Journal of Chemical Education Print *© Software ¢ Online * Books ‘Owned and Published by THE DIVISION OF CHEMICAL EDUCATION, INC, OFTHE AMERICAN CHEMICAL SOCIETY Demonstrating Electron Transfer and Nanotechnology: A Natural Dye-Sensitized Nanocrystalline Energy Converter Greg P. Smestad and Michael Gratzel Reprinted from Journal of Chemical Edveation, Vol. 75, pp 752-756, June 1998. Copyright ©1998 by the Divison of Chamical Education ofthe American Chemicol Society Reprinted by permission of the copyright ownerDemonstrating Electron Transfer and Nanotechnology: A Natural Dye-Sensitized Nanocrystalline Energy Converter Grog P. Smestad Solar Energy Materials and Solar Cells, PO. Box 51038, Pacific Grove, CA 93950 Michael Griitzel Insitute of Physical Chemisry, ICP.2, Swiss Federal lative of Technology, CH.1015, Lausanne, Switzerland ‘A unique sola cll fabrication procedure has been de- veloped, using natural anchocyanin dyes extracted fom berries Iecan be reproduced with a minimum amount of resources, providing aninterdsciplinary approach for lowerdvision under graduate students earning the basic principles of biological extraction, physical chemistry, spectroscopy, environmental science, and electron transfer. Electron transfer isthe basis ofthe energetics tha drives che processes of life on Earth. It ‘occuss in both the mitochondrial membranes of living cells and the thylakoid membranes in phocosyathetic cells of green plants and algae (J). Although we depend on the products of this electron and energy tanser inthe form of petroleum and agricultural products, one ofthe greatest challenges ofthe 21st century is that we have ye o create deviees that can be used to tap directly into the ulimate source ofthis energy on an economic scale. An experimental lab procedure was there fore created to illustrate the connections berween natural and manmade solar conversion within a three-hour lab period. Technical Background Nanocrystalline dye-sensitized solar cells (Fig. 1) are promising synthetic nanomachines based on principles similar to the processes in natural photosynthesis. Both use an of- ganic dye to absorb the incoming light and produce excited electrons. film of interconnected nanometcrsized titania dioxide particles replaces nicotinamide adenine dinucleotide phosphate (NADP) and carbon dioxide as the electron ac- ceptor, and iodide and triodide (I, Is) replace water and oxygen as the electron donor and oxidation product, respec- tively. A recent review by Meyer in this Journal reported on progres in understanding this biomimetic approach to en- cexgy conversion (2) Like the coupled processes of photosyn- thesis and respiration found in the biosphere, the light- driven electrochemical process in the nanocrystalline solar cells regenerative and forms a closed cycle that converts light energy into useful forms. Although laboratory dye-sensitized nanocrystalline TiO> solar ces have achieved greater than 10% conversion efficiencies of sunlight to elecrrical power and photocurrent ousputs greater than 16 mA/em?, the syn- thetic ruthenium bipyridyl-based dyes used to attain high con- venion efficiencies ae difficule for the novice to synthesize, purify, and use (3). We have therefore developed a procedure that uses flavonoids and chlorophylldes as sensitizers forthe nanocrysalin solar cell Flavonoids such as anthocyanins are present in the leaves, fuits, and flowering structures ofall land plants. They function in the protection against the dam- aging effecs of UV light and as attractors for plant pollina- tors such as insects and birds (4). Remarkable for thei sabil- iy, these anthocyanin pigments may be used as natural wa- ter-based subsizutes fr the ruthenium bipyridyl dyes (5-7), 752 ‘This simplified procedure for solar cell oF photodetector fabrication has been successfully used in introductory under- graduate chemistry classes atthe California State University Monterey Bay, as a demonstration to more than 1000 high school science students attending the Illmac International Congress for Chemical Techniques in Basel, Switzerland (November 1996), and to 2nd graders in Pacific Grove, Cali fornia.’ Depending on how much preparation is made before the lab period, the procedure can be employed as a guided laboratory experiment in introductory or advanced college chemistry classes. This experimenc gives a concrete example of how concepts such as oxidation and reduction, optics, and spectroscopy can be used co understand che photosynthetic processes occurring in green plants (8). In an incerdiscpli- nary approach vo the teaching of science, the chemistry lab ight -# Counter Blctrode ‘Transparent conduelng ‘Glass Transparent conducting coating and ‘atalyet Bloctron Injetion Electrlyee odide’Tiodide) Dye "T0g nanserystala (Diameter = 20 \- ‘enometers) ‘vee 13 mrioaiae toate Figue. 1. Dyesenslized TOs solar call. The photoercited dye trans fore on elocron tothe semicondvcting TO; layer via elecron in jection. The injected eleciton is then transponed through the po- ‘ous TiO, layer and collected bythe conductive SnO; layer on the gloss surface. Wiin the electro, the mediator (//) undergoes ‘oxidation a the dye and regeneration ot the eatlyatcocted counter clocrode os curent flows through the eleckica load Journal of Chemical Education * Vol. 75 No. 6 June 1998 * JChemEd.chem.wise.educlass may work collaboratively with a biology class to extract the dye, or with a physis cas to determine the curent= voltage and power-ousput characteristics of the resulting dye- sensitized phoroclectrochemical sla cll. Experiments Equipment and Materials 1 Conductive (in donde coated) anspazen gs: re- ut commercial (2.5 em 25 cm) TEC 10 or TEC 15 gis an be purchared from one of several suppli- ex Hartford Glass Co Inc, PO. Box 613, Hartford Cig, IN 47348; phone 765/348-1282 Fax 7657348- 54355 email bareglas@nerual.ner, or Pillngson, [Libbey Owens Ford, #11 Madson Ave, 20. Box 799, “Tolelo, OH 43697-0799; phone 419/247-4517 2. Twelve pan of cllidal titanium done powder: Degussa P25 TiO, Degussa USA, 3500 Embassy Parkway, Akzos, OF 44333; phone 330/668-2235 or Degussa AG, D-6000, Prankfur 11, Germany 3. Iodide eecrolye solution in dropper bottle 05 M potassium odie ined with 0.05 M iodine in water Fre ethylene geal 4. Heat sour ovat gun or paine-sspper gun Leiner Model Horwind 8, Avsmbly Supplies Con, 11835 Carmel Men, Rd, Suite 1304, San Diego, CA’ 92128, phone 619/451-1859; o Stein! Typ. 3449, Insalation Sspply Coz phone 800/657-7715. An oven o aol bone can alo be wed 5. Miscellaneous supplie and equipment: Blackberics,rspberics, pomegranate eds, or gicen crus lever binder clipe, Scorch ape, ls sting od, absorbant tian paper ler pape sft graphite pencl or eaned carbon rod taken from an allie battery Overhead projector or cungten halogen ight source Vole-ohm meter 500-chm poceatomeer, hookup wie XY recorder (optional) “Motor opin: Maxon 2522.846.12.112.000, Maxon Interelectrie Co, AG, CH-6072 Sachielo/OW, Switzerland: URL brp/howu: maxonmotorcom: ot “Mabueki RF-330TK 07800, Mabuch Moro, 3001 ‘West Big Beaver Rd, Suite 520, Toy, MI. 48084; phone 248/616-3100, Capacitor (optional): 10,000 microfarad, single polarity Procedures Duting the entire procedure, care should be tken nor to touch the face ofthe elecrodes. The glass plates should be held with tweezers or by the edges ofthe las. Ifthe con- ‘ductive las is available and deposition of the TiO, layer caried out by the instructor or in a preliminary lab, the primary part of the experiment (starting with “Stain the ‘Titanium Dioxide”) can be carried out within a 3-hout lab period. We ako suggest thatthe iodide electrolyte be prepared before the lab period. Deposit the Titanium Dioxide Layer Depositing the nanocrystalline TiO, film requires pre paring a solution containing commercial colloidal TO, powder, masking 2 cleaned conductive glass plate, applying 8nd distributing the solution on the conductive glass plate, IChemEd.chemwisc.edu * Vol. 75 No. 6 June 1998 * Journal of Chemical Education and sintering the resulting hin film layer. The resulting THO, film is 7—10 um thick with a porous structure that enhances the efficiency of both light absorption and electron collec: tion in a way similar co the thylakoid membrane of green plants (I, 1. ‘A commercially avaiable glas plate coated with a con- ductive layer of fluorine-doped Sa, may be eu (2.5 em x 2.5 em) and used asthe staring material for the electrodes. If this is not possible, standard soda lime glass can be coated with a layer of conductive Sb-doped SO, in an adivonal 3-hour preliminary lb. To do this, spray ati solution on lass that hs been heated on a hotplate 450-550 °C. The {in solution is prepared by dissolving 25 g of SnCl,5H,0 in 6 mL of methanol and heating the solution 50°C, then ‘adding 2 ml. of en Sb,0, solution. This Sb dopane solution is prepared by dissolving |g ofSb;Oy in 3 ml. of HCl'methanol. For a complete discussion of the