showed increasing decline, but the voltage still remained
high. The voltage for the beet remained relatively stable at around 200 mV, though it declines
slightly through the curve. It only declined slightly when the sunlight was removed at 18
seconds.

5.2 Inittial Synthetic Dyes

The first three synthetic dyes were tested on larger conductive glass plates, with an area of 4 cm2.
The following table summarizes the result of these experiments:

Dye Current (micro-Amperes) Voltage (mV)

Styryl 7 70 90
Coumarin 153 150 200
Gallium 40 80
 Table.1 Current and Voltages of Synthetic Dyes
In each case, the current and voltages were lower than expected. The Styryl 7 dye and Gallium
dye both produced very small voltages, showing that there are deficiencies in the solar cell. The
deficiencies both seem to be attributed to the dye. The Styryl 7 did not bind to the titanium
dioxide layer. The titanium dioxide layer is usually stained the color of the dye, but the Styryl 7
color did not remain on the dye after it was removed from the solution. This dye may not be
compatible with titanium dioxide.

The Gallium dye stained the titanium dioxide a very light blue color. This dye may not be very
highly absorbent of photons or only absorbs in a narrow wavelength range, leading to the low
results from the Gallium solar cell.

Of the first three synthetic dyes, the Coumarin 153 solar cell produced the best results. It
produces a voltage similar to that of the fruit solar cells. The current is higher than those
achieved by the fruit dyes, though it is lower on a per area basis. The synthetic dyes were tested
on an area four times that of the fruit solar cells.

5.3 Ruthenium Bipyridal Dye

Coumarin 153, Gallium (III) phthalocyanine chloride and Styrl 7 were purchased, synthesized
and thoroughly tested during the fall semester and proved to be ineffective for the required
applications. After several discussions with Professor Rastogi, it was decided that the more
expensive ruthenium B3 (N4) dye would be purchased in an effort to prove that significant
power could be produced from these small area cells. A chemical manufacturer in Australia
named DyesolTM was able to provide one hundred milligrams of ruthenium bipyridyl dye and
advised to synthesize in ethanol. While combining the dye with the ethanol it was observed that
small particulates would not dissolve. An ultrasonic water bath was easily able to break down the
particulates resulting in a homogenous liquid dye.

Logic would suggest that a more uniform, dark color would lead to an increased rate in light
absorption and thus increase the likelihood of enhanced efficiency. While experimenting with the
initial three synthetic dyes all titanium dioxide samples were placed face up in a Petri dish where
the dye was applied with a dropper until the surface was covered. This process was repeated
several times until the surface retained the color of the respective dye, shown in figure 4. Prior to
using the first batch of ruthenium bipyridal dye, Prof. Rastogi suggested submerging the cell in a
bath of the dye until all color had been removed by the nano-pores of the titanium dioxide.
Extending the amount of time which the titanium dioxide had to soak in the N3 dye along with
the immersion technique, vastly improved the dye absorption and increased efficiency was
achieved. This extension in time however greatly increased the time for one photovoltaic cell to
be completed. The difference in color associated with a longer soak time can be seen in figure
20.

Figure 20. Full bath and longer soak results in darker samples

5.4 Changing Sealants

The 832 Dow Corning multi-surface sealant was the chosen method of sealing the photovoltaic
cells from atmospheric conditions in the original cell fabrication trials. The silicone sealant
proved to be difficult to apply and would remain tacky to the touch even twenty four hours after
application. This was not sufficient for the needs described in the customer requirements matrix.
After consulting with Bob Kaub and the staff in the student design shop, a resin based two part
epoxy sealant was chosen mostly due to the fact that it totally seals within minutes. The chemical
characteristics of the sealant were researched to ensure that the sealant would not chemically
interfere with the process taking place inside of the photovoltaic cell. Switching from the silicone
to the epoxy sealant was beneficial because now construction, cleaning and testing could now
occur in a span of hours not days.
The epoxy seal not only significantly decreased the time necessary to obtain a proper seal from
atmospheric conditions, but also had an overall greater aesthetic appeal. As shown in figure10
the grey Dow Corning seal looked unfinished and poorly applied whereas the clear epoxy sealant
leaves a clean finish.

5.5 Resistance Variable

An unknown variable was causing the tail end of the voltage vs. current graph to display
uncharacteristic behavior. Discussing these results with Professor Rastogi, he explained that the
main reason this characteristic in the plot was due in part to the large resistance being provided
by the carbon backing. Throughout this senior project a liquid carbon backing with an isopropyl
alcohol base would act as an electron donor for the potassium electrolyte solution. This carbon
backing had a resistance of approximately one to five kilo-ohms after application and drying
onto the conductive glass plate. This large resistance was believed to be the reason for the “tail”
of our I-V curves to have the result as shown in Figure 26. Professor Rastogi suggested that we
heat our carbon coated conductive glass just the same as we would our titanium dioxide coated
conductive glass. The hope of this process was to dramatically reduce the overall resistance.
After approximately twenty minutes in the convection oven the resistance dropped to astounding
range of one hundred to three hundred ohms. This dramatic decrease in resistance led to a large
increase in current output.

