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Eosin -Y and Rose Bengal sensitized solar cell characteristics of N-doped

nanocrystalline TiO2 films

Abstract : Here in, the Eosin-Y and Rose Bengal sensitized solar cell characteristics of
N-doped nanocrystalline TiO2 films prepared by using Doctors Blade method are
investigated. The films are obtained from the N-doped nanocrystalline TiO2 powders
prepared by using simple hydrolysis route followed by annealing at 400 0C for 2 h. The
resultant powder/ films are characterized by using X-ray diffraction, Raman
spectroscopy, scanning electron microscopy, thickness profiler and UV-Visible
spectroscopy. The structural studies revealed the evolution of pure nanocrystalline
anatase TiO2 phase (crystallite size ~ 13 nm) in resultant powders. The morphological
studies with SEM indicated the varied shaped agglomeration of primary spherical
particles. The band gap energy and absorbance of resultant powder are found to be 2.88
eV and 0.79 respectively. The better photovoltaic performances: (i) VOC = 0.45 V, JSC
= 0.963 mA/cm2, FF = 59.23 % and = 0.52 % using Rose Bengal dye, (ii) VOC =
0.45 V, JSC = 9.67 mA/cm2, FF = 41.27 % & = 1.27 % using Eosin Y dye with
polyiodide electrolyte are obtained for the dye sensitized solar cells (DSSCs) made by
using photoanodes based on N-doped TiO2 films.

Keywords: Nanocrystalline TiO2; Hydrolysis; DSSC; Eosin-Y dye; Rose Bengal dye

I. Introduction

A new type of solar cells: dye-sensitized solar cells (DSSCs) developed by ORegan and
Grtzel in 1991, have been attracting much attention over last decade as potential low-cost
alternative to commercial silicon based solar cells due to their ease of fabrication and high
photo-conversion efficiencies[1-3]. Titanium dioxide is one of the most promising materials
for photochemical energy conversion processes. However, its wide band gaps of 3.0 eV and
3.2 eV for the rutile and anatase phases respectively require UV light for the excitation of
electron-hole pairs. This limits its applicability to efficient solar energy conversion because
only 5 - 7 % of the solar spectrum lies in the UV range accessible by pristine TiO2. Thus, in
order to increase the light absorption in the visible range of spectrum, a narrowing of the
band gap of TiO2 would be desirable. For some time, this goal has been addressed with
impurity (cationic/anionic) doping of TiO2[4].This approach can lead to an increased visible
light absorption due to the formation of dopant induced band gap states. The advantages of
TiO2 have been previously summarized by several excellent articles [1-3]. TiO2
nanoparticles explicit the following special properties: (i) greatly enhanced surface area
giving effective exposure to light and facilitates the photochemical reactions on the surface,
(ii) enhanced photo induced charge transport useful for harvesting and donating of photo
induced electrons [5-6]and (iii)no depletion layer formation on the surface, which profoundly
changes the photoelectrochemical properties. These effects are also expected to benefit the N-
doped TiO2 system. In order to utilize the advantages of properties of nanosized materials, N-
doped TiO2 nanoparticles received considerable interests in the recent years [7-12].In recent
years, great progress has been made in TiO2 doping materials, such as metal doping (Zn, La
and Ta) [13-16]and nonmetal doping (N and B) [17-22] of these materials. The N-doping
TiO2 materials proved to be suitable semiconductor candidates for DSSCs. However, no
reports are available in literature indicating the photovoltaic performance of N-doped TiO2
films prepared by using Doctors Blade method for Rose Bengal, Eosin-Y dyes and polyiodie
electrolyte solution. In view of this, the main objective of present work was to develop
DSSCs based on TiO2 films by taking advantage of N-doping for their better photovoltaic
performance for Rose Bengal and Eosin-Y dye. For this purpose, nanocrystalline N-doped
TiO2 films were prepared on indium tin oxide (ITO) substrates by using Doctors Blade
method from the N-doped TiO2 powders synthesized by simple hydrolysis route at titanium
tetra isopropoxide (TTIP):aqueous ammonia molar ratios 1:12 (Ti:N) followed by annealing
treatment. The resultant powders were characterized by using XRD, Raman spectroscopy,
TEM and UV-Visible spectroscopy. The effect of TTIP: aqueous ammonia ratio on the
optical properties and photovoltaic performance of different dye for DSSCs was evaluated.
The results pertaining to preparation, characterization and measurement of optical-
photovoltaic properties of DSSCs based on N-doped TiO2 film are presented in this paper.