SnO, coating procedures, please refer to rf 9 “The TiO, solution i prepared by incremental addicion ‘0 20 mL of nitric or acetic acid solution (pH 3-4 in deion- ined wate) 0 12 of ealoidal TiO, powder (Degussa P25) in a morear while grinding with a pede. Ech Lom. addition ofthe dilute acidic solution proceeds only after the previous ‘mixing and grinding as produced a uniform lump-fiee past. ‘Asan alternative tothe atid solution, 0.2 mi of acetylacetone in I ml of water can be added to the TiO, powder, this i followed by the addition of 19 ml of water, again in 1-mL increments while pinding (10,11). Avot-ohim meter should be used to:check which side ofthe glass is conductive; the reading should be erween 10 and 30 02. Four pieces of Scotch (GM) adhesive tape ate applied tothe face of the conductive lass plate ro mask a 1-2 mm strip a cree ofthe four edges, and 2 4-5 mm stip is masked on the fourth side. Half of the tape extends from the edge of the pass tothe table ata 45° angle to secure the glass. This tape wil form a mold oF channel 40-50 im deep into which the TIO, solution can flow, while masking a strip ofthe conductive glass so that an clectrical contac can later be made. Three drops ofthe water based TiO; solution are distributed uniformly on the plate {Approximately 5 yLJem:) by sling a glas rod over the plate (Gee Fig, 2). The film is then allowed to dry in az. Aer one minute, the ape is carefilly moved and the film is annealed and sintered in an air sueam at 450 °C for 30 minutes A hhocaie gun or tube furnace may be employed to heat the film, of an alcohol or natural-gas burner can be used if che film is held on a rng stand at the tip of the fame for 10 minutes. The TiO,coated conductive glast is allowed :o slowly cool to om temperature. Ic ean be stored in ait for later use, Figure 2. Deposition and disbution of he TOs so- lution on the conductive gloss. A ropid horizontal ‘motion of the gloss rod wil coat the mosked glost plate with o uniform layer of TiO; nanoparticle. 753Figure 3. Cyonin 0” complex formed via the adsorption of the dye from solution onto the tanium dioxide surface, The sugar (glucose is liked tothe chromophore by on e+ ter nkage atthe 3 position, Stain the Titanium Dioxide with the Dye Fresh of frozen blackberries, raspberries, or pomegranate sceds ae crushed with 3-4 drops (1/2 ml.) of wate, filtered, and used as a crude dye solution. Alternatively, the film can simply be placed on top of crushed bersis to which a small amount of water has been added. The extract obtained by soaking red Hibiscus ta leaves in water at room temperature ray also be used. Several fuits and leaves contain antho- cyanins that, although colored, may not chelate to the TiO, surface (eg. strawberries). These pigments are not suitable forthe dye-sensitized cell. A requirement for the dye struc- ture is that it posses several =O or -OH groups capable of chelating co the Ti! sites onthe titanium dioxide surface (see Fig. 3). A mixture of eyanin 3-glycoside and cyanin 3- rutinoside are the main (sugar-bound) anthocyanin pigments from California blackberries (Rubus ursinu)) and are excel- lent narural dyes for sensitization (13). For an advanced class, the cyanin may be further purified by crushing the becres in rmethanol/acetic acid/water (25:4:21) and passing the filtered ‘extract through a Sephadex LH 20 (Pharmacia) column in the same solvent (13) ‘Soak separate TiO,-coated glass places for 10 minutes in cach of the various types of eyanin extracts, If white TiO, «an be seen upon viewing the stained film from either side of the supporting glas plate, then the film should be placed back in che dye for 5 more minutes. Adsorption of cyanin to the surface of TiO; and complexation to Ti sites i rapid, forming. complex capable of electron injection (Fig. 3). The dlark-purplestained film is washed first in water and then in «chanol or isopropanel, and gently blotted dry with a tissue If the cyanin-stained clectrode is not used immediately, it should be stored in acidified deionized water (pH = 3~4, acetic acid) in a closed dark-colored bottle: ‘As an option for an advanced classes, a second type of diye can be obtained from chlorophyll. Ths is accomplished by using the naturally occurring enzymes that leave che phytol tail and convere chlorophyll into a chlorophyllide possessing carboxyl groups capable of chelating tothe surface ofthe TiO; particles (/2). Natural dyes derived fom chlorophyll and Cu hhave achieved significant