Solar

Energy Conversion: Making a Dye-Sensitized TiO2 Solar Cell

Objectives: Students will be able to:
Explain how a dye-sensitized solar cell (DSSC) works
Prepare a DSSC using crushed blackberries, to serve as the source of sensitizer molecules
Explain why sensitizer molecules are required for successful operation of the DSSC
Explain why high surface area TiO2 is vital to the successful operation of the DSSC
Explain why I-/I3- electrolyte is needed
Explain why DSSCs require certain colors of light in order to generate the most power

California Content Standards:
Physics:
Conservation of Energy and Momentum:
2.h. Students know how to solve problems involving conservation of energy in simple systems
with various sources of potential energy, such as capacitors and springs.

Waves:
4.e. Students know radio waves, light, and X-rays are different wavelength bands in the
spectrum of electromagnetic waves whose speed in a vacuum is approximately 3 x 108 m/s
(186,000 miles / second).

Electric and Magnetic Phenomena:
5.a. Students know how to predict the voltage or current in simple direct current (DC) electric
circuits constructed from batteries, wires, resistors, and capacitors.

Chemistry:
Conservation of Energy and Stoichiometry:
2.a. Students know how to describe chemical reactions by writing balanced equations.

Acids and Bases:
5.a. Students know acids are hydrogen-ion-donating and bases are hydrogen-ion-accepting
substances.

Solutions:
6.a. Students know the definitions of solute and solvent.

Biology/Life Sciences:
Cell biology:
1.f. Students know usable energy is captured from sunlight by chloroplasts and is stored through
the synthesis of sugar from carbon dioxide.

Earth Sciences:
Energy in the Earth System:
4.a. Students know the relative amount of incoming solar energy compared with the Earths
internal energy and the energy used by society.
4.b. Students know the fate of incoming solar radiation in terms of reflections, absorption, and
photosynthesis.

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High School Lesson Plan
 Solar Energy Conversion: Making a Dye-Sensitized TiO2 Solar Cell


Biogeochemical Cycles:
7.a. Students know the carbon cycle of photosynthesis and respiration and the nitrogen cycle.

Investigation & Experimentation:

1.a. Students will select and use appropriate tools and technology to perform tests, collect data,
analyze relationships, and display data.
1.l. Students will analyze situations and solve problems that require combining and applying
concepts from more than one area of science.


Before you begin, you may want to watch the DSSC videos to prepare the lab:
http://www.youtube.com/caltech and click on Resources for Teachers on the right.

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High School Lesson Plan
 Solar Energy Conversion: Making a Dye-Sensitized TiO2 Solar Cell


Background:
A solar cell is a light sensitive material that can collect solar energy and convert it into
electrical/chemical energy (see Physics lesson). In this lab you will create a solar cell that mimics the
architecture used in natural photosynthesis. The solar cell that you will create will be made of readily
available materials: TiO2 paste (essentially white pigment, that absorbs little light), anthocyanin dye
(from blackberry juice), electrolyte (I2 iodine and KI potassium iodide solution), and conductive glass
(it is transparent, but acts like a metal).

A solar cell works similarly to a leaf on a plant. The chlorophyll dye (chlorophyll a) in a leaf (see Biology
lesson) absorbs solar energy and converts it into chemical energy (sugar); a solar cell takes solar energy
and converts it into electrical energy, but creates no net chemicals and thus is termed regenerative.
Leaves store net chemical energy and are termed photosynthetic.

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HO

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O N N
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Mg
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Chlorophyll a

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Blackberries contain a strongly light-absorbing dye molecule called anthocyanin, which occurs in many
types of fruits and berries. It is the compound that gives blackberries, raspberries, blueberries, and
pomegranates their color. These dyes can be extracted and used in a dye-sensitized TiO2 solar cell to
absorb light and convert the lights energy into electricity.

