(2008)3 pp.149-.j60 Physicalia l\,4as.

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CHARACTERIZATION TiO2TOWARDSHIGHER OF INCIDENT PHOTON-TO-CURRENT EFFICIENCY DYE IN SENSITIZED SOLARCELLS*

W. Moonsl,K. Vandewall,P. Robaeysl,G. Krishnal and J. Mancal'2 Materiaalonderzoek, universiteitHasselt, Wete nsch apspark1, 3590Diepen eek. b z IMEC-IMOMEC vzw, Wetenschapspark 3Sg0Diepenbeek 1,
Summaryof the work, awardedwith the prize ot the best poster presentation Wouter Moons at by the General Scienfific Meeting ofthe BPS at the Universit6 Librede Bruxelles l\y'av 200g on 21,

1lnstituutvoor

Abstract
Worldenergyprovision probably is one of the most challenging engagements the 2.1"t of century. Amongihe novelgeneration solarcell concepts, so called"GrAEel ce " or the Dye Sensitized SolarCell is likelyone of the most promising. is basedon the spectral lt sensitization a thin ceramic mesoporousmembraneby suitabletransitionmetal of (=dye). complexes The film consists nanometer-sized of particles colloidal titanium dioxide sintered together allow for chargecarrierlransport. focusing the fundamenial, to By on thoughmostlyignored, processes like sintering the anataseTiO, porouslayer and dye soaking, incfeasein IPCE is observed. an Duringthe brief heatingof the mdso-porous film,calcination the TiO, particles of takes place.This calcination monitored is in-situby electrical measurements. tuningthe dye coverage porousTiO2,light absorption By of is enhanced,and suTface traps are decreased.In this work the adsorption kjneticsof ruthenium-based havebeenstudiedby measuring optical dyes the absofbance spectra of the sensitized filmsusingUV-Vis spectroscopy. resulting The effective aDsoroance curyes as functionof time were successfully fltted as pseudosecond-order chemicalsorption processes.Both presentedcharacterization techniquesresultedto be efficienttools towards betterunderstanding further a and improvements dye sensitized of solarcells

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lntroduction
and researchers effect by Becquerel[1]' Ever since the discoveryof the photoelectric couldbe sunlight with have been enthralled the idea that freelyavailable engineers power' into and captured converted electrical by a 'thatgenerates photovoltage solarcells,i'' a device known The mostcommonly The semiconductor in a lightuponit, incorporate pn-junction a semiconductor' shining on Dependent the solarspectrum' a has material to be ableto absorb largepartof the moreor lessclose in the ol properties the material lightis absorbed a region absorption and if pairs are generated When photonsare absorbed'electronhole to the surfiace. they can reachthe junctionwherethey are separated is their recombination prevented mostcaniers like semiconductors silicon absorbing field.Evenfor weakly by an electric the whichseparates emitterand base nearthe surface'The pn-junction are generated for probability free a high collection layer is very closeto the surfacein orderto have [2] in have principtes beendescribed manypublications [3]' The carriers.. operating Sofar,thescienceofso|arce||shasbeendominatedbydevicesinwhichthejuncti

betweeninorganicsolid-statemateria|s,usua|lydopedformsofcrySta||ineoram

silicon.lnrecentyears,novelclassesofphotovoltaicmaterialsystemshaveimer interest' of become broader solarcellscuFently and suchas, nano-crystalline organic cellsor into solar organic and into roughly molecular polymdr Thesecellscanbe divided and flallayer systems bulkheterojunctionsl4]' cheapto fabricate(theexpensive solarcells,whichare relatively Thesethird generation neededfor the processes and high-temperature high-vacuum and energy-intensive on flexiblesubstrates'and can be traditionaldevicescan be avoided),can be used

shapedortintedtosuitdomesticdevicesorarchitecturalordecorativeapp|icationsl5 for system solarlight photovoltraic a developed molecular ln 1991GreEeland O'regan of basedon the speclralsensitization to [4' and harvesting Gonversion electricitylG] lt is of The metalcomplexes' Jilmconsists transition Dy membrane suitable a thin ceramic

nanometer-sizedcol|oida|titaniumdioxideparticlessinteredtogethertoa||owforch give thesemembranes chromophore' with Whenderivatized a suitable transport' carrier

l
150

extraordinaryefficienciesfor the conversionof incident photons into electric current (IPCE).These cells are referred as "Gratzel to cells"or .Dye Sensitized Solar Cells" (DSSC).

