1. OU NanoLab/NSF NUE/Bumm & Johnson Nanocrystalline Dye Sensitized Solar Cell

2. OU NanoLab/NSF NUE/Bumm & Johnson Outline Motivation History Cell Schematic Useful Physics Construction Procedure Preparation and deposition of TiO 2 (10-50 nm diameter) Preparation of dye and staining semiconducter Carbon Coating counter- electrode Assemblage Electric Output Data Analysis Conclusion

3. OU NanoLab/NSF NUE/Bumm & Johnson Motivation Economically feasible harnessing of solar energy Reduce fossil fuel usage and subsequent pollution Provide usable energy to inaccessible and economically challenged communities Modeling of biological photochemical systems Improvement of current photographic methods

4. OU NanoLab/NSF NUE/Bumm & Johnson History 1839: French physicist Antoine-Cesar Becquerel observed that shining light on an electrode submerged in electrolyte would create an electric current. 1941: American Russell Ohl invented a PN junction silicon solar cell The dye sensitized solar cell was developed in 1992 by Graetzel (EPFL, Laussane, Switzerland) and utilizes nanocrystalline TiO 2 as the photoabsorber

5. OU NanoLab/NSF NUE/Bumm & Johnson Solar Panel Cost Initially solar panels were expensive (>$2000 per watt in 1950s). Thus their use was limited to very special applications such as powering space satellites. Today solar panels are less than $4 per watt.

6. OU NanoLab/NSF NUE/Bumm & Johnson What’s on the Horizon? First Generation:Single and polycrystalline wafer cells Second Generation:Thin film cells Third Generation:Thin film cell efficiency is increased by using multiple layers in tandem and matching the band gaps of each layer to a different region of the solar spectrum.

7. OU NanoLab/NSF NUE/Bumm & Johnson Evolution of the Efficiency of the Steam Engine

8. OU NanoLab/NSF NUE/Bumm & Johnson Schematic of the Graetzel Cell

9. OU NanoLab/NSF NUE/Bumm & Johnson Useful Physics The adsorbed dye molecule absorbs a photon forming an excited state. [dye*] The excited state of the dye can be thought of as an electron-hole pair (exciton). The excited dye transfers an electron to the semiconducting TiO 2 (electron injection). This separates the electron-hole pair leaving the hole on the dye. [dye* + ] The hole is filled by an electron from an iodide ion. [2dye* + + 3I -  2dye + I 3 - ]

10. OU NanoLab/NSF NUE/Bumm & Johnson Useful Physics Electrons are collected from the TiO 2 at the cathode. Anode is covered with carbon catalyst and injects electrons into the cell regenerating the iodide. Redox mediator is iodide/triiodide (I - /I 3 - ) The dashed line shows that some electrons are transferred from the TiO 2 to the triiodide and generate iodide. This reaction is an internal short circuit that decreases the efficiency of the cell.

11. OU NanoLab/NSF NUE/Bumm & Johnson Key Step – Charge Separation Charge must be rapidly separated to prevent back reaction. Dye sensitized solar cell, the excited dye transfers an electron to the TiO2 and a hole to the electrolyte. In the PN junction in Si solar cell has a built-in electric field that tears apart the electron-hole pair formed when a photon is absorbed in the junction.

12. OU NanoLab/NSF NUE/Bumm & Johnson Chemical Note Triiodide (I 3 - ) is the brown ionic species that forms when elemental iodine (I 2 ) is dissolved in water containing iodide (I - ).

13. OU NanoLab/NSF NUE/Bumm & Johnson Construction Procedure TiO 2 Suspension Preparation TiO 2 Film Deposition Anthrocyanin Dye Preparation and TiO 2 Staining Counter Electrode Carbon Coating Solar Cell Assembly

14. OU NanoLab/NSF NUE/Bumm & Johnson Preparing the TiO 2 Suspension Begin with 6g colloidal Degussa P25 TiO 2 Incrementaly add 1mL nitric or acetic acid solution (pH 3-4) nine times, while grinding in mortar and pestle Add the 1mL addition of dilute acid solution only after previous mixing creates a uniform, lump-free paste Process takes about 30min and should be done in ventilated hood Let equilibrate at room temperature for 15 minutes

15. OU NanoLab/NSF NUE/Bumm & Johnson Deposition of the TiO 2 Film Align two conductive glass plates, placing one upside down while the one to be coated is right side up Tape 1 mm wide strip along edges of both plates Tape 4-5 mm strip along top of plate to be coated Uniformly apply TiO 2 suspension to edge of plate 5 microliters per square centimeter Distribute TiO 2 over plate surface with stirring rod Dry covered plate for 1 minute in covered petri dish