Chemical Formula: C15H10O6
OH

O

HO O

OH
OH

Anthocyanin (Blackberry Dye)

Brian ORegan and Michael Grtzel at the cole Polytechnique Fdrale De Lausanne in Switzerland
made the first efficient DSSC. The approach used in DSSCs has many advantages over other solar energy
conversion technologies because of its simple device construction and inexpensive TiO2 particles and
dyes that can be fine-tuned to increase their light-absorbing properties. Although there is still much
room for improvement, state-of-the-art DSSCs converts solar energy into electricity with efficiencies
over 10%, rivaling some silicon-based technologies (commercial silicon is typically around 10 15%).
These devices use specially prepared dyes that absorb a great deal more sunlight than the anthocyanin
dyes extracted from the blackberries.

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High School Lesson Plan
nd then turn off the heat so the film can gradually

Solar Energy Conversion: Making a Dye-Sensitized TiO2 Solar Cell

For dye.
to prepare the this laboratory,
Obtain one the students
(1) blackberry will make a and
DSSC using dyes extracted from a blackberry. The
blackberry will be crushed, thus releasing its dyes. Then, electrodes that contain a thin layer of white
ula. Add 3-4TiOdrops of deionized water and continue
2 paste will be soaked in the crushed blackberries so that the electrodes become colored and absorb
uice. You can filter
visible light. this with a Bchner funnel or

The electrodes are made using a paste of extremely small particles of TiO2 (nanoparticles) that are
spread enough
node) and place out in a thin layer on transparent
blackberry dye on conductive
the glass electrodes. The thickness of the TiO2 thin film
ends up being roughly the thickness of a human hair. The particles provide a huge surface area for the
it there for dye molecules to bind, and they provide an electron pathway for the generated electrical current to be
10 minutes. In the meantime, prepare
collected. The dyed electrode goes from white to dark purple when dyed. A significant portion of light
is absorbed by the dye, even though only a single layer of dye molecules is attached to the surface.
erry dye from the electrode using deionized water
al). Gently The
blotfinal
the steps include drying the electrode and then assembling the device with an additional electrode
electrode dry using a Kimwipe.
to form a sandwich solar cell. The device has two electrodes, the dyed TiO2 photoelectrode (left side
in the picture below F:SnO2 (FTO)) and a counter electrode. An electrolyte solution is introduced
between the two electrodes and is composed of potassium iodide and iodine/triiodide.

side of the After
second a dye piece of absorbs
molecule glass. a Itphoton
will take onless
it takes a than 1 picosecond (1012 s) to split this excited
electron into an electron accommodated by TiO2 and a positive vacancy on the dye, termed a dye cation.
ion as a catalyst for the redox electrolyte. Check
Subsequently, the dye cation relays its positive charge to an iodide ion in solution and restores the dye
to its original state. Current is generated when the electrons in TiO2 move through an external circuit
and recombine with the oxidized iodide species at the counter electrode. The picture below shows the
energetics of a finished blackberry-sensitized TiO2 solar cell and its operation under sunlight
illumination. This process is more specifically described by the following equations:
n the lab bench.
Place the counter electrode on top
overed by the counter
On the TiO2 electrode,
electrode (anode): but thereTiO2is about
Dye + photon TiO2Dye* e- in TiO2 and Dye+;
In the electrolyte solution: Dye + 2 I {possible intermediate} Dye + I2-; 2 I2- I- + I3-;
+ -
on both electrodes. See figure 4.
On the graphite-coated counter electrode (cathode): I3- + 2 e- 3I-;
where Dye* is the common notation used when an electron has absorbed a photon
two binder clips. They should be placed on the

op of the
ectrode
der clips,
solution is
nia film
Figure 4. Assembled PV cell with binder clips

and electrodes.
The solar power conversion efficiency of these types of berry-sensitized TiO2 DSSCs can reach ~0.7%
with demonstration cells attaining 1 2 mA/cm2 of photocurrent and 0.5 V when using an overhead
projector as a simulated sun illumination source. Students typically observe photovoltages well over
400 mV and good photovoltaic cell stability. Attaching many cells electrically in series results in larger
voltages as they are additive; attaching them in parallel results in larger photocurrents.