5.6 Testing Voltage versus Current

Once the initial design was set, testing variations based on engineering judgment was crucial to
the overall direction of the analysis. By determining from the initial cells that a thin, even and
uniform dyed titanium dioxide would yield the best results.

The efficiency of a solar cell can be calculated by measuring the short circuit current, open
circuit voltage, and maximum power produced by the cell. Using a power supply and computer
data acquisition software, the current through the solar cell was measured for a range of supplied
voltages. The solar cell was tested both under darkness and illumination by tungsten-halogen
lamp. In this case, a blackberry stained solar cell on the larger conductive glass plates was used
because it yielded the largest measured current at over 3 milliamperes. The solar cell was tested
from the range of -1 volt to 1 volt at intervals of 0.1 volts, leading to 21 data points. Since
electron flow is forced through the solar cell, higher voltages cannot be used otherwise
components of the cell may be damaged. An efficient dye-sensitized solar cell naturally operates
between 0.4 – 0.7 volts; the testing voltage should be kept near this range.

Figure 21: Current (Amperes) versus Voltage (Volts) for Blackberry Solar Cell Without Illumination
Figure 22: Current (Amperes) versus Voltage (Volts) for Blackberry Solar Cell Under Tungsten-Halogen Lamp

Comparison of Figure 21 and Figure 22 shows the solar cell positively responds to light. In
Figure 21, the current goes through the origin at zero volts. In Figure 22, the current is much
higher at 4 mA at 0 volts. In general, the current is higher at each point in the solar cell under
tungsten-halogen lamp illumination. Each curve takes on a noticebly different shape. The cell
without light has a “S-shaped” curve because the current decreases with voltage, while the
illuminated cell has a concave shape because the current continues to increase over the span of
voltage. This shows the cell is producing power.

5.7 Calculating Efficiency

 Figure 23: Current (Amperes) versus Voltage (Volts) for Blackberry Solar Cell Under Illumination
Focus on Maximum Power Produced As Shown By Rectangle

As shown in Figure 23, to determine the power produced by a solar cell, the rectangle with
maximum area under the curve in the fourth quadrant must be determined. It must be in the
second quadrant, where voltage is negative and current is positive, because this is where the
maximum power produced by a solar cell is located. The maximum power produced by the cell
can be calculated from:

Pmax = I × V

where P is the maximum power, I is current, and V is voltage. The voltage and current are those
for the maximum area rectangle under the curve.

Pmax = 0.3 Volts * (1.96 * 10-3 Amperes)

Pmax = 5.9 * 10-4 Watts

A common measure of solar cell efficiency is the fill factor. The curve in Figure 23 takes on a
concave shape. The shape of the curve of an ideal solar cell will be a rectangle, with current
constant over the voltage range of the solar cell. The fill factor is a ratio which measures how
well this curve matches a rectangle in the ideal case. Fill factor is defined as:

Pm
FF =
I SCVOC

where FF is the fill factor, Isc is the short circuit current, and VOC is the open circuit voltage. The
short circuit current is the y-intercept of the IV curve, while open circuit voltage is the x-
intercept.

FF = (5.9 * 10-4 Watts)/( 3.9*10-3 Amperes * .5 Volts)

FF = 0.30

The fill factor is low in this case. Solar cells with over 10% efficiency typically achieve fill
factors over 0.7. The low fill factor is mostly likely due to the crude blackberry dye used. Using a
ruthenium bipyridyl dye could result in a much higher fill factor.

Typically for solar cells, efficiency is:

PM
η=
E × AC

where η is efficiency, PM is maximum power, E is the irradiance, and AC is the surface area of the
solar cell. E is typically taken to be 1000 W/m2 to simulate testing a solar cell on a bright day.
Using this measure, the efficiency of the solar cell is calculated.

η = (5.9 * 10-4 Watts)/(100 W/m * 0.0004 m2)

η = 0.0001475 = 0.1475%

This value of efficiency is low, considering typical silicon solar cells achieve efficiencies of 10%.
However, dye-sensitized solar cells achieve lower efficiencies than silicon solar cells and
blackberry dye severely limits the efficiency. The use of a ruthenium bipyridyl dye would result
in efficiency over 5%.