16. OU NanoLab/NSF NUE/Bumm & Johnson Deposition of the TiO 2 Film (cont.) Anneal TiO 2 film on conductive glass Tube furnace at 450 o C 30 minutes Allow conductive glass to cool to room temperature; will take overnight Store plate for later use

17. OU NanoLab/NSF NUE/Bumm & Johnson Examples: TiO 2 Plate Good Coating: Mostly even distribution Bad Coating: Patchy and irregular The thicker the coating, the better the plate will perform

18. OU NanoLab/NSF NUE/Bumm & Johnson Preparing the Anthrocyanin Dye Natural dye obtained from green chlorophyll Red anthocyanin dye Crush 5-6 blackberries, raspberries, etc. in 2 mL deionized H 2 O and filter (can use paper towel and squeeze filter)

19. OU NanoLab/NSF NUE/Bumm & Johnson Staining the TiO 2 Film Soak TiO 2 plate for 10 minutes in anthocyanin dye Insure no white TiO 2 can be seen on either side of glass, if it is, soak in dye for five more min Wash film in H 2 O then ethanol or isopropanol Wipe away any residue with a kimwipe Dry and store in acidified (pH 3-4) deionized H 2 O in closed dark-colored bottle if not used immediately

20. OU NanoLab/NSF NUE/Bumm & Johnson Carbon Coating the Counter Electrode Apply light carbon film to second SnO 2 coated glass plate on conductive side Soft pencil lead, graphite rod, or exposure to candle flame Can be performed while TiO 2 electrode is being stained

21. OU NanoLab/NSF NUE/Bumm & Johnson Assembling the Solar Cell Remove, rinse, and dry TiO 2 plate from storage or staining plate Place TiO 2 electrode face up on flat surface Position carbon-coated counter electrode on top of TiO 2 electrode Conductive side of counter electrode should face TiO 2 film Offset plates so all TiO 2 is covered by carbon-coated counter electrode Uncoated 4-5 mm strip of each plate left exposed

22. OU NanoLab/NSF NUE/Bumm & Johnson Assembling the Solar Cell Place two binder clips on longer edges to hold plates together (DO NOT clip too tight) Place 2-3 drops of iodide electrolyte solution at one edge of plates Alternately open and close each side of solar cell to draw electrolyte solution in and wet TiO 2 film Ensure all of stained area is contacted by electrolyte Remove excess electrolyte from exposed areas Fasten alligator clips to exposed sides of solar cell

23. OU NanoLab/NSF NUE/Bumm & Johnson Measuring the Electrical Output To measure solar cell under sunlight, the cell should be protected from UV exposure with a polycarbonate cover Attach the black (-) wire to the TiO 2 coated glass Attach the red (+) wire to the counter electrode Measure open circuit voltage and short circuit current with the multimeter. For indoor measurements, can use halogen lamp Make sure light enters from the TiO 2 side Multimeter light solar cell

24. OU NanoLab/NSF NUE/Bumm & Johnson Measuring the Electrical Output Measure current-voltage using a 500 ohm potentiometer The center tap and one lead of the potentiometer are both connected to the positive side of the current Connect one multimeter across the solar cell, and one lead of another meter to the negative side and the other lead to the load

25. OU NanoLab/NSF NUE/Bumm & Johnson Data Analysis Plot point-by-point current/voltage data pairs at incremental resistance values, decrease increments once line begins to curve Plot open circuit voltage and short circuit current values Divide each output current by the measured dimensions of stained area to obtain mA/cm 2 Determine power output and conversion efficiency values

26. OU NanoLab/NSF NUE/Bumm & Johnson Results Current: –One solar cell: 0.11 - 0.19 mA –Two cells in parallel: 0.164 - 0.278 mA Voltage: –One solar cell: 0.30 – 0.40 V Resistance: –Very large. Fig. 1: “How many nano - physicists does it take to screw in a lightbulb?”

27. OU NanoLab/NSF NUE/Bumm & Johnson Questions What have we learned about the relationship of solar cell to photosynthesis and solar energy? How can you improve the procedure or design? How does this ultimately relate to other things we've learned in NANOLAB?

28. OU NanoLab/NSF NUE/Bumm & Johnson Further Reading Konarka Technologies (Graetzel cells)http://www.konarkatech.com/http://www.konarkatech.com/ PV Power Resource Site http://www.pvpower.com/http://www.pvpower.com/ US DOE Photovoltaicshttp://www.eere.energy.gov/pv/http://www.eere.energy.gov/pv/ Key Center for Photovoltaic Engineeringhttp://www.pv.unsw.edu.au/http://www.pv.unsw.edu.au/ National Center for Photovoltaicshttp://www.nrel.gov/ncpv/http://www.nrel.gov/ncpv/ NRELs Photovoltaic Information Indexhttp://www.nrel.gov/ncpv/masterindex.htmlhttp://www.nrel.gov/ncpv/masterindex.html