research article spectroscopic and morphological studies of...

Hindawi Publishing CorporationInternational Journal of PhotoenergyVolume 2013 Article ID 582786 11 pageshttpdxdoiorg1011552013582786

Research ArticleSpectroscopic and Morphological Studies ofMetal-Organic and Metal-Free Dyes ontoTitania Films for Dye-Sensitized Solar Cells

Gabriella Di Carlo1 Daniela Caschera1 Roberta G Toro1 Cristina Riccucci1

Gabriel M Ingo1 Giuseppina Padeletti1 Luisa De Marco2 Giuseppe Gigli234

Giovanna Pennesi5 Gloria Zanotti5 Anna M Paoletti5 and Nicola Angelini5

1 Institute for the Study of Nanostructured Materials (ISMN) CNR Via Salaria km 29300 Monterotondo 00015 Rome Italy2 Center for Biomolecular Nanotechnologies (CBN) Fondazione Istituto Italiano di TecnologiaEnergy Platform Via Barsanti Arnesano 73010 Lecce Italy

3 National Nanotechnology Laboratory (NNL) CNR Istituto Nanoscienze co Distretto Tecnologico Via Arnesano km 573100 Lecce Italy

4Department of Mathematics and Physics ldquoE De Giorgirdquo University of Salento Via per Arnesano 73100 Lecce Italy5 Institute of Structure of Matter (ISM) CNR Via Salaria km 29300 Monterotondo 00015 Rome Italy

Correspondence should be addressed to Gabriella Di Carlo gabrielladicarloismncnrit andNicola Angelini nicolaangeliniismcnrit

Received 13 July 2013 Accepted 27 August 2013

Academic Editor Giuseppe Calogero

Copyright copy 2013 Gabriella Di Carlo et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

We have investigated the spectroscopic behavior of three different sensitizers adsorbed onto titania thin films in order togain information both on the electron transfer process from dye to titania and on the anchorage of the chromophore ontothe semiconductor We have examined by UV-Vis and fluorescence spectroscopy the widely used ruthenium complex cis-di(thiocyanato)bis(221015840-bipyridyl-441015840-dicarboxylato)ruthenium(II) (N719) the more recently developed organic molecular 3-(5-(4-(diphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (D5) and a push-pull zinc phthalocyanine sensitizer (ZnPc) Threetype of titania films with different morphology characterized by SEM and FT-IR measurement were considered a mesoporoustransparent film deposited by spin-coating (TiMS) a semiopaque film deposited by doctor-blade from mesoporous titania(TiMS DB) and a semiopaque filmdeposited by doctor-blade formcommercial P25 titania (P25 DB)Theuse of TiMS is responsiblefor the adsorption of a higher amount of dye since the mesoporous structure allows increasing the interfacial area between dye andtitania Moreover the fluorescence emission peak is weaker when the sensitizers are adsorbed onto TiMS These findings suggestthat mesostructured films could be considered the most promising substrates to realize photoanodes with a fast electron transferprocess

1 Introduction

Dye-sensitized solar cells (DSSCs) are receiving increasingattention during the last decades since they are considereda viable and cost-effective technology for the conversionof sunlight into electricity [1ndash3] In these devices metal-organic or metal-free dyes are chemically adsorbed ontoa wide band gap semiconductor oxide [1ndash8] The working

principle of a DSSCs system is based on the photochemicaland photophysical processes upon photoexcitation of thedyes by visible light electrons are excited from the groundstate of the dye to its excited state and then their injectioncan occur from the excited dye into the conduction band ofthe semiconductor

To achieve a high power conversion efficiency the elec-tron injection process must be certain and faster than

2 International Journal of Photoenergy

the competing fluorescence and nonradiative processes Thisphotoinduced electron transfer leads to the production ofphotocurrent and consequently it is crucial to the deviceefficiency [1ndash3]

In DSSCs the sensitizer is one of the critical componentsas it absorbs sunlight and induces the charge separationprocess In order to enhance power conversion efficiencies ofDSSCs it is imperative to improve the light-harvesting abil-ity of the dyes It is also fundamental to investigate and tooptimize the dye-substrate interaction that is involved in theelectron transfer process [9]

Ruthenium sensitizers such as cis-di(thiocyanato)-bis[221015840-bipyridyl-441015840-dicarboxylic acid] ruthenium (II)(N3) or its bistetrabutylammonium (TBA) salt counterpart(N719) in combination with thick titania films (gt12ndash15mm)have shown solar-to-electric power conversion efficienciesup to 11 [2 10] Several groups have also developedmetal-free organic sensitizers that are less expensive andobtained efficiencies in the range of 4ndash8 [11ndash15] Interesthas been recently devoted to the design of sensitizers that areable to absorb at the near infrared region by extending thespectral range for the photocurrent generation with respectto Ru-complexes Porphyrins and phthalocyanines are beingcurrently considered to this specific aim and meaningfulresults have been achieved [16ndash18]

The critical factors that influence sensitization are theexcited-state redox potential which should match the energyof the conduction band edge of the semiconductor substratethe light-harvesting ability and the electron transfer processthat is influenced by the electronic coupling between thelowest unoccupied molecular orbital (LUMO) of the dye andthe TiO

2conduction band One of the major factors for low

conversion efficiency of many organic dyes in the DSSC is theformation of dye aggregates on the semiconductor surfaceTherefore to obtain optimal performance aggregation ofdyes needs to be avoided by promoting the chemisorptiononto the substrate and by increasing the surface area of thesemiconductor oxide High surface area substrates can alsopromote the adsorption of a larger amount of dye moleculesenhancing the light-harvesting efficiency However in orderto improve the power conversion efficiency of photoanodesfor DSSCs it is necessary to achieve both optimal morpho-logical properties and fast electron transport [19ndash22]

To gain information about the photoinduced electrontransfer process from the sensitizers to the semiconductorsand indications about the linkage between dye and substratethe study of the spectroscopic features of chromophores ontothe semiconductor is of crucial importance Absorption andsteady-state emission spectral features can give informationon the dye interaction with the substrate since they areinfluenced by the chemical environment of the sensitizers andhence it is expected that the structural and chemical natureof the sensitizers and the structural properties of titaniasubstrates have a key role in determining the final spectralfeatures of the chromophore Moreover time-resolved fluo-rescence decay can provide insights into the electron injectionprocess since it is competitive with fluorescence relaxationElectron injection is found to generally occur with a timemuch shorter than the excited-state lifetime of typical dyes

therefore time-resolved fluorescence decay studies are veryuseful to understand these dynamic photoinduced processes

Herein for the purpose of comparison three differentdyes were examined the widely used inorganic rutheniumcomplex cis-di(thiocyanato) bis(221015840-bipyridyl-441015840-dicar-boxylato)ruthenium(II) (N719) the more recently developedorganic molecular 3-(5-(4-(diphenylamino) styryl)thiophen-2-yl)-2-cyanoacrylic acid (D5) [15] and the push-pullzinc phthalocyanine sensitizer (ZnPc) [23] The dyes wereadsorbed onto three types of thin film titania substratesmesoporous transparent titania deposited by spin-coating(TiMS) mesoporous titania deposited by doctor-blade(TiMS DB) and commercial P25 titania deposited bydoctor-blade (P25 DB) Titania films were characterizedby scanning electron microscopy (SEM) and by Fouriertransform infrared (FT-IR) spectroscopy whereas the dye-sensitized films were studied by UV-Vis and fluorescencespectroscopy

2 Experimental Section

21 Preparation of Titania Thin Films

211 Transparent andMesoporous Films Mesoporous titaniafilms were synthesized using the P123 block copolymer astemplate in order to obtain an ordered porous structurewith a controlled geometry The titania precursor solutionswere prepared according to the procedures described in theliterature using pluronic surfactant [24]