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High School Lesson Plan
Page 3 of 4
 Solar Energy Conversion: Making a Dye-Sensitized TiO2 Solar Cell


STUDENT LABORATORY PROCEDURE (Day 1)

Materials and Supplies:
Per class
1 bottle of Nanoparticle TiO2 Paste* (this contains a mix of TiO2 nanoparticles, water, and
surfactant)
2 Multimeters with probes*
1 Hot plate

Per group of 2 students
2 Transparent Conductive Glass Plates (FTO Electrodes)* (one electrode is 2.5 cm long x 2 cm
wide and the second is 2.5 cm long x 1 cm wide)
1 roll of 3MTM Scotch tape#
1 Pipette*
1 Paste spreader (this can be any rigid straight edge, i.e. glass stirring rod, glass slide, pipette)
1 Tweezer* or tong
1 Graphite pencil*

*Provided in the Juice from Juice kit
#
If need be, fewer can be used as groups can share

Preparing TiO2 Electrode (See http://www.youtube.com/watch?v=RYO09FdCN5I for a demonstration):

1. Split the students up into groups of two, for up to 30 students in total.

2. Take the larger, 2.5 cm x 2 cm, conductive glass electrode and ensure that the conductive side is
facing up; do this by using the multimeter probes to measure resistance across two points on the
glass surface. Share the multimeters between groups. Ensure that the multimeter is set to
resistance mode () on any setting. (Carefully handle the sides of the glass electrodes and avoid
touching the faces of the electrodes.) If no resistance is measured turn the electrode over and
measure again. Typical resistances should be around 10 30 ohms.

3. Tape the electrode down to a clean, sturdy surface so that the tape masks off ~1.5 cm (bigger is
better) down along the length of the electrode (Figure 1a). This will create a lane down the center
of the electrode where the TiO2 paste will be spread.

4. Using a pipette, drip a few (~10 20) drops of the TiO2 solution halfway down the center of the
plate and immediately squeegee the solution down and up once with the paste spreader. The tape
should act a bumper, allowing for an even coating of the center lane (Figure 1b, c). If a TiO2 film
does not coat the entire exposed surface (Figure 1c), quickly drip a few more drops of TiO2 on the
exposed areas and re-squeegee the entire film. Allow the electrodes to dry, undisturbed, for a few
minutes. During this time, rinse the pipette with water to remove the leftover TiO2 paste.

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High School Lesson Plan
 Solar Energy Conversion: Making a Dye-Sensitized TiO2 Solar Cell

Figure 1 (a, b, c). Steps for depositing TiO2 paste and doctor blading. The middle lane should be
almost as wide as you can make it. Only put paste near one edge and pressing with little force, squeegee
down and back up each once; you should not need to repeat the process.


4. Remove the 3MTM Scotch tape from the dried TiO2 electrode. Carefully wipe any remaining white
paste off the bottom of the glass using a moist paper towel.

5. Note about hot plates: You can place the electrodes onto a cold hot plate so the students do not burn
their fingers. Then turn the hot plate on. It will take extra time to heat up. The teacher can monitor
the hot plate, and turn it off at the end of the day. Then, the hot plate will be cool to the touch for
the next class with no fear of students burning their fingers.

Using tweezers or tongs, carefully place the TiO2 electrode onto a hot plate. The electrode is ready,
i.e. fully sintered, after it darkens in color and then turns bright white (~30 min). Use tweezers or
tongs to remove the electrode from the hot plate, handling it only on the edges. Allow the
electrode to cool for 15 minutes by setting it on a designated tray. (Caution: Cooling too quickly can
cause the glass electrode to fracture.)

Classroom management tip: Make a diagram of the layout of students electrodes, and place them
on the hot plate in that order. That way, students will know they are working with the electrode they
made.

6. Take the other smaller, 2.5 cm x 1 cm, piece of conductive glassthis will be the counter electrode.
Use a multimeter to find the conductive side (see step 1). Use a golf pencil to coat the entire surface
with graphite (pencil lead).

