TitaniumDioxideSolarCell

AdaptedbyLaurenCassidyandThomas.C.Keane,Ph.D.
Purpose:Thepurposeofthislabistocreatethentesttheefficiencyofdyesensitizedtitaniumdioxide
solarcells. ThisexperimentwasoriginallydevelopedbyGregSmestadoftheInstitute forChemical
Education,MadisonWI.
LearningObjectives:
1) Explainingeneralhowsolarcellsoperate
2) Identifyrealworldapplicationsofsolarcells
Introduction:Solarcelltechnologyisusedtoconvertsolarenergyintoelectricalenergywhichcanbe
usedtopowerelectricaldevices.Solarcellsarealreadyusedtosupplementorreplacedependenceon
conventionalenergysourcesinfewhomesandbusinesses.Thereisthepotential,however,forfurther
developmentandwideracceptanceof solarcellusetobetheanswertothegrowingenergysituation.
In coming photonsfromthesun exciteelectronsintheTiO2/anthrocyanindyecomplex.Theseelectrons
aretransmittedthroughtheSnOconductivecoatingtothemultimeter.Electronscomefromthe
multimeterbackintotheconductingSnOcoatingonthecarbon (sootcoated)platewhichdonates
electronstotheKI3electrolyte.Thisreducestheelectrolyte,whichdonates theextraelectronstothe
TiO2/dyecomplex,completingthecycleofelectronflow[1].
Anthrocyaninsarenaturallyoccurringdyesfoundinplants. Theyarewhyraspberriesareredand
contributetotheautumncolorofleaves.[2]
AnthocyaninContentinmgper100gfreshweight
Cranberry
Blackcurrant
Currant,red
Grape,Merlotfruit
Raspberry,red
Raspberry,black
Blackberries

60
250
15
120
40
300
200

Adaptedfromatableat http://eng.ege.edu.tr/~otles/ColorScience/anthocyanins.htm

Structureofananthrocyanin

WheretheRgroupsarenonexistent,OHorOCH3

Materials:
20resistanceSnOcoatedglass plates
NanocrystallineTiO2,AldrichBatch#18521HH
Mortar/pestle
99.7%aceticacidSigmaAldrichbatch#03228LD(orglacialaceticacid)
Distilledwater
TitronX100surfactantSigmalot#06621EH(orcleardishdetergent)
Multimeter(withbothneedleprobesandbananaclips)
Clearplastictape
Hotplate
Glassstirringrod
Ethanol
KI3 electrolytesolution
CH2Cl2
Acetone
Candle/matches
Paperclamps/Binderclips
Tweezers
BerryJuices
BingCherry,Oregonlot#PCBX3A
Raspberry,PriceChopperGradeA
BlackBerry,Driscollsorganic
Procedure:
1. Onascaleinthehood,weigh out1.5gofnanocrystallineTiO2.TransfertheweighedoutTiO2 to
amortar.Thisshouldbeenough tocoatatleast6SnOglassplates.

2. Prepareverydiluteaceticacidbyadding0.1mL 99.7%aceticacidto 50mL ofdH2O tomakea

solutionof0.035Maceticacid.Thiswillbemorethanenoughforonepersonandthevolume
caneitherbesharedbetweentwopeopleorcanbe coveredwithparafilm andsetasidefor
later.

3. TotheTiO2 add45dropsofTitron X100and1pipetfullof 0.035Maceticacid.Grindusingthe

pestle.Continueaddingmore0.035Maceticacid,dropwise,until themixturehasobtainedthe
consistencyofthintoothpaste.Itisbetterto erronthesideofslightlymoreaceticacidadded
thanlessaceticacidaddedsinceitisundesirableforthemixturetodryout.

4. Usingthemultimeterwiththeneedleprobesattached,determinetheconductivesideof6SnO
coatedplates.Whiledoingthis,checktheresistanceacrosstheplatesbyplacingtheneedlesat
pointsA,DorB,C.Keeptrackofanyanomaliesobserved.

5. Applypiecesof tapetothreesidesofeachplate ontheconductiveside.Thetapeshouldoverlap

theslide~2mm,withtheexcesstapebeingallowedtohangoffthesideortuckedunder itself to
preventitfromstickingtothelabbench. Donottapethebottomsideoftheslide.

6. Usingaglassstirringrod,applytheTiO2 mixturetotheplate,spreadingitoutsuchthata thin,

consistentcoatingofTiO2 isspread.Atthispoint,more0.035Maceticacidcanbeaddedif
clumping/flakingoccurs,butthisshouldbeavoided becauseitcouldcausetheTiO2 coatingto
betoothin.