In a typical synthesis 14mL of concentrated HCl wereslowly added to 21 g of titanium(IV) ethoxide at room tem-perature In another flask 065 g of P123 were dissolved in 6 gof 1-butanol and subsequently added to the titanium solutionThe system was kept under stirring at room temperaturefor 3 hours The as-prepared solution of titania precursorwas deposited on FTO conducting glass substrates (Dyesol15Ω sqminus1) by spin-coating at 2400 rpm After aging at 25∘Cfor 2 days optically uniform and transparent films wereobtained These films were calcined at 350 for 30 minutesusing a ramp rate of 1∘Cmin to remove the template and theresidual organic precursors TiO

2electrodes were obtained

by deposition of three layers with a final calcination at350∘C for 2 hours and were labeled as TiMS (Table 1) Theresulting mesoscopic oxide film was around 1 120583m thick andtransparent

212 Semiopaque Films from Mesoporous Titania Mesopo-rous titania powder was prepared from the solution of tita-nium (IV) ethoxide and P123 described above after aging at25∘C for 5 days and subsequent calcination at 350∘C for 4hours using a ramp rate of 1∘Cmin according to a recentlypublished procedure [25]

Titania films were prepared from mesoporous titaniapowder by using the doctor-blade technique according toa procedure described elsewhere [26] Dried powder wasdispersed in ethanol (EtOH) treated with ultrasonic bathfor 30min then stirred at 50∘C for 1 h This procedure wasrepeated three times in order to obtain a homogeneous and

International Journal of Photoenergy 3

Table 1 Details about the preparation of titania films

Sample TiO2 sourceDepositiontechnique

TiMS Alcoholic solution of titanium(IV)ethoxide and P123 Spin-coating

TiMS DBMesoporous titania powder prepared

from alcoholic solution oftitanium(IV) ethoxide and P123

Doctor-blade

P25 DB Commercial P25 titania powder Doctor-blade

opalescent colloidal suspension The latter was mixed withethylcellulose (5ndash15mPalowasts) previously dissolved in ethanol(10 ww) and stirred again at 50∘C overnight Terpineolwas added and the resulting mixture was further stirred for6 h Finally ethanol was removed by a rotary evaporator toobtain pastes suitable for doctor-blade deposition The pastehad the following weight percentage composition TiO

2 4

ethylcellulose 2 terpineol 94 The so-obtained titaniapaste was deposited on the FTO conducting glass (Dyesol15Ω sqminus1) Two edges of the FTO glass plate were coveredwith a layer of adhesive tape (3M Magic) to control thethickness of the film successively the titania paste was spreaduniformly on the substrate by sliding a glass rod along thetape spacer After drying the coated plates were sintered inair for 1 h at 450∘C and labelled as TiMS DB (Table 1) Theresulting mesoscopic oxide film was around 1 120583m thick andsemiopaque

213 Semiopaque Films from Commercial Titania Referencetitania films were prepared from commercial P25 titaniapowder by using the doctor-blade technique according toa procedure described elsewhere [26] Briefly acetic acidwater and ethanol were added drop by drop into a mortarcontaining P25 titanium dioxide nanoparticles (provided byEvonik Degussa) The TiO

2dispersion was transferred with

excess of ethanol into a beaker for stirring a sonication stepsthen anhydrous terpineol and ethyl cellulose (previouslydissolved in ethanol) were added After further stirring andsonication steps the dispersion was concentrated by rotaryevaporator The final colloidal paste was characterized by thefollowing composition (wtwt) 5 TiO

2 05 acetic acid

25 ethylcellulose 87 terpineol and 5 ethanol The so-obtained titania paste was deposited on the FTO conductingglass (Dyesol 15Ω sqminus1) Two edges of the FTO glass platewere covered with a layer of adhesive tape (3M Magic) tocontrol the thickness of the film successively the titania pastewas spread uniformly on the substrate by sliding a glassrod along the tape spacer After drying the coated plateswere sintered in air for 1 h at 450∘C and labelled as P25 DB(Table 1) The resulting mesoscopic oxide film was around1 120583m thick and semiopaque

22 Adsorption ofDyes ontoTitania Films Thedye-sensitizedfilms were prepared using a 02mM N719 solution (ditetra-butylammonium cis-bis(isothiocyanato) bis(221015840-bipyridyl-441015840-dicarboxylato)ruthenium(II)) which was obtained by

dissolving the dye in a mixture of acetonitrile and tert-butylalcohol (1 1 volume ratio) The titania films were immersedinto the N719 solution overnight at room temperature Afterthat all the dyed films were washed with acetonitrile andstored in the dark

A similar procedure was used for the adsorption of D5and ZnPc The D5 dye was dissolved in acetonitrile to obtaina dye concentration of 02mM whereas the solution of ZnPcwas obtained by dissolution in ethanol (089mg of dye in10mL of ethanol)

23 Characterization UV-vis spectra of the films were col-lected in the wavelength range 300ndash870 nm using a dou-ble beam spectrophotometer V-660 (Jasco) equipped withan integrated sphere The absorbance of the dye solutionwas measured using a quartz cell of thickness 1 cm Theabsorbance of dye-TiO

2systems was recorded using 60mm

integrated sphereSteady-state fluorescence spectra for dyes solution and

dyes-TiO2films were recorded in a Jobin Yvon Fluorolog3

spectrofluorometer using grids of 5 nm for the excitation and5 nm for emission

Time-resolved fluorescence measurements were carriedout by a time-correlated single-photon-counting (TCSPC)system (Horiba-Jobin Yvon) Time-resolved measurementsare carried on exciting the samples using a 405 nm pulsedlaser diode and collecting the emission decay at the cor-responding maximum emission wavelength for the specificanalysed dye The fluorescence decay profiles were analysedthrough decay analysis software (DAS6a HORIBA Scientific)to a multiexponential decay equation The quality of the fitswas checked by examining the residual distribution and the1205942 valueBoth steady-state and time-resolved fluorescence mea-

surements of thin films TiO2systems were collected in right-

angle (RA) configuration with a tilt angle of 30∘ to minimizesubstrate scattering effects

Fourier transform infrared (FT-IR) spectrawere collectedusing a Jasco 4100 FTIR spectrophotometer equipped withan attenuated total reflectance (ATR) unit The samples forthe analysis were prepared through preliminary drying at120∘C

FE-SEM characterizations were carried out with a high-brilliance LEO 1530 field emission scanning electron micro-scope apparatus equipped with an INCA 450 energy-dispersive X-ray spectrometer (EDS) and a four-sectorbackscattered electron detector (BSD) Before the analysisthe surfaceswere coatedwith a thin layer of carbon in order toavoid charging effects The carbon coating was deposited byusing an Emitech sputter coater K550 unit a K 250 carbon-coating attachment and a carbon cord at a pressure of 1 times10minus2mbar in order to produce a carbon film with a thicknessof a few nanometers

3 Results and Discussion

The spectral properties of different dyes have been comparedin order to investigate the electron transfer process from the


N

N

HO

HO

O

N

O

N

RuNCS

NCS

O

O

N N

N

N

N

N

N

N

Zn

N

S

CN

COOH

HOOC

Ominus

N+

Ominus

H3C 3

2

CH

3CH

3CH

t-Bu

t-But-Bu

N719

D5

ZnPc

Figure 1 Chemical structure of the dyes N719 D5 and ZnPc

dye to the conduction band of titania films that is respon-sible for the production of photocurrent in DSSCs Metal-organic and metal-free dyes were adsorbed onto transparentand semiopaque mesoporous titania thin films and onto asemiopaque film form commercial P25 titania In particularwe have investigated the behaviour of a ruthenium complex(N719) an organic dye (D5) and a zinc phthalocyaninesystem (ZnPc)The chemical structure of these dyes is shownin Figure 1

All the dyes have been adsorbed onto titania filmswith different morphology a mesoporous transparentfilm deposited by spin-coating (TiMS) a semiopaquefilm deposited by doctor-blade from mesoporous titania(TiMS DB) and a semiopaque film deposited by doctor-blade form commercial P25 titania (P25 DB) Thepreparation of the films was properly tailored in orderto get thin substrates with a comparable thickness of about1 120583m