Figure 1: Schematic operation the Dye-Sensitized of SolarCell

presentation the operation principle givenin Figure The heartof the A schematic is 1. of deviceis a mesoporous oxidefilm (see Figure typically 2), 10pmthick,whichis made of tiny nano-crystals, interconnected allow electronic to conduction take place.Oxides to suchas TiOzZnO,SnOz suchas CdSe,are the preferred and Nb2O5or chalcogenides , compounds[8]. till now, titanium Up dioxidehas been the material choicefor these of applications. Unfortunately, becauseof its large band gap (3_3.2eV), TiO, intrinsicly part of the solar emissionand so has low conversion absorbsonly the ultraviolet efficiencies. solutionlies in the separation the opticalabsorption The of and charge-

151

in absorbing the visible transfersensitizer' using an electron generating functions, gap' Photowith to region injectchargecaniersintoa substrate a wideband spectral excitalionofthesensitizer(S)resu|tsintheinjectionofane|ectroninthecond donation by restored eleclron stateofthe dyeis subbequently Theoriginal bandof TiOz. '-TiO2'usuallyan organicsolvent in impregnated the porous from the eleclrolyte, in coupleis used'Thusresults a suchas the iodide/triiodide redoxsystem, containing networkwith an enormouscontactarea betweenthe two types of three dimensional walkmodel[9]' The by tansportis bestdescribed a random wherecharge materials, band of the intercepts recapture the conduction by of regeneration the sensitizer iodide as 3) TiOzlayer(seeFigure is sputtered a holedye.A dense by electron the oxidized in The at layerto reducerecombination the electrode' iodideis regenerated blocking withPlatinum' coated typically at of tum by the reduction triiodide the counter-electrode' load' The the through external migration via The circuitis beingcompleted electron the between Fermi to conesponds the difference generated underillumination voltage overallthe of in levelof the electron the solidand the redoxpotential the electrolyte' chemical any powerfrom lightwithoutsuffering permanent electric devicegenerates transformation[10]' AM1'5(Air solarcell is 7% under of efficiency this Dyesensitized overall The reported mass1.5)f6l [7t.

TheAMl.Sconversionpowerefficiency1lAMl.sofaphotovoltaicdeviceisgivenb

n no*'"=P-ffm=FFv**
where

--

,-l'=-

v.i,""
v*J*

wherePo,uristheoutpute|ectricalpowerofthedeviceunderil|umination,Prnist cell' %" is the reference by on incident the deviceas measured a calibrated intensity cunent denslty;m is the spectral ooen circuitvoftale, and Js" is the short-circuit in for factorthat accounts deviations the spectraloutputof the solarsimulator mismatch

152

with respectto the standardAM1.5 spectrumand deviationsin the spectralresponseof cell;FF is the fill factor. the deviceunder measurewith respectto that of the reference novel deviceconceptshave been Great effort has been made to improvethe efficiency: developed,new materialshas been tested, different layer techniqueswhere applied. that 11% in of Theseeffortsresulted an efficiency approximately [8] [11][12] lt appears for one decade now the efficiency of nano-structuredcells has been essentially researchprogress.['13] despitesignificant slagnating though We investigatedwith an alternativeapproach,the effects of the fundamental, mostlyignored,processeslike sinteringand soakingthe anataseTiO2porouslayer, on the IPCE.

printed TiO, Screen Figure l\resoporous 2:

Ti02 Figure3: Dense sputtered

Experimental
For the productionof substrates,we distinguishtwo types: the first substrates are regular microscopeglasses,the second type are patternedFluorinedoped Tin Oxide ConductiveOxide (TCO),which will act as a (FTO) glasses.The latter is a Transparent

153

an cathode,respectively anode in the DSSC.'TWopattemswere etched uslng the one Iithography, with inter{igital structures otherwlth planesufaces' All substrate-s -de-ionizeA water, ultrasonically cleaned in soap water, rinsed Mth were lhoroughly to ensurea fat anddustfree substrate this rinsedIn Acetoneand boiledin lsopropanol, for good adhesion.The FTO substtateswere sputtered in a home made sputter 1 3) layer(seeFigure of approximately00nm a to installation establish denseTio2-antase with screenprinted a thick and will act as a holeblocklnglayer'All subsfates werethen The pasteis dried and sinteredin a from Solaronix. @mmerdalTiO2paste,purchased of fumaceto ensurepercolation the TiO2nanoparticles'

0.2nE Fusg+lblA

a
a

tr|drdrtrd TBA (B) Ru-dyes Rr535 (C)Ru-s3s.bis Figure 4: (A)Absorbance ten The obtainedsampleswere then dividedin seven groupssach group containing gthanolsoluiioncontalning commercial a in wre immersed an The substrates samoles. of or basddye (seeFigure4). Foralt groups,concentration temperature the Ruthenium was solution changed. pure Afrer time periods,variatingfrom th to 196h, all substrateswere rinsed wllh usinga W-Vis was measured ethanolto withdrawthe excEssof dye.The absorbance meter. layer,whichwill with a thin (3onm)Platinum The cathodelayers(FTO)were sputtered to the elecfolyte' The anodeandcathode layerfor elecirondonation act as a catalyzing

are assembled with a hot meltspacer.The complete cellswere vacuumfilled together with an electrolyte, consistedof 50m[.4 tri-iodidein acetonitrile, sealed and ready to be tested.