7. Carefullyremovethetapefromtheplatesandset themonahotplateinthehoodtodry.The
hotplateshouldbeleftonhighforatleast30minutes.DuringthistimetheTiO2 coatingwill
turnbrownastheorganicsolventisevaporatedoff.Whenthe TiO2 becomeswhiteagain,the
platesaredoneandtheyshouldbeallowedtocoolbyturningoffthehotplate.
8. Storethefinishedplatesinaclean,drylocation,preferablyinaglassdishwithanevaporating
dishforalid.Itisimperativetokeepthefinishedplatesfreeofmoistureandtomakesurethe
TiO2 coatingisnotscratched.
9. Isolatetheanthrocyanindyesfromtheberriesby mashingthem,separately,inthepresenceof
acetone.About35berriesofanytypeareneededtoextracttherequiredquantityof
anthrocyanin.Thiscanbedonebyplacing theberriesinasmallbeakerwith5mLofacetone
(exactvolumenotimportant)and mashingwithaglassstirringrodtilltheberryhasdecolored
andtheliquidabovetheberryishighlycolored.
10. PlacetheTiO2 coatedplatescoatedsidedowninberryextractandletsitforaminute.Acolor
changeshouldbeobservedastheTiO2 takesuptheanthrocyanindye.Rinsetheplateswitha
smallamountofethanoltoremoveexcessdyeandberrypieceswhichmaystillbepresentin
theextract.
11. Whiletheplatesare drying,determinetheconductingsideofSnOplates,equalinnumberto
thosewhichwerecoated.Againusethesameconventionfordeterminingresistanceandnote
anylargevariations.
12. Setupacandlesuchthatitcanstandindependentlyinsomeholder. Lightthecandleand,using
tweezers, soottheplatesbymovingthem,conductingsidedown,throughtheflame.
13. Usinga Kimwipe,removeabout2mmofsootfromthreeedgesoftheplate.

14. Usingtwopaperclamps,clampthesootedplatetothedyedTiO2 suchthattheuncoatedsides

stickoutfromeitherend. Becarefulnottoscratchorundulyrubtheplatestogether.

15. Add23dropsofthe KI3 solutiontoanopenendoftheclampedplatesandallowittofilter

throughbycapillaryaction.
16. Afterthe KI3 hasspreadthroughtotheotherendoftheclampedcell,attachthered alligator
clipofthemultimetertothesootedsideandtheblackendtotheTiO2 dyedside.Recordthe
current,resistance andvoltage* ofeachcellinthesun.Alsonotethedaysweatherconditions
(cloudy,partlycloudy,fullsun),andthetimeofday.
*NOTE: Youwillnotbeabletoreadtheresistanceofanassembledcelldirectly.Todeterminethe
resistanceusetheequationformphysicsclassV=IR(voltage=current/resistance).Besuretowatch
yourunits.
PartII
1. Prepare thesolarcellcomponentsasinpartI,butinsteadofusingjust KI3solutionmix
approximately 5mLof KI3solutionwith5mLofCH2Cl2 inthehood.
2. Applythismixturetothecellasonewould the KI3inPartI,beingcarefultoobservethefactthat
thismixturewillhaveafairlyhighvapor pressure.
3. Testthevoltage,currentandresistanceofthiscellrelativetotheKI3onlycell
4. Totakethisfurther,combinedifferent amountsof KI3 and CH2Cl2 toseewhichyieldsthebest
current.
PartIII
1. Prepare thesolarcellcomponentsasinpartI,butinsteadofusing berryjuices,usetoluene
suspendedquantumdots.
2. Eithersubmergethe TiO2 inquantumdot/toluenemixture,orcarefullydripthedot/toluene
suspensionontotheTiO2 surface.
3. Allowtheplatestodry.Inthisinstanceitwonthurtthedyeifthe platesarewarm.Between
drips oraftersubmersion,gentlywarmtheplatestodriveofftoluene.
4. Testthevoltage,currentandresistanceofthiscellrelativeto thebestperformingberrycell.

Questions:
1)
2)
3)
4)

WhatistheoxidationnumberofthetitaniuminTitaniumdioxide?
Whatisaproblemwiththesesolarcells,andwhatcouldbedonetoimprovethem?
Whatis thefunctionoftheKI3 electrolyte?
Wouldone expecta greatercurrenttoregisteronaclearsunnydayorapartlycloudyday?
Why?

5) Giventherelativeconcentrationsofanthrocyaninsinthevariousberries,whichwouldyou
suspecttoproducethehighestcurrent? Why?Whatdidyouobserve?
6) Ifoneweretopreparetwocellsthesameway(usingthesamematerials)whatwould
contributetodifferencesincurrent/voltage/resistance?Wasanydifferencenoticed?
PtII
7) WhatisnoticedabouttheKI3/CH2Cl2mixture?
8) WhatdoyouobservethatisdifferentwhentheKI3/CH2Cl2 isaddedtothesolarcellversuswhen
straightKI3 isadded?
9) WhatisasimpleexperimentaltechniquewhichcouldbeappliedtopreventtheKI3/CH2Cl2
mixturefromdrippingoutofapasturepipette?
PTIII
10) Wouldadotperformthesameastheanthrocyanin?
11) Whatcolordoesthe TiO2/dotcoatedsurface turnwhentheKI3 isadded?
12) Whataretwobenefitsandtwoconcernsonewouldhavefromusingdotsoveranthrocyanins?