31 FTIR Characterization The surface functional groups oftitania substrates play an important role in the chemisorptionof the dyes Indeed the sensitizers that we are consideringin this work are usually bonded to titania through theircarboxylic groups which interact with hydroxyl groups attitania surface

ATR-FTIR measurements were used to investigate theamount of hydroxyl groups in the different titania films andthe spectra are displayed in Figure 2 Furthermore by theseanalyses it is also possible to get more information on thepresence of carbon species in the samples

The ATR-FTIR spectra show similar trends but withsome significant differences The bending vibration band ofthe surface hydroxyl groups is observed at about 1630 cmminus1

4000 3500 3000 2500 2000 1500 100092

94

96

98

100

TiMS

Abso

rban

ce (a

u)

Wavenumber (cmminus1)

P25 DBTiMS DB

Figure 2 ATR-FTIR spectra of titania thin films (a) P25 DB (b)TiMS DB and (c) TiMS

and the corresponding stretching vibration peak is located at3200ndash3600 cmminus1 [27 28] From these spectra a significantlyhigher amount of hydroxyl groups was noticed in transparenttitania thin films (TiMS)This could be attributed to the lowersinterization temperature (350∘C instead of 450∘C used forDB films) that allows preserving a high amount of hydroxylsurface groups and it seems also reasonable to assume that itcould be also related to a higher surface area On the contrarythe film from Degussa P25 has the lowest amount of surfacehydroxyl groups

Analyzing the FTIR spectra it can also be observed thattitania films contain carbon groups Indeed the peaks at


Table 2 Peak position of UV-Vis absorbance and fluorescenceemission

Sample 120582Abs (nm) 120582Em (nm)N719 310 386 537 728N719P25 DB 478 726N719TiMS DB 474 719N719TiMS 492 720D5 300 479 630D5P25 DB 468 605D5TiMS DB 469 623D5TiMS 472 618ZnPc 352 613 687 694ZnPcP25 DB 689 695ZnPcTiMS DB 692 698ZnPcTiMS 689 702

about 1000ndash1100 cmminus1 suggest the presence of TindashOndashC bonds[27] Furthermore the peak at about 1400 cmminus1 has beenattributed to asymmetric bending vibrations of CndashH bonds[27 28] The observation from FTIR that the films containTindashOndashC and CndashH bonds indicates the presence of residualorganic groupsThe intensity of these signals for P25 DB andTiMS is comparable whereas the residual carbon content isapparently lower for TiMS DB film (Figure 2)

32 Morphological Investigation Further insights into thestructural properties of titania films were obtained throughFE-SEM analysis The micrographs of titania surface filmsprepared by doctor-blade (Figure 3) reveal that when com-mercial P25 was used for the formulation of the paste thephotoanode surface consists of small nanoparticles withvoids into the structure By using mesoporous titania thephotoanode surface is composed of small nanoparticles anda porous structure can be observed It is worth to noticethat in TiMS DB the surface morphology is more uniformwith the presence of small pores that could increase theinterface betweendye and titania whereas larger voids are notdetected

In TiMS prepared by spin-coating the surface mor-phology is completely different The films are furthermorecompact and can be observed the presence of domains withan ordered structure The latter are mesoporous channelswhich are responsible for a nanoporous structure and highsurface area

33 UV-Vis and Fluorescence Measurements In order to gaininformation on the anchorage of the chromophore onto thesemiconductor and on the electron transfer process from thedyes to titania the spectroscopic features of the dye solutionsand of the dye-sensitized titania films have been investigated

The absorption and the steady-state fluorescence spectraof the free dye solutions and the corresponding dye-sensitizedTiO2films were recorded and the data are summarized in

Table 2The absorption spectra of N719 sensitized TiO

2films

along with the reference spectrum of the free dye in an

acetonitrile and tert-butyl alcohol solution (1 1 volume ratio)are shown in Figure 4 In particular the UV-vis absorptionspectrum of N719 solution is dominated by two broad bandsat around 386 and 537 nm generally assigned to a Metal-to-Ligand Charge-Transfer (MLCT) transition in which an elec-tron is transferred from Ru to one of the bipyridine ligandsand an intense UV absorption at around 310 nm attributedto an electronic transition between the 120587-120587lowast orbitals ofthe dcbpyH ligands [29ndash31] When the N719 molecules areadsorbed onto the surface of mesoporous TiO

2films the

MLCT band at 537 nm becomes predominant and shifts atlowerwavelengths depending on the consideredTiO

2system

The measured blue shifts for all the dye-sensitized TiO2

systems are reported in Table 2 as it can be seen it is higherfor the N719 adsorbed onto TiO

2films obtained by doctor-

blade (P25 and TiMS DB) whereas it is lower for the N719adsorbed onto transparent TiO

2obtained by spin-coating

technique (TiMS) The observed shifts in the absorptionspectra are probably due to chemical interactions betweenthe dye and the semiconductor TiO

2surface which modify

HOMO and LUMO levels of the adsorbed complexes withrespect to those of the free dye At the same time we wouldlike to underline the higher absorption intensity shown bythe transparentN719TiMS systemswith respect to the otherTiO2systems which may indicate that this transparent layer

can adsorb more N719 molecules compared with the otherTiO2layers having the same thicknessThis is also confirmed

by the intense red coloration of the TiMS sample after the dyeadsorption These findings are in agreement with ATR-FTIRresults previously discussed since the most intense peaks inUV-vis spectra of dye-sensitized TiMS films is promoted bythe presence of a high number of surface hydroxyl groups

A similar trend has been also found in the case of themetal-free organic dye D5 adsorbed on TiO

2mesoporous

systems (Table 2) Two absorption bands at 479 nm and300 nm are visible in the Uv-Vis spectrum of dye solutionthe band in the UV region corresponds to a 120587-120587lowast transitionof the conjugated molecules whereas the band in the Viscan be assigned to an intramolecular charge-transfer statebetween the diphenylaniline electron donating moiety andthe cyanoacetic acceptor [15] When the dye is attached toTiO2surface a blue shift of the absorption maximum at

479 nm is found (Table 2) Also in the case of D5 the trans-parent TiMS thin films have the highest intense absorptionband and the lowst blue shift with respect to those observedfor D5TiMS DB and D5P25 DB thus indicating a higherdye uptaking

The fluorescence measurements of N719 and D5 sensi-tized mesoporous TiO

2systems reported in Figures 5 and

6 show the characteristic fluorescence emission of the freedyes but shifted to lower wavelenghts In the case of N719(Figure 5) for example upon excitation at 120582ex = 510 nm thesolution has an emission maximum at 728 nm which shiftsat 725 719 and 720 nm for N719P25 DB N719TiMS DBand N719TiMS respectively In analogy the D5 sensitizedTiO2systems have a blue shift in the emission spectra

(Figure 6) that depend on the TiO2system More interesting

if we consider the intensity of the emission band for both ofthe two sets of samplewe observe that they decrease following


(a) (b)

(c)

Figure 3 FE-SEM images of surface titania films (a) P25 DB (b) TiMS DB and (c) TiMS

300 400 500 600 700 8000

02

04

06

08

1

Abso

rban

ce (a

u)

Wavelength (nm)

N719N719P25 DB

N719TiMS DBN719TiMS

Figure 4 Uv-Vis absorbance for N719 solution and N719 sensitisedTiO2systems

the order P25 DB gt TiMS DB gt TiMS The reduction inthe emission intensity is thus more evident in the case oftransparentmesoporousTiO

2layer andwehypothesized that

it can be associated in first approximation to a better andmore

650 700 750 800

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

Inte

nsity

(cou

nts)

Wavelength (nm)

N719N719P25 DB

N719TiMS DBN719TiMS

Figure 5 Steady-state fluorescence emission for N719 solution andN719 sensitised TiO

2systems

efficient electron injection process from the excited state ofthe dye to the conduction band of the semiconductor