In dye-sensitized solar cells, the efficiency is often measured using the following formula:

i ph × VOC × FF
η=
E
I SC
i ph =
AC
where iph is the integral photocurrent density, VOC is the open circuit voltage, FF is the fill factor,
and E is the intensity of light. The integral photocurrent density is the short circuit current
divided by the surface area of the cell.

iph = (3.9 * 10-3 Amperes)/(0.0004 m2)

iph = 9.75 Amp/m2

η = (9.75 Amp/m2)(0.5 Volts)(0.30)/(1000 W/m2)

η = 0.0014625 = 14.625%

This returns a similar efficiency to the other formula.

The spring semester’s data was collected using the Keithley 2602 power source meter, as
compared to the Keithley 2400 used last semester. The power source meter provides the voltages
at various ranges and intervals, while measuring the current through the solar cell. The Keithley
2400 only measured data at very discrete points and ran slowly. It collected data at every 0.05
Volts. It also was subject to jumps and spikes in the data due to randomness and a poor
connection.

The Keithley 2602 and software was able to collect data more quickly than the previous model.
It also collected more data points, leading to smoother curve. Accurate data points were produced
because the Keithley 2602 collected five points per voltage point and then averaged the values.
Cells were initially tested with a digital multimeter to check the voltage and current output of the
cell. However, this test only gives a generally idea of the efficiency of the solar cell. In order to
determine the exact efficiency, the current-voltage curve must be determined. To derive the
current-voltage curve (I-V curve or I-V characteristic), a range of voltages must be supplied to
the solar cell. These voltages will produce a certain current within the cell. These currents reveals
how well the cell is working.

The I-V characteristic is useful for more than calculating the efficiency of the solar cells. The I-V
characteristic helps “troubleshoot” the cell by analyzing the shape of the curve. As shown below,
different curve shapes reveal problems with the solar cell. Ideally, the I-V curve should take on a
rectangular curve shape, as shown below.

Figure 24: Ideal Curve

This shape produces a solar cell with higher efficiency. A curve with a steep upward slope and
highly concave shape, as shown below, implies a lower shunt resistance. This implies that the
internal current shorts.
 Figure 25: Cell with Shunt Resistance

A curve that starts off flat and then spikes upward implies higher series resistance. This implies
that the back contact is poor.

Figure 26: Cell with Series Resistance

Below is a plot of the data from the most efficient solar cell:
 Figure 27: I-V Characteristic for Current Photovoltaic Solar Cells

While this cell displayed the greatest current achieved, it still shows some shunt resistance,
showing that even higher efficiencies are possible with these cells. Using the formulas previously
mentioned, the efficiency of the cell is 0.5%.

Conclusion

The titanium dioxide dye-sensitized solar cell is a very exciting product with real world
applications when further research increases the efficiency of these relatively inexpensive cells.
When creating these cells in large quantities it became clear just how many variables are
included in the sensitive chemical reactions which create energy. For example, the titanium
dioxide’s consistency was a major concern because of its delicate nature when sintering. The
acetic acid solutions needed to be tested to ensure they fell within the correct ph range. Our
sealant was scrutinized to ensure that no air could penetrate the cell, drying the electrolyte
solution which destroys the cell. The carbon backing needed to be prepared and heated to reduce
the high resistance. Should the long list of complications be addressed in one DSSC cell, all of
our energy needs could in effect be solved.
References

[1] Energy Information Administration, Electric Power Monthly U.S, Department of Energy
(June 2005); available at hup://ww w.eia.doe.govJcncllfleleclrid ty/epmJchapJ.pdj

[2] Energy Information Administration, Electric Power Monthly U.S, Department of Energy
(June 2005); available at hup://ww w.eia.doe.govJcncllfleleclrid ty/epmJchapJ.pdj

[3] Michael Grätzel (2006). The magic world of nanocrystals, from batteries to solar cells.
Current Applied Physics: An official journal of the KPS, 6S1 e2-e7.

[4] Loucas Tsakalakos (2008). Nanostructures for photovoltaics. Materials Science and
Engineering, R62 175-189.

[5] Michael Grätzel (2004). Conversion of sunlight to electric power by nanocrystalline dye-
sensitized solar cells. Journal of Photochemistry and Photobiology, 164 3-14.

[6] Greg P. Smestad (June 1998). Demonstrating Electron Transfer and Nanotechnology: A
Natural Dye-Sensitized Nanocrystalline Energy Converter. Journal of Chemical Education, 75
(6), 752-756.

[7] Chris X (?). Titanium Dioxide Dye-Sensitized Solar Cells

[8] Greg P. Smestad (June 1998). Demonstrating Electron Transfer and Nanotechnology: A
Natural Dye-Sensitized Nanocrystalline Energy Converter. Journal of Chemical Education, 75
(6), 752-756.