II. Experimental

A. Synthesis of N-doped TiO2 powder

A 25 ml of Ti precursor: titanium tetraisopropoxide (TTIP) (Spectrochem Chem., AR grade)

and 25 % aqueous ammonia [molar ratio- TTIP:aqueous ammonia = 1:12] were slowly added
to 100 ml of double distilled water (DDW). This hydrolysis was carried out under vigorous
stirring in an ice bath. A white precipitate obtained was washed with DDW for 10 times by
using centrifuge. The precipitate was dried at 80 0C for 1 hr in an oven. This as-dried
precipitate was annealed at 400 0C for 4 hr. This gave light yellow colour powder. As-
annealed powder was used for further study.
B. Preparation of N-doped TiO2 films

As-annealed N-doped TiO2 powder with ratio Ti:N = 1:12 was used for the preparation of
films on thoroughly cleaned conducting indium tin oxide (ITO) substrates by using Doctors
Blade method. Initially, ITO substrates were washed with detergent and DDW. The
substrates were boiled in concentrated chromic acid (0.5 M) for 1 hr and then kept in it for 5
hr. After this treatment, the substrates were rinsed with DDW and then ultrasonically cleaned
in acetone for 15 min. Finally, the substrates were rinsed with acetone and then dried under
IR lamp. The 0.50 gm of N-doped TiO2 powder was ground with 0.25 gm of polyethylene
glycol (PEG, M.W. 20,000) by using pestle-mortar and by adding few drops of dilute acetic
acid for 30 min. to produce a lump free paste. Three edges of thoroughly cleaned ITO
substrate were masked with TISCO tape by keeping the area = 1 cm2 free for the deposition
of film. The thickness of tape loaded over the substrate was between 10 - 11 m. The
unmasked region of ITO substrate was completely filled with the lump free paste of N-doped
TiO2powder. This film was dried under halogen lamp for 30 min. The average thickness of
the films measured by surface profiler was found to be 10.14 m. Finally, theresultant films
were subjected for the fabrication of dye sensitized solar cells (DSSCs).

C. Characterization of powders and films

The as-annealedpowder was characterized by using different physical techniques. The X-ray
diffraction pattern (XRD) of powder was recorded by using Bruker D8 Advance (filtered
CuKradiation with = 1.5406 ) diffractometer. The Raman spectrum was recorded by
using JobinYvonHoribra LABRAM-HR spectrometer in wavelength range: 100 - 700 nm.
The XRD pattern and Raman spectrum were used for phase analysis of resultant powder. The
morphological study of powder was done by using high resolution transmission electron
microscopy (HRTEM) [Model: TECNAI G2-20- TWIN, (FEINETHRLANDS)].The sample
for HRTEM analysis was prepared by drying the solution drops of powder on carbon-coated
copper grid. Image processing and interplanar distance evaluation were performed with the
help of micrograph TIA software. The value of thickness of resultant film was obtained by
using KLA Tencor P -16+ Surface profiler.

D. Fabrication of dye sensitized solar cell

In fabrication of DSSC, the resultant N-doped TiO2 film was initially kept in 0.3 mM
solution of Eosin -Y dye and Rose Bengal dye in ethanol for 24 hr at room temperature (RT)
separately. The colour of film was found to be changed due to absorption of dye and
formation of complex with Ti(IV).Then film was rinsed with DDW and ethanol and dried in
tissue paper gently. The carbon coated ITO was used as counter electrode. The carbon along
the perimeter of three sides of the carbon-coated ITO was removed by using a cotton swab.
The counter electrode was placed (carbon coated side touching to film) on the top of dye
loaded N-doped TiO2 film. This sandwich was used as DSSC. The few drops of electrolyte
solution of polyiodide (1 M potassium hydroxide + 1 M potassium iodide + 0.5 M iodine) in
actonitrile [23] were poured from exposed side of DSSC. The solution gets absorbed into
DSSC by capillary action.