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High School Lesson Plan
 Solar Energy Conversion: Making a Dye-Sensitized TiO2 Solar Cell


STUDENT LABORATORY PROCEDURE (Day 2)
Materials and Supplies:
Per class Per group of 2 students
1 bottle of I-/I3- Electrolyte Solution* 1 TiO2 electrode (made Day 1)
2 Multimeters with probes* 1 Graphite-coated Counter electrode (made Day 1)
4 Alligator clips* 1 Plastic baggie or large centrifuge tube (used to
1 Overhead projector crush the berries)#
1 2 blackberries#
For extension (optional) 2 binder clips*
1 Commercial silicon solar cell* 1 pipette*
1 roll of Black electrical tape 1 squirt bottle of isopropanol (IPA) or ethanol#
2 Multimeters with probes* 1 squirt bottle of distilled water#
15 Alligator clips* 1 Tweezer* or tong
1 Light-emitting diode (LED)* 1 Waste beaker#
1 Aqueous KCl solution*

*Provided in the Juice from Juice kit
#
Fewer can be used as groups can share

Dyeing the TiO2 Electrode and Assembling the DSSC:

1. Prepare the dye by thoroughly crushing 1 2 blackberries in a baggie by squeezing the outside of
the baggie or in a centrifuge tube with a straight utensil.

2. Take the cooled electrode and place it into the blackberry solution in the baggie or centrifuge tube
for ~5 minutes. (Use tweezers or tongs to handle the electrode.) Ensure that the electrode is fully
submerged (add more water if necessary). The white TiO2 paste should turn purple throughout so
there is no white left. Continue with the next step while you wait.

3. Using a beaker to catch your waste fluid, rinse the dyed TiO2 electrode with the bottle of distilled
water. Then thoroughly rinse again with isopropanol or ethanol into the same waste beaker. Allow
the dyed electrode to dry for 5 10 minutes.

4. Assemble the dyed TiO2 electrode (larger
dyed electrode) with the counter electrode
(the one with graphite) using 2 binder clips
to form a sandwich thin-film cell. Follow
the picture to the right, and make sure the
graphite coating is touching the purple
dyed TiO2 surface and avoid overlapping
the bare glass electrodes (the sides). The
thinner graphite-coated electrode should
line up with the TiO2 line but is offset so
that an alligator clip can be attached to
each individual electrode.

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High School Lesson Plan
 Solar Energy Conversion: Making a Dye-Sensitized TiO2 Solar Cell


5. Using a pipette, fill the space between the two electrodes with the iodide/triiodide (I-/I3-) electrolyte
solution. Allow the solution to wick up between the electrodes by capillary action. Alternate
removing/reattaching each binder clip, one at a time, to facilitate this action. The space between
the glass electrodes should turn slightly yellow and be entirely wetted by the solution.

6. To test your solar cell, clip the positive terminus (red) of the multimeter probe to the graphite
electrode and negative terminus (black) to the TiO2 electrode using alligator clips.

Measure the voltage and current obtained in room light, under the overhead projector and outside
in the sunshine with the dye-sensitized electrode facing the light source. (What happens to the
parameters if you flip the DSSC over so that the light is going through the counter electrode first?)
Record your results in the data table. To measure voltage, switch the indicator to DCV (Direct
Current Voltage) (upper left on the Cen-Tech Multimeter) to the lowest setting, 200m. If it reads a 1,
the voltage is too large for that setting and you must switch to the next level, 2000m, by turning it
clockwise. Continue this process until you observe a reading other than 1.

To measure current, switch the indicator to DCA (upper right on the Cen-Tech Multimeter) to the
lowest setting, 200. Again, if you see 1 on the display, switch the indicator clockwise to the next
setting and repeat until a meaningful value is obtained.

Do not forget to record the weather conditions (sunny, cloudy, etc.). Calculate the power output of
your DSSC as the product of the current and voltage for each condition investigated.