The UV-Vis absorption spectra of the compound ZnPcin EtOH and on mesoporous TiO

2films are displayed in


500 550 600 650 700 750

0

1000000

2000000

3000000

Inte

nsity

(cou

nts)

Wavelength (nm)

D5D5P25 DB

D5TiMS DBD5TiMS

Figure 6 Steady-state fluorescence emission for D5 solution andD5 sensitised TiO

2systems The emission intensity values for D5

sensitised TiO2systems are multiplied by a factor 5

Figure 7 The UV-Vis absorption spectrum of ZnPc exhibitsan intense Soret band (300ndash400 nm) due to the 120587-120587lowast tran-sition with charge-transfer character and a strong Q bandcentered at 687 nm [32] In addition compared with thesolution the zinc phthalocyanine derivative on mesoporousTiO2films show broader absorption spectra extended to

800 nm suggesting the formation of aggregate on the surfaceof the semiconductor [33] The absorption spectra of thephthalocyanine adsorbed onto TiO

2systems exhibit a small

red shift (Table 2) that may be due to the presence of car-boxylic protons of phthalocyanine which upon adsorptionon TiO

2 release the proton and bind to Ti4+ centresThe Ti4+

sites act as electron withdrawing and produce the observedred shift in the absorption bands [34]

Figure 8 shows the steady-state fluorescence emissionspectra (120582ex = 400 nm) of ZnPc solution the typicalphthalocyanine emission band centred around 700 nm iseasily visible [35] The ZnPcP25 DB ZnPcTiMS DB andZnPcTiMS exhibit a strong Q band emission peak at695 nm 698 nm and 702 nm respectively In analogy to theother two dyes when ZnPc is adsorbed onto the TiO

2layers

a net decrease in the emission intensity can be observed thussuggesting the possibility of an electron injection process

Time-correlated single-photon counting (TCSPC) mea-surements are performed to obtain information about thedecay times of the relaxed excited state at S

1of the dye

interacting with the semiconductor materials As reportedby several studies [18 23 36 37] TCSPC measurements canbe useful to evaluate the photoelectron injection dynamicsin dye-sensitized semiconductor films In Figure 9 the time-resolved emission kinetics for the three dyes in solutionand the correspondent dye sensitised TiO

2systems are

shown In particular the emission decay measurements arecollected at 120582em = 730 nm (Figure 9(a)) for N719 at 120582em =640 nm (Figure 9(b)) for D5 and at 120582ex = 700 nm for ZnPc(Figure 9(c))

Fluorescence emission decay curves of the N719 solutionhave been deconvoluted by a biexponential function while

300 400 500 600 700 800

Abso

rban

ce (a

u)

Wavelength (nm)

ZnPc ZnPcP25 DB

ZnPcTiMS DB ZnPcTiMS

Figure 7 Uv-Vis absorbance for ZnPc solution and ZnPc sensitisedTiO2systems

650 675 700 725 7500

100000

200000

300000

400000In

tens

ity (c

ount

s)

Wavelength (nm)

ZnPc ZnPcP25 DB


Figure 8 Steady-state fluorescence emission for ZnPc solution andZnPc sensitised TiO

2systems The emission intensity values for

ZnPc5 sensitised TiO2systems are multiplied by a factor 5

for N719 interacting with different TiO2based films the

decays have amore complex behaviour and need a three com-ponent exponential function The results shown in Table 3reveal that for dye solution the most significative time value(1205911) is about 3 ns (119860

1= 93) and a little percent of molecules

decay with a time of 1205912= 277 ns (119860

2= 7) The longer decay

is comparable with time decay reported in the literature forN719 systems [38] while the shorter excited-state lifetimeindicates an enhancing of the nonradiative deactivationchannels probably due to the presence of protons on carboxylgroups [39] The 120591

1= 3 ns value appears to be retained in

N719-TiO2systems but the corresponding amplitude (119860

1)

decreases from 93 in solution to 30 in solid state Also thelongest time decay in solution (120591

2= 277 ns) is preservedwhen

the dye is adsorbed on TiO2surface but this value is lower


6 8 10 12 14 16 18 20 22 24 26 28 30100

1000

Cou

nts

N719N719P25 DBN719TiMS DB

N719TiMS

Time decay (ns)

Prompt

(a)

10

64 8 10 12 14 16 18 20

100

1000

Cou

nts

D5PromptD5P25 DB

D5TiMS DB

D5TiMS

Time decay (ns)

(b)

Prompt

10 20 30 40 50 60 70

10

100

1000

Cou

nts

Time decay (ns)

ZnPcZnPcP25_DBZnPcTiMS_DB

ZnPcTiMS

(c)

Figure 9 Fluorescence kinetics of (a) N719 solution and N719 sensitised TiO2systems (b) D5 solution and D5 sensitised TiO

2systems and

(c) ZnPc solution and ZnPc sensitised TiO2systems

(1205912= 15 ns in solid state) because dyemolecules are now closer

to each other than in solution and this results in the quench-ing phenomena In addition a third shorter time appears(056 ns for N719P25 DB 041 ns for N719TiMS DB and036 ns for N719TiMS) that can be related to the electrontransfer process from the excited state of the dye to theconduction band of the semiconductor

Lifetime of D5 dye in solution is analysed by a threeexponential component function and the result of 014 nsassociated with the most significative amplitude (119860

1= 80)

presents a good agreement with analogous systems [40]However for D5 sensitised TiO

2systems the resolution of

the TCSPC setup does not allow for resolving numericallythe changes in lifetime They are all sub 001 ns a time

close to the time response of the detector Nevertheless justfrom a qualitatively point of view it is interesting to observethat D5TiMS system seems to have the sharpest decayprofile with respect to D5TiMS DB and D5P25 DB Thebetter quenching effect could be related to a different dye-TiO2interaction that could promote electron injection in

semiconductor bandsIn the case of ZnPc solution the fluorescence emission

decay exhibits a monoexponential behaviour with a lifetimeof 3 ns comparable for values reported in the literature forunsubstituted phthalocyanine systems [18 41]

ZnPc sensitised TiO2systems fluorescence emission

decays instead are analysed using a three component expo-nential function and the results are summarized in Table 3


Table 3 Lifetime decay of dye-TiO2 systems

Sample 1205911(ns) 120591

2(ns) 120591

3(ns) 119860

1() 119860

2() 119860

3() 1205942

N719 289 277 mdash 93 7 mdash 12N719P25 DB 344 158 056 32 20 48 12N719TiMS DB 274 145 041 33 20 47 12N719TiMS 260 156 036 32 15 53 12D5 014 063 161 80 9 11 10D5P25 DB lt001 mdash mdashD5TiMS DB lt001 mdash mdashD5TiMS lt001 mdash mdashZnPc 3 12ZnPcP25 DB 205 048 005 24 29 47 13ZnPcTiMS DB 246 087 013 21 23 56 11ZnPcTiMS 187 078 011 10 33 57 12

From the fitting results the 1205911component is preserved in

solid state systems even if the molecule population asso-ciated to this decay mechanism decreases to 10ndash20 Thecomponent 120591

2 observable only in solid state systems can be

associated to a quenching effect with a mechanism similarto the behavior of J aggregates in solution [42] The fastertime decay component in dye-TiO

2system (120591

3) could be

in principle indicative of an efficient injection occurringat the interface between dye molecules and semiconductorsurface Mesoporous TiO

2systems present 120591

3decay very

similar in value (013 ns for ZnPcTiMS DB and 011 ns forZnPcTIMS) while ZnPcP25 DB shows a quite lower 120591

3

component about 005 nsThe two observed fast time decays 120591

2and 120591

3in dyes-

TiO2systems could be also attributable to a contemporary

presence of different injection processes due to differentpossible configurations of ZnPc molecules when they areinteracting with TiO