energy conversion efficiencies (2.6% and 9.4 mA/em:), but these results require pigment purifi- ‘ation and the coadsorption of other compounds on the TiO, surface (14). As a simplified procedure, fresh young green leaves are ground in a mortar with 2-3 mL. of acetone. Lemon or citrus tree leaves have been successfully used, but several other species can be tested as well. The dack-green acztone solution obtained from this procedure is filtered into a dark-colored (or aluminum-foil covered) botde, and five or six 4%4-mm pieces of unground leaves ate placed inthe 754 container An unstained (white) TiO, film is also placed in the borle and additonal acetone is added until the fl i completely covered by the solution. The solution is left co react for24 hours ina dark place, tallow time forthe enzymes to react with the chlorophyll as wel as forthe attachment of the dye to the TiO,, After 24 hours, the electode should be sexined to light green-yellow color. Before assembly, this stained electcode is washed in acetone and blotted dry Ifthe seained electrode is not used immediately, ic should be stored in the acetone and chlorophyllde solution until che electrode is ready to be assembled into the lightdetector device. Chto- marography can be used to compare the purity of the crude ‘extract with the enzyme-processed materials (12. Prepare the Carbon-Coated Counter Electrode ‘While the TiO, electrode is being stained in the berry juice or chlorophyll solution, the counter electrode can be ‘made fom another (2.5%2,5-em) piece of conductive SO; coated glass. A graphite rod or soft pencil “lead” is used to apply a light carbon film tothe entice conductive side of the plate, This thin carbon layer serves as a catalyst for the ‘wiodide-to-odide regeneration reaction. No masking or ape is required for this electrode, and thus the whole surface is catalyst coated. A longer-lasting coating a can be obtained by annealing the carbon-coated counter electrode at 450 °C for a few minutes. The counter electrode should be washed with ethanol and gently blotted dry before the device is assembled. As an alternative to the carbon coating, the counter electrode can be prepared by chemically depositing a transparent fine-grained platinum layer (3,11) ‘Assemble Device and Determine Output Characteristics The eyanin-stained TiO, electrode is carefully zemoved fiom the storage bortle or the staining solution and rinsed with water I is important to dry the stained clectode and to remove the water fom within the porous TiO, film before the iodide elecrolyte is applied to the film. One way to insure this isto rinse the elecrade wich ethanol or sopropanol before gently bloting it dry with tissue paper. The dred electrode [5 then placed on the table so that the film side is face up, and the catalys-coated counter clectrode is placed on tp 50 that the conductive side of the counter electrode faces the ‘TiO, film. The ewo opposing glass plates are offct so thar all of the THO, is covered by the counter electrode, and the 4-mm step of glass not coated by TiOs is exposed (see Fig. 4). The two exposed sides ofthe device will be the contact Figure 4. Assombled solar call or detector showing offset gloss pote, clips, and elec trical contact points The tained TO, layer ie in contact wih the cerboncooted conde ‘ve layer. ight enters the sandwich through the TiOzcooted gloss plate, which is the fnode of the electro: chemical device Journal of Chemical Educotion * Vol. 75 No. 6 June 1998 * JChemEd.chem.wise.edopoints for the negative and positive electrodes so that elec- tricity can be extracted to test the eel. Two binder clips are used to hold the plates together loosely at the other edges One or wo drops of the iodideliodine eleeroyte solution can then be placed a the edges of the plates and the rwo binder clips are altenately opened and closed while in place. The liquid is drawn into the space beeween the electrodes by cap- illry action, and can be seen to “wet” the stained TiO; film. ‘The completed solar celllight detector can be aken out- side and measured under illumination by sunlight. To protect the cell from damage by excessive UV light, a plastic ler Variable Load Figure 5. Two posible experimen setup for measuring the current volage characteristics ofthe finished device. Volioge (V] ie meo- sured by 0 volmeter ond cure] by another meter set to 0-5 mA ‘col. The top circuit con be used tobias the eal beyond the power Producing portion ofthe I=V curve