Data Table (include units for voltage and current)
Room light Overhead projector light Outside light
Weather conditions:


DSSC
Voltage
DSSC
Current
DSSC
Power
Silicon Cell
Voltage
Silicon Cell
Current
Silicon Cell
Power

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High School Lesson Plan
 Solar Energy Conversion: Making a Dye-Sensitized TiO2 Solar Cell


Extensions and Wrap-Up of Lessons:
Comparison to the Silicon Solar Cell:

7. Measure the exposed area of your DSSC. Using black electrical tape, mask off an area on the
commercial silicon solar cell that is approximately the same area as your DSSC.

8. Measure the voltage and current obtained for the silicon solar cell (see Physics lesson) under the
light conditions used for the DSSC. For the measurement on the overhead projector, attach two
binder clips to the silicon cell in the same way as the DSSC, so that the silicon cell is parallel to the
projector lens and at a similar height as the DSSC. Record your results in the data table. Compare
these results to those you obtained for your DSSC. What happens when you insert a colored filter
between the DSSC and the light? Does the same thing happen when you use the silicon solar cell?
Does the color matter? Why?

Using the Power from the DSSCs to Power a Light-Emitting Diode (LED):

9. Choose several DSSCs with the best performance and connect them back-to-back in series using
alligator clips. The connection between every pair of cells must be from a dyed TiO2 electrode on
one to a graphite counter electrode on the other. The final ends of the connected cells should be
hooked up to the LED. How many of them are needed to power the LED? Does it matter which lead
from the serially connected DSSCs is connected to which lead of the LED? (The answer is yes so try
both combinations.)

10. Measure the current and voltage of the serially connected DSSCs. Based on the current, how many
silicon solar cells would need to be connected in series to light the LED? Try it out. Based on the
voltage, how many silicon solar cells would need to be connected in series to light the LED?

11. Connect another set of DSSCs in series and attach this circuit in parallel to the original one. What
happens to the current, voltage, and LED intensity in this case?

Storing the Power from the DSSCs in Chemical Bonds as a Fuel:

12. As we all know, the sun sets locally every night. Thus, it would be ideal if a DSSC could truly mimic
natural photosynthesis and store the power it generates into chemical bonds as a useful fuel.
Hydrogen (H2) is a clean fuel that can be burned just like gasoline. Using the DSSCs and/or silicon
solar cell connected in series, attach the final leads of each to the graphite in a golf pencil. Here, the
order does not matter. Your instructor may have to shave off some of the excess wood around the
graphite with a blade so that there is enough protruding for you to connect the alligator clip leads.

13. Immerse the graphite pencils in a small beaker of KCl solution (from the chemistry lesson), and
illuminate the cells using the overhead projector. Look closely for bubbles forming on either of the
ends of graphite immersed in the solution. Be patient; it may take a few minutes.

14. If this does not work, replace the graphite pencil that is directly connected to the final DSSCs
graphite counter electrode with a small piece of copper foil. Immerse the foil and the graphite from
the other electrode into the same solution and repeat the illumination experiment. Again, look for
bubbles on the graphite end of the pencil immersed in the solution. Be patient; it may take a few
minutes. If this does not work, try attaching more DSSCs or silicon solar cells in series.

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High School Lesson Plan
 Solar Energy Conversion: Making a Dye-Sensitized TiO2 Solar Cell


Checking for Understanding: Analysis Questions to Ask Your Students.

1. Where does the power come from when we are using the solar cell? (What causes the electrons in
the dye to move?)





2. What side of the glass electrode did you apply the TiO2 layer? (Conductive or nonconductive?) Why?





3. When the dye loses an electron, is the dye oxidized or reduced?




4. Graphite is made up of layers of carbon. What is our source for graphite when we coat our counter-
electrode with it? What do you think will happen to the performance of the DSSC if it was
illuminated through this electrode first?