E. Measurement of optical and photovoltaic properties

The UV-Visible spectrum of as-annealed powder was recorded by using theV-670, JASCO
spectrometer in the wavelength range () = 200 - 800 nm. The UV-Visible spectrum was
used to obtain the optical properties: band gap energy (Eg) and absorbance of powder. The
current density (J) - voltage (V) characteristic curves for different DSSCs were recorded at
the input power = 1000 W/m2 of incident light from neon lamp on DSSCs having area = 1
cm2 by using solar simulator (Newport Corporation's Oriel Sol2A Class ABA solar
simulation systems). The schematic diagram for solar simulator used for measurement of
photovoltaic properties of different DSSCs is given in fig. 1. The photovoltaic properties
(VOC, ISC, Vmax, Imax, Pmax, FF, RS, RSH and ) of different DSSCs were obtained
from J-V characteristic curves and data recorded by using solar simulator.

III. Result and discussion

1. X-ray diffraction

Fig. 2 gives the X-ray diffraction pattern for asannealed powder (with ratio, Ti:N = 1:12)
prepared in the present work.All reflections in the XRD pattern are found to be perfectly
matching with the peaks given in the JCPDS data file for tetragonal anatase TiO2 [PDF-21-
1272] phase. This indicates the formation of tetragonal anatase TiO2 phase in as-annealed
powder. In given XRD pattern, the slight shifting of all reflections towards the higher side of
respective diffraction angles is found.This is due to incorporation of anionic N in TiO2 lattice
with tetragonal anatase symmetry. The value obtained ford spacing for (101) plane is found
to be 0.3468 nm.The lowerd spacing value as compared to pure TiO2 [d101 = 0.3520 nm]
in case of N-doped TiO2 powder (with Ti:N ratio 1:12) is due the compressive strain arising
from the differences in the bonding characteristics between nitrogen and oxygen as reported
in literature [24 - 25]. The values obtained for lattice parameters, a (= b) and c are found to be
0.3670 nm and 0.9443 nm respectively.

These values of lattice parameters are matching with the data reported for the tetragonal
anatase TiO2 [PDF-21- 1272] phase.The value for crystallite size (D) obtained by using the
Scherrer formula,

where, k = 0.89, = 0.1541 nm (for CuK radiation), and = full width at half maximum
of (101) peak and = Braggs diffraction angle is found to be 12.82 nm.This indicates the
nanocrystalline nature of the as-annealed powder.

2. Raman spectroscopy

Fig. 3 gives the Raman spectrum for as-annealed powder with Ti:N ratio as 1:12. The
spectrum shows well defined peaks, the absence of overlapping peaks and absence of any
shoulders towards the lower as well as higher Raman shift sides. This observation indicates
the formation of phase pure material in as-annealed powder. This also shows well crystalline
nature of powder with low number of imperfect sites. The spectrum shows the 5 Raman
active modes centred around 144.2, 196.3, 395.3, 515.2, and 636.7 cm1. Above
observations are matching with the Raman spectrum given for the single crystal tetragonal
anatase TiO2 having six Raman active modes (A1g + 2 B1g + 3 Eg) at 142 2 cm1 (Eg),
194 3 cm1 (Eg), 393 2 cm1 (B1g), 512 1 cm1 (A1g), 519 cm1 (B1g) and 634
2 cm1 (Eg) [26]. This clearly indicates the formation of single phase TiO2 with tetragonal
anatase symmetry in as-annealed powder with Ti:N ratio as 1:12.The Raman spectrum shows
only one active mode between 510 - 525 cm-1 instead of two active modes: 512 1 cm1
(A1g), 519 cm1 (B1g). This might be due to the nano-crystalline nature of the as-annealed
powder. This is consistent with the XRD observations.

3. Transmission electron microscopy

Fig. 4 (a) shows high resolution transmission electron microphotograph of as-annealed
powder with Ti:N ratio as 1:12. It shows nanocrystalline nature of material of N-doped TiO2
powder. The particles are spherical in shape. The average particle size is noted to be 15 nm.
In fig. 4 (b), the TEM photograph shows more number of crystalline grains having diameters
between 10 - 15 nm in a structured matrix. Further, the selected area electron diffraction
(SAED) [given as inset in fig. 4 (b)] shows the diffused ring pattern indicating thereby the
nano-structured nature of N-doped TiO2powder. The processing and interplanar distance
evaluation with the help of micrograph TIA software is presented in fig. 4(b). From this
figure, the interplaner spacing is found to be 0.225 nm. This value of interplaner spacing is
for (004) plane of anatase TiO2 [27]. The observed value of interplaner spacing for (004) is
found to be lower as compared to interplaner spacing for (004) plane = 0.237 nm for pure
anatase TiO2. This is due to coordinated nitrogen incorporation in the O-Ti-O lattice via.
dopant-dopant interactions. This is consistent with XRD observations presented for (101)

