Materials Letters 220 (2018) 218–221

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Synthesis and characterisation of SnO2 nanostructures for

Dye-Sensitized Solar Cells
R. Vasanthapriya a, N. Neelakandeswari b,⇑, N. Rajasekaran b, K. Uthayarani a, M. Chitra a, S. Sathiesh kumar c
a
Department of Physics, Sri Ramakrishna Engineering College, Coimbatore 641022, Tamilnadu, India
b
Department of Chemistry, Sri Ramakrishna Engineering College, Coimbatore 641022, Tamilnadu, India
c
Department of Nanoscience and Technology, Sri Ramakrishna Engineering College, Coimbatore 641022, Tamilnadu, India

a r t i c l e i n f o a b s t r a c t

Article history: Tin Oxide (SnO2) is a wide band gap n-type semiconducting material having good chemical stability, elec-
Received 14 January 2018 trical and optical properties. SnO2 nanostructures were prepared by surfactant assisted solvothermal
Received in revised form 23 February 2018 technique at different pH conditions and used as n-type layer for Dye-Sensitized Solar Cell (DSSC) fabri-
Accepted 25 February 2018
cation. Herein we report the characterization of SnO2 nanostructures by various techniques like Fourier-
Available online 26 February 2018
transform Infra Red spectroscopy (FT-IR), Ultra – Violet and Visible Spectroscopy (UV-Vis),
Photoluminescence (PL), Powder X-Ray diffraction (XRD) and Scanning Electron Microscopy (SEM).
Keywords:
SnO2 prepared at pH – 8 and 10 were used for the fabrication of DSSC and the efficiency was relatively
SnO2
Solar cell materials
higher at pH 8.
DSSC Ó 2018 Elsevier B.V. All rights reserved.
Thin film
Solvothermal
Photovoltaics

1. Introduction by Solvothermal method and the structural and optical properties

The revolutionary works on the DSSC by O’Regan and Gratzel in
the field of photovoltaics motivated the researchers to work on
DSSC, owing to their easy manufacturing processing, low cost
and high photon to current conversion than silicon based solar
cells [1]. The photoanode is one of the most important components
in DSSCs. Among TiO2, SnO2 and ZnO, in addition to transparent
conducting electrodes, SnO2 finds its applicability in gas sensing
devices, photo electrode materials in DSSC . Compared to TiO2,
SnO2 shows a larger band gap and creates fewer oxidative holes
in the valence band under UV illumination, thereby minimizing
the dye degradation rate and improving the long term stability of
DSSCs [2]. SnO2 is a good electron acceptor since its conduction
band edge lies at 0.5 V more positive than that of TiO2 [3]. The pho-
toanode material of DSSC requires large surface area, high dye
binding capability and amorphous nature. This has been accom-
plished by nanostructured SnO2 which motivates to synthesise
the material to give good efficiency.
Compared to other synthetic protocols, solvothermal route is
favoured owing to its low temperature process. In this present
study, SnO2 nanoparticles are prepared for the DSSC fabrication
⇑ Corresponding author.
E-mail address: neela@srec.ac.in (N. Neelakandeswari).
are studied.
2. Experimental details
0.1 M microemulsion of SnCl2 was prepared using ethanol in
presence of the surfactant (sodium dodecyl sulphate). To the
microemulsion, 0.1 M aqueous solution of Hexamethylene tetra-
mine was added dropwise with constant stirring at pH – 8 and
10 and the suspension was allowed to stir for 1 h and transferred
to a 250 ml Teflon lined stainless steel autoclave maintained at
100 °C for 1 h. The autoclave was cooled to room temperature,
solid sample obtained was filtered, washed several times with dis-
tilled water and ethanol separately, dried at 100 °C for 3 h and cal-
cined at 700 °C for 3 h. The samples prepared at pH 8 and 10 were
named as S1 and S2 respectively.
2.1. Fabrication of DSSC
SnO2 paste was prepared by mixing SnO2 nanopowders with tri-
ton X (1 0 0) and coated on an FTO substrate as reported earlier [4].
The films were dried under ambient conditions, annealed at 450 °C
for 15 min.
Then, the films were cooled to room temp, edges were covered
with adhesive tape and immersed in 0.1 M aqueous solution of