2surface one is more favourable than

the other

4 Conclusions

The steady-state measurements and fluorescence emissiondecay of the dye-sensitized titania films suggest that the trans-parent mesoporous titania film (TiMS) could be responsiblefor a more efficient electronic injection when N719 and D5are used as sensitizers Indeed the emission peak of thesedyes has a lower intensity onto TiMS and a faster time decaywas observed In the case of ZnPc the fluorescence emissiondecay is faster if the dye is adsorbed onto P25 DB Probablythe formation of dye aggregates hinders the diffusion intothe mesoporous structure and only the external surface areacan interact with the sensitizer The mesoporous structureof TiMS could not be accessible to ZnPc aggregates with aconsequent lower performance

These findings suggest that mesoporous titania filmscould be considered the most efficient substrates for theadsorption of N719 and D5 to realize a photoanode with highefficient electronic injection

In fact as spectroscopic measurements showed theN719TiMS presents the highest UV-vis absorbance value

compared to the other TiO2substrates but the highest

decrease in fluorescence emission intensity These resultssuggest a strong interaction between the dye and the TiO

2

substrate and this condition is particularly favourable toenhance the electron injection

Acknowledgment

This work has been supported by the Italian project EFORmdashEnergia da Fonti Rinnovabili (Iniziativa CNR per il Mezzo-giorno L 1912009 art 2 comma 44)

References

[1] B OrsquoRegan and M Gratzel ldquoA low-cost high-efficiency solarcell based on dye-sensitized colloidal TiO

2filmsrdquo Nature vol

353 no 6346 pp 737ndash740 1991[2] M Gratzel ldquoSolar energy conversion by dye-sensitized photo-

voltaic cellsrdquo Inorganic Chemistry vol 44 no 20 pp 6841ndash68512005

[3] L M Goncalves V De Zea Bermudez H A Ribeiro and A MMendes ldquoDye-sensitized solar cells a safe bet for the futurerdquoEnergy and Environmental Science vol 1 no 6 pp 655ndash6672008

[4] M K Nazeeruddin A Kay I Rodicio et al ldquoConversionof light to electricity by cis-X2bis(221015840-bipyridyl-441015840-dicarbox-ylate)ruthenium(II) charge-transfer sensitizers (X = Clminus BrminusIminus CNminus and SCNminus) on nanocrystalline TiO

2electrodesrdquo

Journal of the American Chemical Society vol 115 no 14 pp6382ndash6390 1993

[5] L Giribabu K Sudhakar and V Velkannan ldquoPhthalocyaninespotential alternative sensitizers to Ru(II) polypyridyl complexesfor dye-sensitized solar cellsrdquoCurrent Science vol 102 no 7 pp991ndash1000 2012

[6] A Mishra M K R Fischer and P Buuerle ldquoMetal-free organicdyes for dye-Sensitized solar cells from structure propertyrelationships to design rulesrdquo Angewandte Chemie vol 48 no14 pp 2474ndash2499 2009

[7] G Calogero and G D Marco ldquoRed Sicilian orange and purpleeggplant fruits as natural sensitizers for dye-sensitized solarcellsrdquo Solar Energy Materials and Solar Cells vol 92 no 11 pp1341ndash1346 2008

[8] G Calogero J-H Yum A Sinopoli G Di Marco M Gratzeland M K Nazeeruddin ldquoAnthocyanins and betalains as light-harvesting pigments for dye-sensitized solar cellsrdquo Solar Energyvol 86 no 5 pp 1563ndash1575 2012

[9] E RoncaM Pastore L Belpassi F Tarantelli and FDeAngelisldquoInfluence of the dye molecular structure on the TiO

2conduc-

tion band in dye-sensitized solar cells disentangling chargetransfer and electrostatic effectsrdquo Energy amp EnvironmentalScience vol 6 no 1 pp 183ndash193 2013

[10] M K Nazeeruddin F De Angelis S Fantacci et al ldquoCombinedexperimental and DFT-TDDFT computational study of photo-electrochemical cell ruthenium sensitizersrdquo Journal of theAmer-ican Chemical Society vol 127 no 48 pp 16835ndash16847 2005

[11] D P Hagberg J-H Yum H Lee et al ldquoMolecular engineeringof organic sensitizers for dye-sensitized solar cell applicationsrdquoJournal of the American Chemical Society vol 130 no 19 pp6259ndash6266 2008


[12] K Hara T Sato R Katoh et al ldquoMolecular design of coumarindyes for efficient dye-sensitized solar cellsrdquo Journal of PhysicalChemistry B vol 107 no 2 pp 597ndash606 2003

[13] T Horiuchi H Miura K Sumioka and S Uchida ldquoHigh effi-ciency of dye-sensitized solar cells based onmetal-free indolinedyesrdquo Journal of the American Chemical Society vol 126 no 39pp 12218ndash12219 2004

[14] S Kim J K Lee S O Kang et al ldquoMolecular engineeringof organic sensitizers for solar cell applicationsrdquo Journal of theAmerican Chemical Society vol 128 no 51 pp 16701ndash167072006

[15] D P Hagberg T Edvinsson T Marinado G Boschloo AHagfeldt and L Sun ldquoA novel organic chromophore for dye-sensitized nanostructured solar cellsrdquo Chemical Communica-tions no 21 pp 2245ndash2247 2006

[16] X-F Wang and H Tamiaki ldquoCyclic tetrapyrrole based mole-cules for dye-sensitized solar cellsrdquo Energy and EnvironmentalScience vol 3 no 1 pp 94ndash106 2010

[17] F Silvestri M Garcıa-Iglesias J-H Yum et al ldquoCarboxy-14-phenylenevinylene- and carboxy-2 6-naphthylene-vinyleneunsymmetrical substituted zinc phthalocyanines for dye-sensitized solar cellsrdquo Journal of Porphyrins and Phthalocya-nines vol 13 no 3 pp 369ndash375 2009

[18] G Rossi G Zanotti N Angelini et al ldquoBridged phthalocyaninesystems for sensitization of nanocrystalline TiO

2filmsrdquo Inter-

national Journal of Photoenergy vol 2010 Article ID 136807 11pages 2010

[19] P Wen Y Han and W Zhao ldquoInfluence of TiO2nanocrystals

fabricating dye-sensitized solar cell on the absorption spectra ofN719 sensitizerrdquo International Journal of Photoenergy vol 2012Article ID 906198 7 pages 2012

[20] S K Deb ldquoDye-sensitized TiO2thin-film solar cell research at

the national renewable energy laboratory (NREL)rdquo Solar EnergyMaterials and Solar Cells vol 88 no 1 pp 1ndash10 2005

[21] L De Marco M Manca R Giannuzzi M R Belviso P DCozzoli and G Gigli ldquoShape-tailored TiO

2nanocrystals with

synergic peculiarities as building blocks for highly efficientmulti-stack dye solar cellsrdquo Energy amp Environmental Scienceno 6 pp 1791ndash1795 2013

[22] L De Marco M Manca R Giannuzzi et al ldquoNovel prepara-tion method of TiO

2-nanorod-based photoelectrodes for dye-

sensitized solar cells with improved light-harvesting efficiencyrdquoJournal of Physical Chemistry C vol 114 no 9 pp 4228ndash42362010

[23] G Zanotti N Angelini A M Paoletti et al ldquoSynthesis of anovel unsymmetrical Zn(ii) phthalocyanine bearing a phenylethynyl moiety as sensitizer for dye-sensitized solar cellsrdquoDalton Transactions vol 40 no 1 pp 38ndash40 2011

[24] S Y Choi M Mamak N Coombs N Chopra and G AOzin ldquoThermally stable two-dimensional hexagonal meso-porous nanocrystalline anatase meso-nc-TiO

2 bulk and crack-

free thin film morphologiesrdquo Advanced Functional Materialsvol 14 no 4 pp 335ndash344 2004

[25] L De Marco G Di Carlo R Giannuzzi et al ldquoHighly efficientphotoanodes for dye solar cells with a hierarchical meso-ordered structurerdquo Physical Chemistry Chemical Physics vol 15pp 16949ndash16955 2013