[9] Michael Grätzel (2004). Conversion of sunlight to electric power by nanocrystalline dye-
sensitized solar cells . Journal of Photochemistry and Photobiology, 164 3-14.
Appendix A: Requirements Matrix

The requirement matrix completed in the beginning weeks of the project was crucial to the most
important aspect of the design process, organization. Clearly defining each aspect of the entire
project for the instructors and advisors approval was an effective way of elaborating on the
processes taking place. The first semester saw many changes to the requirement matrix as the
project began to evolve and details changed.

Test Plan
Derived Derived - Derived to meet
Shall # Shalls Requirements Requirements Req.
2. b. Use
Create Voltage
nanofibers Testing
Build and study the through various Program to
components of a means to Efficiency must Measure
Shall #1 Titanium Dye create solar meet at least 2 - Current
Sensitized Thin Film cell, while 5% Output
Solar Cell actively Calculate
studying all its Area Under
components Curve for
Efficiency
Using UV lamps
Must try at least
Study, test and and natural
3 various dyes
demonstrate the sunlight, test 2.a. Digital
Shall #2 Experiment with
properties of the working solar Multimeter
different methods
working solar cell cell for
of production
efficiency limits
Design a simple
software
package which
will effectively Animation
Create simulation 3. b. Visual
test the output Software to
software for and
Shall #3 voltage based Display Effect of
photovoltaic cell Software
on absorbed Wavelength of
analysis Check
sunlight. With Absorption
emphasis on
sesitivity to UV
light radiation.
 With a more
specific
understanding
of a
photovoltaic
Research new
solar cells 3.c.
materials for design
Shall #4 contruction and Software
of new photovoltaic
internal Check
cell
reactions,
creatively
research new,
low cost
materials
2.b. Use
Using the
Voltage
created
Testing
software
Program to
package, test
Measure
Simulation test of the newly
Shall #5 Current
new materials researched
Output
material's
Calculate
properties for
Area Under
future build
Curve for
considerations
Efficiency
Create the new
2.b. Use
material
Voltage
previously
Testing
researched and
Program to
perform "real
Efficiency must Measure
world" test for
Shall #6 Test new design meet at least 5- Current
efficiency in
10% Output
both laboratory
Calculate
and natural
Area Under
settings (UV
Curve for
Lamp/Direct
Efficiency
Sunlight)
Appendix B: Block Diagram

The block diagram is a symbolic representation of the scope of this senior design project. By
simplifying the entire process into a few key steps, an objective observer can easily ascertain the
decision making and can give objective advice.
Appendix C: Budget

Materials Labor
• Acetic Acid - $10 • $100 per hour x 10 hours a week x 3 people

• Nitric Acid - $10 Total Labor = $3,900

• Glycol - $10

• Titanium Dioxide Powder – $30 Laboratory Space

• Sealant - $75 • Economy Solid Tube Furnace - $1,560

• Dyes - $120 • Digital Scale $125

• Iodine - $40 • 400 ml beakers x 2 - $10

Total Materials = $221 • Mortar and Pestle - $26

Total Cost of Semester = $5,842.01

This is overall budget summary for the first semester. The senior project provided $100 dollars
per person, therefore the total budget was $300 for a group of three. In order to begin work on
the solar cell, initial supplies such as mortar & pestle and chemicals, were purchased at
Binghamton University Science Store. Sealant was purchased online, while the convection oven
and lamp were purchased locally. Conductive glass plates, titanium dioxide, laboratory space,
and synthetic dyes were provided by Professor Alok Rastogi.
Appendix D: Budget

Materials Labor
• Acetic Acid - $10 • $100 per hour x 10 hours a week x 3 people

• Nitric Acid - $10 Total Labor = $3,900

• Glycol - $10

• Titanium Dioxide Powder – $30 Laboratory Space

• Sealant - $75 • Economy Solid Tube Furnace - $1,560

• Dyes - $120 • Digital Scale $125

• Iodine - $40 • 400 ml beakers x 2 - $10

Total Materials = $221 • Mortar and Pestle - $26

Total Cost of Semester = $5,842.01

This is the entire budget breakdown from the first semester of the senior design project. The
materials were paid for by the allotted three hundred dollars from the class fund. All laboratory
space and supplies were provided by Professor Rastogi.
Appendix E: In lab pictures

1. Testing TiO2 layer sintering with the hotplate at 450 degree F; result was unsuccessful
due to the heat could not concentration focus on the cell enough.

2. Testing TiO2 layer sanitizing by the Furnace at 450 degree F; result was successful.

3. Testing TiO2 layer sanitizing by the convection oven at 450 degree F; result was
successful.

4. Prototyping natural dyes from Black berry, Beet root and Pomegranate juice.
5. Prototyping standard dyes from Coumarin 153, Styrl 7 and Gallium (III) Phthalocyanine
chloride.
6. Assembly with the liquid Graphite and insert the electrolyte solution and seal off to
isolate the moisture from air.
7. Testing efficiency and compare the result by natural light or lamp and through computer
program.