Results and Discussion

Annealing
were patterned that 25pm interdigital Fluorine doped Tin Oxide (FTO) substrates so structureswere obtained.These substraleswere screen-printedwith a TiO2paste and wereconducted. annealed whilein-situ resistance measurements profiles,see Figure 5 and can be This resultedin time vs. temperature/current interpretedin such way that the ideal temperatureprofile can be produced to get sufficient percolationwithout destroying the meso-porousnetwork. The ideal profile incorporate different temperature will the materials usedin the Ti02 pasteand the binders without creating cracksin the layer.Cracks due timeto burn-out thesechemical will clearlybe shownin the measurement a suddendecrease as in to a rapidheating conduction. when an increase conduction followed in is Percolation the nanocrystals observed of is by a slow decreasewherethe crystalsgrow. Theoretically, best results are obtainedwhen the surface area availablefor dye while still havinga continues network allowfor electron to chemisorption maximum is conduction. plols can be made-By Arrhenius While plotting currentin function temperature, the of ln fittingthe activation energya conduction modelcan be derived. this caseconduction hopping is governed thermal by activated [14][15][16].

155

* o

pllltb Tmperd$.re Offial'rflt g

I

g ,
E

of for annealing TiO2 Figure5: Timevs.Temperature/Current

l {r {av}
10Vand 100V) of plot Figura6: Arrhenius for annealing TiO2at several.voltage.s-(1v' line ths and the thin solid where the thick solid r,n" t"pt"""ni" the measurement fit. Arrhenius

Dye soaking be pholons should is Lightabsorption a key factorof solarcellssinceabsorbed in are SolarCells(DSSC) soaked a dye Dye into converted electrons. Sensitized dye' bythechosen can dyes, Ru-based andsoabsorption betuned typically solution,

156

Adsorption kinetics TiOzwere undertaken, determination dye concentration for the of was done with a UV-Visspectrometer measuring by absorbance 1,a"(535nm). at The time profileof dye adsorption a singleand continues is curve leadingto saturation, suggesting the possiblemonolayer coverageof dye on the surfaceof TiOz. The adsorption experiments were conductedat varioustemperatures C18oC,20oC and 37.50C)and at various concentrations (0.8m9/ml, 0.2mg/mtand 0.02mg/ml). The amount of adsorption variationis shown. lt is seen that temperature significanfly influencesthe adsorptioncapacity.High temperature results in high adsorption, suggesting endothermic an property. The adsorption function timecan be fittedwitha pseudo in of second-order rate: 't 1. 1

i=ne q.'

qr (andqe)is the amount dye adsorbed TiO2at timet (andat equilibrium).is the of on k pseudosecond-order constant dye adsorption, is expressed a function rate of it as of temperature the Arrheniusby typerelationship [17].
lnK=lnA-3

RT

IPCE
Incident Photon current (IPCE)is a technique measure conversion to Efficiency to the of incidentphotonsand the percentage those photonsthat effectively of generated an electron. halogenlamp in combination A with a monochromator used to produce is monochromatic light.This light is passedthrougha beam splitter that the incident so lighton the samplesolarcellis known. IPCEis determined [18]: by
4pce = 1Lue Dcr ' lcce

qrne:Lightharvesting (amount absorbed photons) efficiency of qcrE: Charge injection efficiency rtccE: Charge collection efficiency

t57

+ + +

o.2mglml20qc Ftltes 20rc Ru535 0.02mg/m1 20'C R!535 o.8mgy'ml

+ + ----

37.5oC0.2m9/mlRu535 Zo"Co.2mg/nrlRu535 laoo 0.zmg/rnlnu535

-18'C0 2mg/mlRu535 2o6Co 2s/ml Fu535 Ru535 O-2mSln 37.5"C

0.8 mg/ml20"C Ru535 c2 mg/ml2CfC8u535 o.o2 mg,'ml2o"c Ru535

3ff S?lil?;^ ;:?:*"#:nU'""tJlHH*1.l"':':i's"JT.':i3 ;,,ff *;ff

Belerence Gall Monoafimator
Test Cdl

(lPcE)testsetup to Photon currentEfficiency Figure8r Incident be absorbtion'there should the by saturating dye on the rLHE Since we focusedmainly "'"'nu showsthat other parameter Frg::..n without"n"ng;ng ;nv an increasein lPcE will increase' of dye the efficiency DSSC's the amountof adsorDed by changing

158

|lJ

Wavlengdx{r:m} Figure g: lpCE for DSSCas functionof soakinqtime

Conclusions
An effort has been made to increasethe Incidentphoton to Current Efficiencyof Dye Sensitized Solar Cells by focusing on the sinter process and on the soaking time process Positiveresurts were obtainedby tuningthe sinteringprofirein such way that a conductive network of TiO2 was obtained without destroying the pore size of the mesoporousnetwork. These pores promote the active surface where dye molecules couldanchorand providea directchargeinjectionin the TiO2layer_ substrates were syslematicallyimmersed in solutionswith differentconcentrationat variabre temperatures resurting a moderto describethe dye uptake.This resurted in in a positivechange of lpCE by a factor of 3. The proposed approachthereforeresultedto be efficienttowards a better understanding and improvementof dye sensitizedsolar ce s-

159

Acknowledgements Theauthor likesto acknowledge universiteit the Hasselt xios Hogeschool financial / for support'Furthermore poryspec to the FWo thanksis due to the rwr-sBo project an (Phd.Koen Vandewal) Refurences C.R. ['l] E.Becquerel, Acad. Sci.9, (1839). . i4S
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