meatured using the simplified Circuit shown atthe botom, Photocurtent, /mA ° so 0S Voltage, V/n Figure 6. Typical eurent-volage (IV) curve for @ 4-cn? sunlight ilominoted solr calor ight detector stained with blackbery juice (cyonin). The open circuit volage ond shor ciruit current are ob- toned from the x ond y intercepts, respectively. IChemEd.chem.wisc.edu * Vol. 75 No. 6 June 1998 * Journal of Chemical Education should be placed over the ell. Light should enter the glass "sandwich" through the TiO,-coated glass plate. Maximum, current and voltage output can exsily be determined by at- taching 2 volt-ohm meter directly to the two sides ofthe cel using wites with alligator clips attached to their ends. The negative electrode is the TiO,-coated glass, and should be attached to the black (-) wite of the meter; the postive elec- trode (+) is connected to the counter electrode. Use a ruler 0 ‘measure the dimensions of the ative (stained) area of the so- Jar cell and divide the ourput current by this area. Record the cleerical ourput values and compare the vatious types of dye extraction procedures used. For indoor measurements, the cell can be illuminated by a 50-W (GE 12V or equivalent) tungsten halogen lamp equipped with integral parabolic reflector and UW end IR blocking filter, or placed in the beam of an overhead or slide projector. One can calibrate the indoor light sources by ad- justing the light intensity or distance from the eel tothe light source so that the maximum current values are identical co the outdoor measurements. The fall current-voltage (IV) ‘curves are then measured using a 500-0 potentiometer as 2 variable load (see Fig. 5). Point-by-point current and voltage data can be gathered at each incremental resistance value and plotted on graph paper. A chart recorder can also be used to sweep out the fll curve asthe potentiometer is turned. IF 2 cll dries out, another drop of electrolyte can be added to the edges of che plates to revive it. ‘As an optional demonstration of the electcal power out- put of the TiO, blackberryjuice-sensitzed solar cll, cells can be connected in series to increase the voltage and in parallel to increase the current. This will produce enough electrical out- put to power a small motor. A 10,000 microfarad capacitor can be charged using the solar cells) and then rapidly dis- charged through the motor to illustrate the unequal rates of| storage and depletion of the solar energy represented in fossil fucls. The cell may aso be heat-sealed using a gasket made fom a low-meltng-point polymer film used in food packaging, such as Dupont Suelyn 1702. Unsealed devices can be stored while assembled for several months in sealed containers and revived by washing the electrodes with ethanol (or acetone, for the chlorophyll based cel), blot drying with a tissue in ai, reassembling the cell, and eapplying fresh elecrolyte. Results and Analysis of Data Using the volt-ohm meter, the open-circuit or maximum voltage produced under direct sunlight should be berween 0:3 and 05 V. Switching the meter to current (milliamperes) mode, one should obtain a short-cicuit current of 1-2 mAlem* of | dyed area in bright sunlight. This means that a 2x 2-em? cell should produce at least 3 t0 4 mA. The full /-V plot for 2 typical sunlightiluminatedcyanin-sensitized TiO, film, of active area 4 emi, is shown in Figure 6. For ths cell, the TiO, film was simply placed in berry juice as described above and the counter electrode was carbon coated. Similar outputs are also obtained from chlorophyllide-based cells, which often produce more than 0.6 V. The maximum product of current and voluge (obtained near the “knee" ofthe curve) in Figure 2, is divided by the incoming solar power (approximately 800— 1000 Wim’) to obtain the conversion efficiency of sunlight to electrical energy (15, 16), which is between 1 and 0.5% for anthocyanin or chlorophyllide-based cell. 758Discussion From Figure {, she reactions found in the solace: are dye + light dye" ye" + TIO, + {TOs} + oxidized dye ized dye + #51" dye + "ly Ugly & (eounterclectraded 431 Seurdents ate asked to sketch a diagram ofthese electron transfer ‘vents based 07 the polarity of the ecl. They ate also asked to explain the fibrication and operation of the device and to draw patallels between the eompanencs of the eall and the redox compounds found in photosynthesis. They axe encour aged to draw upon concepts earned in organic, biological, and physical chemistry a8 