[26] S Ito P Chen P Comte et al ldquoFabrication of screen-print-ing pastes from TiO

2powders for dye-sensitised solar cellsrdquo

Progress in Photovoltaics vol 15 no 7 pp 603ndash612 2007

[27] H Jensen A Soloviev Z Li and E G Soslashgaard ldquoXPS and FTIRinvestigation of the surface properties of different preparedtitania nano-powdersrdquoApplied Surface Science vol 246 no 1ndash3pp 239ndash249 2005

[28] T Lopez J A Moreno R Gomez et al ldquoCharacterizationof iron-doped titania sol-gel materialsrdquo Journal of MaterialsChemistry vol 12 no 3 pp 714ndash718 2002

[29] M K Nazeeruddin R Humphry-Baker P Liska and MGratzel ldquoInvestigation of sensitizer adsorption and the influ-ence of protons on current and voltage of a dye-sensitizednanocrystalline TiO

2solar cellrdquo Journal of Physical Chemistry

B vol 107 no 34 pp 8981ndash8987 2003[30] C Perez Leon L Kador B Peng and M Thelakkat ldquoInfluence

of the solvent on the surface-enhancedRaman spectra of Ruthe-nium(II) Bipyridyl complexesrdquo Journal of Physical Chemistry Bvol 109 no 12 pp 5783ndash5789 2005

[31] M J Root B P Sullivan T JMeyer and EDeutsch ldquoThioetherthiolato and 11-dithioato complexes of bis(221015840-bipy-ridine)ruthenium(II) and bis(221015840-bipyridine)osmium(II)rdquoInorganic Chemistry vol 24 no 18 pp 2731ndash2739 1985

[32] C C Leznoff and A B P Lever Eds Phthalocyanines Prop-erties and Applications vol 1 VCH Publishers New York NYUSA 1990

[33] S Mori M Nagata Y Nakahata et al ldquoEnhancement of inci-dent photon-to-current conversion efficiency for phthalocy-anine-sensitized solar cells by 3D molecular structuralizationrdquoJournal of the American Chemical Society vol 132 no 12 pp4054ndash4055 2010

[34] L Giribabu C Vijay Kumar V Gopal Reddy et al ldquoUnsymmet-rical alkoxy zinc phthalocyanine for sensitization of nanocrys-talline TiO

2filmsrdquo Solar Energy Materials and Solar Cells vol

91 no 17 pp 1611ndash1617 2007[35] L Giribabu C V Kumar P Y Reddy J-H YumMGratzel and

M K Nazeeruddin ldquoUnsymmetrical extended 120587-conjugatedzinc phthalocyanine for sensitization of nanocrystalline TiO

2

filmsrdquo Journal of Chemical Sciences vol 121 no 1 pp 75ndash822009

[36] S E Koops and J R Durrant ldquoTransient emission studiesof electron injection in dye sensitised solar cellsrdquo InorganicaChimica Acta vol 361 no 3 pp 663ndash670 2008

[37] V Biju M Micic D Hu and H P Lu ldquoIntermittent single-molecule interfacial electron transfer dynamicsrdquo Journal of theAmerican Chemical Society vol 126 no 30 pp 9374ndash93812004

[38] M K Nazeeruddin S M Zakeeruddin R Humphry-Bakeret al ldquoAcid-base equilibria of (221015840-bipyridyl-441015840-dicarboxylicacid)ruthenium(II) complexes and the effect of protonationon charge-transfer sensitization of nanocrystalline titaniardquoInorganic Chemistry vol 38 no 26 pp 6298ndash6305 1999

[39] M K Nazeeruddin and K Kalyanasundaram ldquoAcid-basebehavior in the ground and excited states of ruthenium (II)complexes containing tetraimines or dicarboxybipyridines asprotonatable ligandsrdquo Inorganic Chemistry vol 28 no 23 pp4251ndash4259 1989

[40] M Ziołek X Yang L Sun and A Douhal ldquoInterrogating theultrafast dynamics of an efficient dye for sunlight conversionrdquoPhysical Chemistry Chemical Physics vol 12 no 28 pp 8098ndash8107 2010

[41] G Gumrukcu G K Karaoglan A Erdogmus A Gul andU Avcıata ldquoA novel phthalocyanine conjugated with foursalicylideneimino complexes photophysics and fluorescence


quenching studiesrdquo Dyes and Pigments vol 95 no 2 pp 280ndash289 2012

[42] X-F Zhang Q Xi and J Zhao ldquoFluorescent and triplet statephotoactive J-type phthalocyanine nano assemblies controlledformation and photosensitizing propertiesrdquo Journal ofMaterialsChemistry vol 20 no 32 pp 6726ndash6733 2010

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


the competing fluorescence and nonradiative processes Thisphotoinduced electron transfer leads to the production ofphotocurrent and consequently it is crucial to the deviceefficiency [1ndash3]

In DSSCs the sensitizer is one of the critical componentsas it absorbs sunlight and induces the charge separationprocess In order to enhance power conversion efficiencies ofDSSCs it is imperative to improve the light-harvesting abil-ity of the dyes It is also fundamental to investigate and tooptimize the dye-substrate interaction that is involved in theelectron transfer process [9]

Ruthenium sensitizers such as cis-di(thiocyanato)-bis[221015840-bipyridyl-441015840-dicarboxylic acid] ruthenium (II)(N3) or its bistetrabutylammonium (TBA) salt counterpart(N719) in combination with thick titania films (gt12ndash15mm)have shown solar-to-electric power conversion efficienciesup to 11 [2 10] Several groups have also developedmetal-free organic sensitizers that are less expensive andobtained efficiencies in the range of 4ndash8 [11ndash15] Interesthas been recently devoted to the design of sensitizers that areable to absorb at the near infrared region by extending thespectral range for the photocurrent generation with respectto Ru-complexes Porphyrins and phthalocyanines are beingcurrently considered to this specific aim and meaningfulresults have been achieved [16ndash18]

The critical factors that influence sensitization are theexcited-state redox potential which should match the energyof the conduction band edge of the semiconductor substratethe light-harvesting ability and the electron transfer processthat is influenced by the electronic coupling between thelowest unoccupied molecular orbital (LUMO) of the dye andthe TiO

2conduction band One of the major factors for low

conversion efficiency of many organic dyes in the DSSC is theformation of dye aggregates on the semiconductor surfaceTherefore to obtain optimal performance aggregation ofdyes needs to be avoided by promoting the chemisorptiononto the substrate and by increasing the surface area of thesemiconductor oxide High surface area substrates can alsopromote the adsorption of a larger amount of dye moleculesenhancing the light-harvesting efficiency However in orderto improve the power conversion efficiency of photoanodesfor DSSCs it is necessary to achieve both optimal morpho-logical properties and fast electron transport [19ndash22]

To gain information about the photoinduced electrontransfer process from the sensitizers to the semiconductorsand indications about the linkage between dye and substratethe study of the spectroscopic features of chromophores ontothe semiconductor is of crucial importance Absorption andsteady-state emission spectral features can give informationon the dye interaction with the substrate since they areinfluenced by the chemical environment of the sensitizers andhence it is expected that the structural and chemical natureof the sensitizers and the structural properties of titaniasubstrates have a key role in determining the final spectralfeatures of the chromophore Moreover time-resolved fluo-rescence decay can provide insights into the electron injectionprocess since it is competitive with fluorescence relaxationElectron injection is found to generally occur with a timemuch shorter than the excited-state lifetime of typical dyes

therefore time-resolved fluorescence decay studies are veryuseful to understand these dynamic photoinduced processes