Answers:
1) Theoxidation#ofOis(1)sotwoOwouldmeanachargeof(2)sotobeneutral,theTImust
be(2+)
2) Some problems couldbethattheKI3 electrolyteisliquidandcandryout,onewouldneedalot
ofraspberriestodothis andraspberriesareexpensive. Itisdifficulttoconsistentlycoatthe
plateswithTiO2.Solutionswouldbereplacetheelectrolytewithsomethingwhichwontdryout
orsealthesidesverywell,useanthrocyanindyefromalessexpensivesource,use/developa
spincoatingtechnique.Anywellthoughtoutproblem/solutionpair.
3) TheKI3 electrolytedonateselectronstothe TiO2/dyematrixandacceptselectronsfromthe
carboncoatedplate.Itservesasabridgemuchlikeasaltbridgeinthevoltaiccell.
4) Onewouldexpectagreatercurrentonaclearsunnydaythanonacloudyone.Thisisbecause
theintensityofthelightwouldbegreaterthereforemorephotonsstrikingthesurfaceofthe
TiO2complexexcitingmoreelectrons.
5) Onewouldactuallyexpecttheblackberrycoated TiO2 platestoyieldthehighestcurrent,
becausetheyhaveahigheranthrocyanincontent.WhatIobservedwasthatofcherry,
blackberry,raspberry,andPbdots.Raspberryproducedthehighestcurrent.
6) SomethinginvolvingthevariableintheamountofTiO2 depositedontheplate,amassive
differenceintheresistanceoftheplate,thelengthoftimetheTiO2 wasmaintainedincontact
withthedyemedium,thesurfaceareacovered byTiO2/dyecomplex,etc
PartII
7) SomethingtotheeffectoftheKI3 andCH2Cl2 dontmixverywell.
8) Thecapillaryactionpullingthemixtureacross theTiO2/dyematrixismuchgreaterthanthatfor
theKI3.
9) Wettingthepipettewouldreducedrippingofthehighvaporpressureliquid.
PartIII
10) Theoreticallyadotshouldperformbetterthananthrocyanins,oratleastamixtureofthem
should.Thisisbecausedotshavetunablebandgapsdependingonthesizeofthedotsoshould
beabletofindtheoptimumabsorptionofphotonsforincomingsolarenergy.
11) WhenusingPbdots,thesurfaceturnsgreenupontheadditionofKI3.Stillworkingonwhyand
Imnotsurewhetherornotthiswouldhappenwithotherdottypes.Mybestsuspicionisthat
eitherthePboranothermetalpresentinthedot,orbotharecomplexedwiththeIodine.
12) Benefits:cantunedotsdependingontheirsize.
Dotsthemselvescanbeusedtocoataconductingsurface.
Drawbacks:Dotsaremoreexpensivethananthrocyanins
Dotsoftencontaintoxicsubstancessuchaslead.

References/FurtherReading
[1]GregP.Smestad (1998). Educationand solar conversion:Demonstratingelectrontransfer. Solar
EnergyMaterialsandSolarCells, Volume55,Issues12, 23July1998,157178.
[2]SemihOTLES. ColorScience:Anthrocyanins.RetrievedApril13,2003,from
http://eng.ege.edu.tr/~otles/ColorScience/anthocyanins.htm
[3]AbstractofHomeMadeSolarCell.RetrievedApril14,2003,from
http://resources.edb.gov.hk/~science/hkcho/5s/wongts.pdf
[4] JintingJiu,SeijiIsoda,MotonariAdachi,andFuminWang.(2007).PreparationofTiO2 nanocrystalline
with35 nmandapplicationfor dyesensitizedsolarcell. JournalofPhotochemistryandphotobiology,
Volume189,Issues23,25June2007,314321.

SupplyListfor10Students
10(20resistance)SnOcoatedglassplates
NanocrystallineTiO2,AldrichBatch#18521HH
10Mortars/pestles
99.7%aceticacidSigmaAldrichbatch#03228LD(orglacialaceticacid)
Distilledwater
TitronX100surfactant Sigmalot#06621EH(orcleardishdetergent)
10Multimeters(withbothneedleprobesandbananaclips)
Clearplastictape
10Hotplates
10Glassstirringrods
Ethanol
KI3electrolytesolution
CH2Cl2
Acetone
10Candles
Matches
Severalpaperclamps
10Tweezers
BerryJuices
BingCherry,Oregonlot#PCBX3A
Raspberry,PriceChopperGradeA
BlackBerry,Driscollsorganic

Placement
Thislab dealswithconceptsthat arecoveredinPhysicscourses,butitisalittlemoreinvolved
thanwhatistypicallydoneinPhysicslabs.Also,theconceptbehindunderstandingquantum
dotsissomethingachievedinanupperlevelchemistrycourse.Itis therefore suggestedthat
this labwouldworkbestinaPhysicalChemistrylab.