https://doi.org/10.1016/j.matlet.2018.02.118
0167-577X/Ó 2018 Elsevier B.V. All rights reserved.
 R. Vasanthapriya et al. / Materials Letters 220 (2018) 218–221
methylene blue for 24 h, washed with distilled water and dried in
air. Cadimium iodide solid electrolyte was deposited by droping
down 5 ll saturated aqueous solution of CdI2 above dye layer
and dried at room temperature. Graphite plate was used as a coun-
ter electrode and was sealed with the working electrode and adhe-
sive tape was used as spacer.
2.2. Characterization
Crystallinity of the samples were identified by X – ray powder
diffraction (XRD) at room temperature on a PANalytical X’pert
PRO X-ray diffractometer using Cu-Ka radiation (k = 1.5406 Å) as
X-ray source. Surface morphology of SnO2 nanoparticles was
imaged using ZEISS ultrafield emission Scanning Electron Micro-
scope. The absorption spectra of the solid samples were recorded
using JASCO UV-Visible spectrophotometer. The photolumines-
cence (PL) spectra were recorded by Agilent fluorescence spec-
trophotometer. Solar cell performance of the fabricated DSSC was
studied using AUTOLAB Electrochemical workstation and
METROHM Solar simulator with 2 sun illumination potential.
Fig. 1. XRD patterns of SnO2 nanoparticles.
Fig. 2. FE - SEM of SnO2 nanoparticles.
219
3. Results and discussion
ATR spectra shows a weak band observed around 1600 cm
1 for
both SnO2 samples is assigned to the vibrational mode of hydroxyl
groups and it is related to the physisorbed water molecules on the
surface. The strong absorption appeared at 687 cm
1 can be
assigned to antisymmetric Sn - O - Sn stretching vibration [5].
All the sharp and strong diffraction peaks observed in the pow-
der XRD pattern of SnO2 (Fig. 1) have been indexed and matched
well with the standard ICDD file no: 41-1445 and it corresponds
to tetragonal rutile phase of SnO2. Peak intensity of SnO2 increases
with pH, which indicates the increase in crystallinity. Average crys-
tallite size was calculated using Scherrer formula [6]
Dc ¼ 0:9k=bcosh
where b is the width at half maximum intensity of the observed
diffraction peak, and k is the X-ray wavelength and it was found to
be 25 nm and 23 nm respectively for S1 and S2. Upon increasing
pH, crystallite size decreases and crystallinity increases in accor-
dance with the report of Jiang et al [7].
FE-SEM image of SnO2 prepared under different pH values are
depicted in Fig. 2. Uniform spherical shaped nanoparticles were
observed in both the samples [8]. When pH increases, the particle
size of SnO2 nanoparticles decreases which is in accordance with
the XRD results.
Fig. 3a shows the UV – Visible absorption spectra of SnO2
nanoparticles and it possess a strong absorption edge between
290 and 350 nm which is lesser than the report [9] and could be
due to Quantum confinement effect.
Fig. 3b shows the room temperature PL spectra of SnO2
nanoparticles prepared from different pH values, with an excita-
tion wavelength of 280 nm. In both the samples, the dominant PL
peaks were observed at 382 nm, 496 nm and 521 nm.
It is evident from the literature that, SnO2 shows complex emis-
sion bands from 318 to 640 nm. Weak emissions observed at 322
nm and 362 nm are correlated to free exciton decay. Intense emis-
sion centred at 382 nm is due to recombination of excited electrons
in the conduction band and a positive hole in the valence band
[10]. Since the band gap corresponding to all the 3 UV emissions
are lesser than the band gap of both S1 and S2 (4.76 and 4.53
eV), these emissions could be correlated to near band edge emis-
sion of SnO2 nanostructures [11]. Radiative recombination due to
defects and oxygen vacancies appear in visible region. In visible
220 R. Vasanthapriya et al. / Materials Letters 220 (2018) 218–221
Fig. 3. (a) UV- Visible Spectra (b) PL spectra of SnO2 nanoparticles.
region both blue and green emission is observed [12]. Low intense
blue emission appeared at 486 nm, 497 nm, 506 nm could be cor-
related to the recombination of conduction band electrons with the
holes at oxygen vacant sites [12]. Green emission observed at 521