5. The TiO2 paste is white and used in many commercial products: white paint, toothpaste, powdered
doughnuts, etc. Why do we need to use the dark-colored dyes from blackberries to make our solar
cell work? (Hint: Think about how light is reflected or absorbed.)




6. A leaf and a solar cell both convert solar energy into another type of energy. What type does a solar
cell make, and what type does a leaf make?





7. The TiO2 paste which is used for this lab to create thin-film dye-sensitized solar cells is made up of
tiny (nanometer sized 25 nm) TiO2 particles. One nanometer (nm) is one-billionth of a meter, or
0.00000001m; what is this number in scientific notation?

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High School Lesson Plan
 Solar Energy Conversion: Making a Dye-Sensitized TiO2 Solar Cell


8. Why is it important to use nanometer-sized particles for the film? Use the words surface area in
your explanation and include an illustration.









9. Draw in the direction in which the electrons move through the dye-sensitized solar cell in the
potential energy diagram below. The photo-excitation yellow arrow is included (light exciting the
dye).

An additional suggestion: ask your students to draw a picture of the electrodes and explain what
happened during each step in the process in their own words. What happened when the LED was lit?
What happened when the H2 fuel was produced?

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High School Lesson Plan
 Solar Energy Conversion: Making a Dye-Sensitized TiO2 Solar Cell


Inquiry Extensions:

The solar cells that have been constructed require a dye (the anthocyanin dye from the blackberry
juice), TiO2 nanoparticles (white paste), and electrolyte (I2 and KI, iodine and potassium iodide) to
function.

What are the effects of removing one or more of these components from the cell? Explain why each
component is crucial for the operation of a dye-sensitized solar cell.
- The electrolyte (I2 iodine and KI potassium iodide)
- TiO2 nanoparticles
- Anthocyanin dye (from the blackberry juice)

The anthocyanin dye from the blackberry juice absorbs green light. What would happen if you filter the
light that the solar cell is exposed to using a green filter? Red filter? Blue filter? Compare this with
what happens when you do the same thing for the silicon solar cell?

What is the effect of using dyes from other fruits/vegetables, i.e. raspberries, pomegranates,
strawberries, beets, or the chlorophyll obtained in the chemistry laboratory? Note the color of the dyed
electrode and the solar cell performance (current and voltage obtained). What are the active dyes in
these fruits/vegetables?

Explain the similarities (via electronic flux arrows) between the two energy level diagrams shown below
with the galvanic cell on the left (from the chemistry lesson) and the dye-sensitized solar cell diagram on
the right. What does the large, dark-blue double arrow represent in each diagram? How is it created in
each cell?

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High School Lesson Plan
 Solar Energy Conversion: Making a Dye-Sensitized TiO2 Solar Cell


References

Cherapy, N.J., Smestad, G.P., Grtzel, M. & Zhang, J.Z. (1997). "Ultrafast Electron Injection: Implication
for a Photoelectrochemical Cell Utilizing an Anthocyanin Dye-Sensitized TiO2 Nanocrystalline Electrode,"
Journal of Physical Chemistry B, Vol. 101, No. 45, Pgs. 9342 9351, Nov. 6, 1997.

Smestad, G.P. (2009). "Optics of Solar Cells," 93rd Annual Meeting, Frontiers in Optics (FiO) 2009/Laser
Science (LS), 25th Conference, Optics for Renewable Energy, Optical Soc. of America, San Jose, CA,
October 11 15, 2009.

Smestad, G.P. (1998). "Education and solar conversion: Demonstrating electron transfer", Solar Energy
Materials and Solar Cells, Vol. 55, Pgs. 157 178, 1998.

Smestad, G.P. & Grtzel, M. (1998). "Demonstrating Electron Transfer and Nanotechnology: A Natural
Dye-Sensitized Nanocrystalline Energy Converter," Journal of Chemical Education, Vol. 75, Pgs. 752
756, June 1998.

Sol Ideas Technology Development (2009). Components of the Solar Cell Procedure. Retrieved from
http://www.solideas.com/solrcell/kitcomp.html.

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