Herein for the purpose of comparison three differentdyes were examined the widely used inorganic rutheniumcomplex cis-di(thiocyanato) bis(221015840-bipyridyl-441015840-dicar-boxylato)ruthenium(II) (N719) the more recently developedorganic molecular 3-(5-(4-(diphenylamino) styryl)thiophen-2-yl)-2-cyanoacrylic acid (D5) [15] and the push-pullzinc phthalocyanine sensitizer (ZnPc) [23] The dyes wereadsorbed onto three types of thin film titania substratesmesoporous transparent titania deposited by spin-coating(TiMS) mesoporous titania deposited by doctor-blade(TiMS DB) and commercial P25 titania deposited bydoctor-blade (P25 DB) Titania films were characterizedby scanning electron microscopy (SEM) and by Fouriertransform infrared (FT-IR) spectroscopy whereas the dye-sensitized films were studied by UV-Vis and fluorescencespectroscopy

2 Experimental Section

21 Preparation of Titania Thin Films

211 Transparent andMesoporous Films Mesoporous titaniafilms were synthesized using the P123 block copolymer astemplate in order to obtain an ordered porous structurewith a controlled geometry The titania precursor solutionswere prepared according to the procedures described in theliterature using pluronic surfactant [24]

In a typical synthesis 14mL of concentrated HCl wereslowly added to 21 g of titanium(IV) ethoxide at room tem-perature In another flask 065 g of P123 were dissolved in 6 gof 1-butanol and subsequently added to the titanium solutionThe system was kept under stirring at room temperaturefor 3 hours The as-prepared solution of titania precursorwas deposited on FTO conducting glass substrates (Dyesol15Ω sqminus1) by spin-coating at 2400 rpm After aging at 25∘Cfor 2 days optically uniform and transparent films wereobtained These films were calcined at 350 for 30 minutesusing a ramp rate of 1∘Cmin to remove the template and theresidual organic precursors TiO

2electrodes were obtained

by deposition of three layers with a final calcination at350∘C for 2 hours and were labeled as TiMS (Table 1) Theresulting mesoscopic oxide film was around 1 120583m thick andtransparent

212 Semiopaque Films from Mesoporous Titania Mesopo-rous titania powder was prepared from the solution of tita-nium (IV) ethoxide and P123 described above after aging at25∘C for 5 days and subsequent calcination at 350∘C for 4hours using a ramp rate of 1∘Cmin according to a recentlypublished procedure [25]

Titania films were prepared from mesoporous titaniapowder by using the doctor-blade technique according toa procedure described elsewhere [26] Dried powder wasdispersed in ethanol (EtOH) treated with ultrasonic bathfor 30min then stirred at 50∘C for 1 h This procedure wasrepeated three times in order to obtain a homogeneous and







Doctor-blade



2 4





2 05 acetic acid


















N

N

HO

HO

O

N

O

N

RuNCS

NCS

O

O

N N

N

N

N

N

N

N

Zn

N

S

CN

COOH

HOOC

Ominus

N+

Ominus

H3C 3

2

CH

3CH

3CH

t-Bu

t-But-Bu

N719

D5

ZnPc







4000 3500 3000 2500 2000 1500 100092

94

96

98

100

TiMS

Abso

rban

ce (a

u)


P25 DBTiMS DB













2films



2films the


2system












2mesoporous









(a) (b)

(c)


300 400 500 600 700 8000

02

04

06

08

1

Abso

rban

ce (a

u)

Wavelength (nm)

N719N719P25 DB

N719TiMS DBN719TiMS





650 700 750 800

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

Inte

nsity

(cou

nts)

Wavelength (nm)

N719N719P25 DB

N719TiMS DBN719TiMS


2systems





500 550 600 650 700 750

0

1000000

2000000

3000000

Inte

nsity

(cou

nts)

Wavelength (nm)

D5D5P25 DB

D5TiMS DBD5TiMS











2layers



1of the dye


2systems are



300 400 500 600 700 800

Abso

rban

ce (a

u)

Wavelength (nm)

ZnPc ZnPcP25 DB



650 675 700 725 7500

100000

200000

300000

400000In

tens

ity (c

ount

s)

Wavelength (nm)

ZnPc ZnPcP25 DB













1)





6 8 10 12 14 16 18 20 22 24 26 28 30100

1000

Cou

nts


N719TiMS

Time decay (ns)

Prompt

(a)

10

64 8 10 12 14 16 18 20

100

1000

Cou

nts

D5PromptD5P25 DB

D5TiMS DB

D5TiMS

Time decay (ns)

(b)

Prompt

10 20 30 40 50 60 70

10

100

1000

Cou

nts

Time decay (ns)


ZnPcTiMS

(c)


2systems and





1= 80)











Sample 1205911(ns) 120591

2(ns) 120591

3(ns) 119860

1() 119860

2() 119860

3() 1205942






2system (120591

3) could be



3decay very


3


2and 120591

3in dyes-




the other

4 Conclusions






2


Acknowledgment


References







2electrodesrdquo







2conduc-












2filmsrdquo Inter-







2nanocrystals with







2 bulk and crack-



















2




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of







Doctor-blade



2 4





2 05 acetic acid


















N

N

HO

HO

O

N

O

N

RuNCS

NCS

O

O

N N

N

N

N

N

N

N

Zn

N

S

CN

COOH

HOOC

Ominus

N+

Ominus

H3C 3

2

CH

3CH

3CH

t-Bu

t-But-Bu

N719

D5

ZnPc







4000 3500 3000 2500 2000 1500 100092

94

96

98

100

TiMS

Abso

rban

ce (a

u)


P25 DBTiMS DB













2films



2films the


2system












2mesoporous









(a) (b)

(c)


300 400 500 600 700 8000

02

04

06

08

1

Abso

rban

ce (a

u)

Wavelength (nm)

N719N719P25 DB

N719TiMS DBN719TiMS





650 700 750 800

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

Inte

nsity

(cou

nts)

Wavelength (nm)

N719N719P25 DB

N719TiMS DBN719TiMS


2systems





500 550 600 650 700 750

0

1000000

2000000

3000000

Inte

nsity

(cou

nts)

Wavelength (nm)

D5D5P25 DB

D5TiMS DBD5TiMS











2layers



1of the dye


2systems are



300 400 500 600 700 800

Abso

rban

ce (a

u)

Wavelength (nm)

ZnPc ZnPcP25 DB



650 675 700 725 7500

100000

200000

300000

400000In

tens

ity (c

ount

s)

Wavelength (nm)

ZnPc ZnPcP25 DB













1)





6 8 10 12 14 16 18 20 22 24 26 28 30100

1000

Cou

nts


N719TiMS

Time decay (ns)

Prompt

(a)

10

64 8 10 12 14 16 18 20

100

1000

Cou

nts

D5PromptD5P25 DB

D5TiMS DB

D5TiMS

Time decay (ns)

(b)

Prompt

10 20 30 40 50 60 70

10

100

1000

Cou

nts

Time decay (ns)


ZnPcTiMS

(c)


2systems and





1= 80)











Sample 1205911(ns) 120591

2(ns) 120591

3(ns) 119860

1() 119860

2() 119860

3() 1205942






2system (120591

3) could be



3decay very


3


2and 120591

3in dyes-




the other

4 Conclusions






2


Acknowledgment


References







2electrodesrdquo







2conduc-












2filmsrdquo Inter-







2nanocrystals with







2 bulk and crack-



















2




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

N

HO

HO

O

N

O

N

RuNCS

NCS

O

O

N N

N

N

N

N

N

N

Zn

N

S

CN

COOH

HOOC

Ominus

N+

Ominus

H3C 3

2

CH

3CH

3CH

t-Bu

t-But-Bu

N719

D5

ZnPc







4000 3500 3000 2500 2000 1500 100092

94

96

98

100

TiMS

Abso

rban

ce (a

u)


P25 DBTiMS DB













2films



2films the


2system












2mesoporous









(a) (b)

(c)


300 400 500 600 700 8000

02

04

06

08

1

Abso

rban

ce (a

u)

Wavelength (nm)

N719N719P25 DB

N719TiMS DBN719TiMS





650 700 750 800

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

Inte

nsity

(cou

nts)

Wavelength (nm)