nm could be related to the recombination of electrons from the
defect sites to the holes at oxygen vacant sites.
3.1. I-V characteristics of fabricated DSSC
I-V characteristics of DSSCs fabricated using SnO2 photoanodes
is presented in Fig. 4. The solar to electrical energy conversion effi-
ciency g, is calculated from the photo current density, open circuit
photovoltage, fill factor of the cell and the power input using the
formula (1),
gð%Þ ¼ ðJSC :Voc:FF=Pin Þ:100
The fill factor (FF) is the ratio between the maximum output
power density available (Jm . Vm) and the maximum power com-
bining short – circuit and open – circuit situations.
Area of the cells = 1 cm2. Fill factor for S1 & S2 are 0.37 & 0.86
respectively .It is clear that conversion efficiency of the DSSC of
S1 & S2 are 0.0044% & 0.0042% respectively. Though the result
obtained is better than the reports for DSSC fabricated with SnO2
photoanode [13], poor efficiency observed in this study could be
due to the use of solid electrolyte. In addition, the dye methylene
blue used absorbs only blue wavelength (495 nm), might also have
descended the efficiency of power generation. Stability studies
Fig. 4. I-V characteristic of the Fabricated DSSC from the prepared sample.
were performed after 40 days of fabrication and the FF calculated
was found to 0.13 and 0.31 respectively for S1 and S2 with corre-
sponding efficiencies of 0.0013 and 0.0014%. Decrease in efficiency
might be correlated to the poor photochemical stability of methy-
lene blue dye. Photovoltaic efficiency generally depends upon sur-
face area of SnO2, extent of dye adsorbed, thickness of the SnO2
film and the effective electron transporter employed. Improvement
of DSSC performance could be achieved by varying the thickness of
the film, use of I3- electrolyte and also commercial dyes like N719,
N3 and D149 planned to carry out in our future work.
4. Conclusion
Spherical SnO2 nanoparticles with uniform size distribution
ð1Þ were prepared by solvothermal method. Crystallinity of the sam-
ples increases and crystallite size decreases with pH. DSSC was fab-
ricated using the prepared SnO2 nanostructures and methylene
blue dye, the efficiency observed is very low. DSSC fabricated with
SnO2 prepared at pH 8 showed 0.0044% efficiency and is compara-
tively better than SnO2 prepared at pH 10. In future, efforts will be
taken to improve the performance of the DSSC by varying various
parameters mentioned earlier.
Acknowledgement
Authors wish to thank DST, India for creating characterisation facil-
ities under DST-FIST (SR/FST/COLLEGE-154/2013 scheme in Sri
Ramakrishna Engineering College, Coimbatore, Tamilnadu, India).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.matlet.2018.02.118.
References
[1] B. O’ Regan, M. Gratzel, Nature 353 (1991), 737–740
[2] N.G. Park, M.G. Kang, K.S. Ryu, K.M. Kim, S.H. Chang, J. Photochem. Photobiol. A
161 (2004) 105–110.
[3] T. Stergiopoulos, I.M. Arabatzis, H. Cachet, P. Falaras, J. Photochem. Photobiol. A
155 (2003) 163–170.
[4] M.M. Rashad, I.A. Ibrahim, I. Osama, A.E. Shalan, Bull. Mater. Sci. 37 (4) (2014)
903–909.
[5] S. Emiroglu, N. Barsan, U. Weimar, V. Hoffmann, Thin Solid Films 391 (2001)
176–185.
[6] S. Chandramouleeswaran, S.T. Mhaske, A.A. Kathe, P.V. Varadarajan, V. Prasad,
N. Vigneshwaran, Nanotech 18 (2007) 38.
 R. Vasanthapriya et al. / Materials Letters 220 (2018) 218–221 221

[7] L. Jiang, G. Sun, Z. Zhou, S. Sun, Q. Wang, S. Yan, H. Li, J. Tian, J. Guo, B. Zhou, Q.
Xin, J. Phys. Chem. B 109 (18) (2005) 8774–8778.
[8] S. Tazikeh, A. Akbari, A. Talebi, E. Talebi, Mater. Sci.-Poland 32 (1) (2014) 98–
101.
[9] N. Bouazizi, R. Bargougui, T. Boudharaa, M. Khelil, A. Benghnia, L. Labiadh, R.
Ben slama, B. Chaouachi, S. Ammar, A. Azzouz, Ceram. Int. 42 (8) (2016) 9413–
9418.
[10] Arik kar, Simanta Kundu, and Amitava patra J.Phys.Chem. C 2011, 115, 118-
124
[11] R. Lotfi Orimi, M. Maghouli, Optik 127 (2016) 263–266.
[12] X. Xiang, X.T. Zu, S. Zhu, L.M. Wang, V. Shutthanandan, P. Nachimuthu, Y.
Zhang, J. Phys. D Appl. Phys. 41 (2008) 225102.
[13] Henry J. Snaith, Caterina Ducati, Nano Lett. 10 (2010) 1259–1265.