4. Optical properties

The evaluation of optical properties is the easiest way to examine the doping effects on the
host metal oxide matrix. The UV-Vis spectroscopy is the most reported technique in the
study of optical properties of material. Most of the studies showed that the N-doped
TiO2nanocrystalline usually exhibit increased absorption between 400 nm and 600 nm,
which is in turn dependent on the preparative conditions [28-30]. Similar trend is observed in
the case of N-doped TiO2 powder [31- 33] prepared in present work. Fig. 5 shows the
UVVisible spectrum of as-annealed powder with Ti:N ratio as1:12. The absorption edge cut
off is shifted to visible region. It shows the effectiveness of N doping for the visible light
sensitivity of TiO2.annealed powder with Ti:N ratio as 1:12.The shifting of the absorption
edge towards visible region is due to incorporation of nitrogen in TiO2 lattice [24].
Improvement of TiO2 photoactivity through nitrogen doping could be determined by light
absorption shift to visible region. It is quantified by band gap energy, which can be calculated
by the equation [34],

Where, Eg = band gap energy (eV) and = 430.48, wavelength of the absorption edge in the
spectrum. The value for band gap energy is found to be 2.88 eV. The value of absorbance is
found to be 0.79. The observed value of band gap energy is found to be lower than the
reported data for TiO2 [35]. The narrowing of Eg and red shift of absorption band edge are
due to the number of reasons [24]. It is combined effect of dopant-induced midgap electronic
states and lattice disorder effects [24]. The replacement of oxygen with nitrogen into OTi- O
lattice gives the modification in electronic states of resultant phase structure [24].The doping
of N in TiO2 lattice creates localized N2p states located above the valence band by about 0.7
eV [36-37] theoretically, and localized states below the conduction band edge experimentally
[32]leading to narrowing of Eg. The lattice disorder effects arise due to the differences in the
bonding characteristics between nitrogen and oxygen along with random distribution of
nitrogen. Further, the oxygen vacancies responsible for the colourcentres and created by
charge imbalance due to N doping in TiO2 lattice is major effect of red shift of absorption
band edge [38]. The charge states of these oxygen vacancies create the electronic states of
different energies within the band, whereas the presence of lattice disorder can cause
broadening of such levels finally leading to the narrowing of Eg as is observed in the present

5. Photovoltaic properties

The figs. 6 (a) and (b) give the current density (J) - voltage (V) characteristic curves for
DSSCs of Ndoped TiO2 films with Ti:N ratio as 1:12 for Rose Bengal and Eosin-Y dyes
respectively. The detailed photovoltaic properties obtained for these films are summarized in
Table I. The better photovoltaic properties are obtained for DSSC of N-doped TiO2 film
sensitized with Eosin - Y dye. This is might be due to the incorporation of nitrogen into TiO2
lattice enhancing the visible light absorption. Further, this can be associated with the
substantial porosity required for absorption of Eosin-Y dye in film material leading to the
optimum photoinjections of electrons to the conduction band of the TiO2 giving the better
photo-conversion efficiency. The obtained efficiency is higher than the earlier report of
Eosin-Y [23].

IV. Conclusions

A one-step hydrolysis route and Doctors Blade method are found to be simple and cheap
ways for the preparation of single phase anatase N-doped TiO2 powders and their films. The
increasing red shift in absorption edge, increasing absorbance and narrowing band gap energy
in N-doped TiO2 powdersare due to oxygen vacancies created by charge imbalance leading
to dopant-induced midgap electronic states and lattice disorder effect due to N-doping. The
superior photovoltaic performance: (i) VOC = 0.45 V, JSC = 0.963 mA/cm2, FF = 59.23
%,= 0.52 % using Rose Bengal dye and (ii) VOC = 0.45 V, JSC = 9.67 mA/cm2, FF =
41.27 %, = 1.27 % using Eosin Y dye with polyiodide electrolyte are obtained for the dye
sensitized solar cells (DSSCs) made by using photoanodes based on N doped TiO2 films with
Ti:N ratio as 1:12.