N719N719P25 DB

N719TiMS DBN719TiMS


2systems





500 550 600 650 700 750

0

1000000

2000000

3000000

Inte

nsity

(cou

nts)

Wavelength (nm)

D5D5P25 DB

D5TiMS DBD5TiMS











2layers



1of the dye


2systems are



300 400 500 600 700 800

Abso

rban

ce (a

u)

Wavelength (nm)

ZnPc ZnPcP25 DB



650 675 700 725 7500

100000

200000

300000

400000In

tens

ity (c

ount

s)

Wavelength (nm)

ZnPc ZnPcP25 DB













1)





6 8 10 12 14 16 18 20 22 24 26 28 30100

1000

Cou

nts


N719TiMS

Time decay (ns)

Prompt

(a)

10

64 8 10 12 14 16 18 20

100

1000

Cou

nts

D5PromptD5P25 DB

D5TiMS DB

D5TiMS

Time decay (ns)

(b)

Prompt

10 20 30 40 50 60 70

10

100

1000

Cou

nts

Time decay (ns)


ZnPcTiMS

(c)


2systems and





1= 80)











Sample 1205911(ns) 120591

2(ns) 120591

3(ns) 119860

1() 119860

2() 119860

3() 1205942






2system (120591

3) could be



3decay very


3


2and 120591

3in dyes-




the other

4 Conclusions






2


Acknowledgment


References







2electrodesrdquo







2conduc-












2filmsrdquo Inter-







2nanocrystals with







2 bulk and crack-



















2




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










2films



2films the


2system












2mesoporous









(a) (b)

(c)


300 400 500 600 700 8000

02

04

06

08

1

Abso

rban

ce (a

u)

Wavelength (nm)

N719N719P25 DB

N719TiMS DBN719TiMS





650 700 750 800

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

Inte

nsity

(cou

nts)

Wavelength (nm)

N719N719P25 DB

N719TiMS DBN719TiMS


2systems





500 550 600 650 700 750

0

1000000

2000000

3000000

Inte

nsity

(cou

nts)

Wavelength (nm)

D5D5P25 DB

D5TiMS DBD5TiMS











2layers



1of the dye


2systems are



300 400 500 600 700 800

Abso

rban

ce (a

u)

Wavelength (nm)

ZnPc ZnPcP25 DB



650 675 700 725 7500

100000

200000

300000

400000In

tens

ity (c

ount

s)

Wavelength (nm)

ZnPc ZnPcP25 DB













1)





6 8 10 12 14 16 18 20 22 24 26 28 30100

1000

Cou

nts


N719TiMS

Time decay (ns)

Prompt

(a)

10

64 8 10 12 14 16 18 20

100

1000

Cou

nts

D5PromptD5P25 DB

D5TiMS DB

D5TiMS

Time decay (ns)

(b)

Prompt

10 20 30 40 50 60 70

10

100

1000

Cou

nts

Time decay (ns)


ZnPcTiMS

(c)


2systems and





1= 80)











Sample 1205911(ns) 120591

2(ns) 120591

3(ns) 119860

1() 119860

2() 119860

3() 1205942






2system (120591

3) could be



3decay very


3


2and 120591

3in dyes-




the other

4 Conclusions






2


Acknowledgment


References







2electrodesrdquo







2conduc-












2filmsrdquo Inter-







2nanocrystals with







2 bulk and crack-



















2




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


(a) (b)

(c)


300 400 500 600 700 8000

02

04

06

08

1

Abso

rban

ce (a

u)

Wavelength (nm)

N719N719P25 DB

N719TiMS DBN719TiMS





650 700 750 800

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

Inte

nsity

(cou

nts)

Wavelength (nm)

N719N719P25 DB

N719TiMS DBN719TiMS


2systems





500 550 600 650 700 750

0

1000000

2000000

3000000

Inte

nsity

(cou

nts)

Wavelength (nm)

D5D5P25 DB

D5TiMS DBD5TiMS











2layers



1of the dye


2systems are



300 400 500 600 700 800

Abso

rban

ce (a

u)

Wavelength (nm)

ZnPc ZnPcP25 DB



650 675 700 725 7500

100000

200000

300000

400000In

tens

ity (c

ount

s)

Wavelength (nm)

ZnPc ZnPcP25 DB













1)





6 8 10 12 14 16 18 20 22 24 26 28 30100

1000

Cou

nts


N719TiMS

Time decay (ns)

Prompt

(a)

10

64 8 10 12 14 16 18 20

100

1000

Cou

nts

D5PromptD5P25 DB

D5TiMS DB

D5TiMS

Time decay (ns)

(b)

Prompt

10 20 30 40 50 60 70

10

100

1000

Cou

nts

Time decay (ns)


ZnPcTiMS

(c)


2systems and





1= 80)











Sample 1205911(ns) 120591

2(ns) 120591

3(ns) 119860

1() 119860

2() 119860

3() 1205942






2system (120591

3) could be



3decay very


3


2and 120591

3in dyes-




the other

4 Conclusions






2


Acknowledgment


References







2electrodesrdquo







2conduc-












2filmsrdquo Inter-







2nanocrystals with







2 bulk and crack-



















2




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


500 550 600 650 700 750

0

1000000

2000000

3000000

Inte

nsity

(cou

nts)

Wavelength (nm)

D5D5P25 DB

D5TiMS DBD5TiMS











2layers



1of the dye


2systems are



300 400 500 600 700 800

Abso

rban

ce (a

u)

Wavelength (nm)

ZnPc ZnPcP25 DB



650 675 700 725 7500

100000

200000

300000

400000In

tens

ity (c

ount

s)

Wavelength (nm)

ZnPc ZnPcP25 DB













1)





6 8 10 12 14 16 18 20 22 24 26 28 30100

1000

Cou

nts


N719TiMS

Time decay (ns)

Prompt

(a)

10

64 8 10 12 14 16 18 20

100

1000

Cou

nts

D5PromptD5P25 DB

D5TiMS DB

D5TiMS

Time decay (ns)

(b)

Prompt

10 20 30 40 50 60 70

10

100

1000

Cou

nts

Time decay (ns)


ZnPcTiMS

(c)


2systems and





1= 80)











Sample 1205911(ns) 120591

2(ns) 120591

3(ns) 119860

1() 119860

2() 119860

3() 1205942






2system (120591

3) could be



3decay very


3


2and 120591

3in dyes-




the other

4 Conclusions






2


Acknowledgment


References







2electrodesrdquo







2conduc-












2filmsrdquo Inter-







2nanocrystals with







2 bulk and crack-



















2




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


6 8 10 12 14 16 18 20 22 24 26 28 30100

1000

Cou

nts


N719TiMS

Time decay (ns)

Prompt

(a)

10

64 8 10 12 14 16 18 20

100

1000

Cou

nts

D5PromptD5P25 DB

D5TiMS DB

D5TiMS

Time decay (ns)

(b)

Prompt

10 20 30 40 50 60 70

10

100

1000

Cou

nts

Time decay (ns)


ZnPcTiMS

(c)


2systems and





1= 80)











Sample 1205911(ns) 120591

2(ns) 120591

3(ns) 119860

1() 119860

2() 119860

3() 1205942






2system (120591

3) could be



3decay very


3


2and 120591

3in dyes-




the other

4 Conclusions






2


Acknowledgment


References







2electrodesrdquo







2conduc-












2filmsrdquo Inter-







2nanocrystals with







2 bulk and crack-



















2




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



Sample 1205911(ns) 120591

2(ns) 120591

3(ns) 119860

1() 119860

2() 119860

3() 1205942






2system (120591

3) could be



3decay very


3


2and 120591

3in dyes-




the other

4 Conclusions






2


Acknowledgment


References







2electrodesrdquo







2conduc-












2filmsrdquo Inter-







2nanocrystals with







2 bulk and crack-



















2




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of









2filmsrdquo Inter-







2nanocrystals with







2 bulk and crack-



















2




















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of













Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

research article spectroscopic and morphological studies of...

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