well as basic physies electronics, and optics. The role of earalysta and enzymes may be dis- cussed in zlation to she exrbon-coated eouncer electrode and dling che cazymatic processing uf the chlorophyll. Since the ‘TiOy and dye serve tine same roles as the silver halide grata and dyes used in photography, paraltel can also be sade between these two photochemical dye-sensitized systems (14) Tr should be apparent, however, chat che phoro-excited elee- trons injected into the TiO, produce electricity in the nano xynllne solae cel instead of forming an image. “The absorprion spectrum of the dye solutions can be taken using 2 standard spectrophotometer. The students can then usc this co decermine the portion ofthe solar specteum (air mass 1.5, 1000 Wim? standard spectrum) where lighe absorption can oseur (13, 75-18). Ic should be mack evident that not all the energy from sunlighr ean be converced into cleetsicalenetgy, only the chemical potential or fee energy 4G, 18), Aconsequence ofthe second law of thermadynamicss that nor more than 33% of solar energy can be converted ino electricity. or work, for a solar converter with 2 single Pigment llaminsied by daylight (19-21). The literatate r= trences can be read to improve the understanding of both the operation principles and the fabsicatioa of nanocrystalline solar eels (2, 22-24), ‘One can offen revive 2 dead cell by disassembling it, ‘washing both electrodes in water, and restaining the TiO in the berry juice, The TiO, is then washed, dred, and aserubled a previously described. When the nanocrystalline eel is n0 Jonger functional, ican be disassembled and the two con- dluctive glass electrodes can he reveled for Foture use, The seained TiO, coated glass can be reeled by wiping off che stained TIO, with a essue dampened with isopropyl or ethyl alcohol. The conductive transparent tin dioxide layer will withstand chis, bur effore should he made not co scratch it ‘The eazbon-costed glass should be used for a counter elec: wade only, and the titanium dioxide-coated glass should be recycled for the stained side of the el Conclusion Concepts of energy and electron transfer are intinduced via the building of the nanocrystalline solar cell or light de~ tector. The advantage of this experiment is that the use of natural products facilitates discussions of biotechnology a6 ‘well as physical and chemical principles. Materials science and semiconductor physics ate emphasized during the deposition of thesinrerad THO, nanocrystalline ceramic film. Caelation and ‘complexation is evident fron the attachment of che dye to the 756 sufice of the TiO, semiconductor paticles, Environmental chemistry can be linked tn chewe concepts via che regenerative cele Found in the ox It should be emphasied vo studcors that the regenration ofthe dye and mediator is muck: lik= the coupled cycles of ensigy sn materiale that have existed con Earth for billions of yeas (8). Since our dominance of these biaycochemical cycles, and in parcicular our use offs fuels may lead to changes i the physical state ofthe plane: fexg, greenhouse eflec ac ozone layer depletion), the xe acon of artificial photosynthetic systems is pot metely to present ourselves with alermatives for powering our sciey, bur itis search for out place in the biosphe Note 1. This procedure x being developed as an education kt Twill be avilable Trem sine Insitate for Chemical Education (erat! fee hence, ORD rice em seit ging Sep ternber 1998. Corscspendence and rogues foe material blo Sep tember shank bs addrsed en Gig Smut ra cad nba to Mra Grae play UBL ftpidronnaep leu ICP lip bemh Tile procedure was persed, pare atthe Imterraional Sfamporum of New Marat for Hyeogen Fark C-Mhocoelae Sy remy Cancun, Manis, Aug 31-Sepe 3, 1997 Literature Cited 12 Basing, ©. LJ. Chem Fc 1985, 62, 659-656 2. Moyes, Gj. Chem, Educ: 1997, 74, 652-656. 5, Nererddin, Ms Kay, A; Radici, 1g Humphny-takes, Rs ‘Mele £. Visa, Py Viachoposlos, Nz Geis, MJ Ame Chon Ser 1993, 175, 638.6390 4, Hasbosne, |. The Hawick Chapean and Hall London, 1975, pp 9TI-1043. J. Cher, Ede 1997, 74, IY76A-LA76B. 5. Hennalone, K: Kumara, G. Ris Kumarasinghe, As Wiyanth, Ki Siimanne, ! Semicond Sei Technol 1995, 10, 689-1693. 6, Tenmakone, Ks Kanata, G. Rs Kenepody 1 Rs Wijayaniha, K Scmisond So Technol 1997, 12, 128-132. Tomoskone, Kz Kamat, GR. Kumarasingbe A. Sitimanne fi Wijyanes, K Porch Phonbil Ae Cher 1997, 198, 193-195, 1 Schwan, T. 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