Materials Science in Semiconductor Processing 40 (2015) 331336

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Materials Science in Semiconductor Processing

journal homepage: www.elsevier.com/locate/mssp

Fabrication of a counter electrode using glucose as carbon

material for dye sensitized solar cells
Rahul kumar, Parag Bhargava n
Department of Metallurgical Engineering and Materials Science Indian Institute of Technology Bombay, Mumbai 400076, India

a r t i c l e i n f o

Keywords:
Carbon material
Counter electrode
Dye-sensitized solar cells

abstract
Carbon material was produced from the graphitization of glucose at high temperature in
flowing argon. The produced carbon material was characterized using Scanning electron
microscopy, Transmission electron microscopy, Raman spectroscopy and XRD. Carbon
slurry of the produced carbon was made in ethanol by using polyvinylpyrrolidone (PVP) as
surfactant. Carbon slurry was coated homogeneously on fluorine doped tin oxide (FTO)
glass by a doctor blade technique and applied as counter electrode for dye synthesized
solar cell. The current density (J) and open circuit voltage (VOC) of fabricated cell was
8.30 mA cm
2 and 0.77 V respectively. The efficiency of the cell was 3.63%, which is
comparable to 5.82% of cell with platinum counter electrode under the same experimental
conditions.
& 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Dye sensitized solar cells (DSSCs) have attracted much
attention due to ease of fabrication, low cost and high
conversion efficiency [12]. The DSSCs consists of a dye
sensitized TiO2 nanocrystalline electrode, liquid electrolyte
acts as a redox couple, counter electrode which collects the
electrons arriving from the external circuit and catalyze


the I3 /I
redox-coupled regeneration reaction in electrolyte [3]. Platinum is the commonly used material to
fabricate the counter electrode for DSSCs due to its high
catalytic activity [4] but high cost of this material is the
major issue. A lot of research is going on to replace the
platinum by other alternatives like carbon materials, conducting polymers, inorganic materials, multiple compounds and composites to fabricate the counter
electrodes for DSSCs [57]. These materials also have good
performances in DSSCs.

Corresponding author.
E-mail addresses: kumarrahul003@gmail.com (R. kumar),
pbmatsc@gmail.com (P. Bhargava).
http://dx.doi.org/10.1016/j.mssp.2015.06.009
1369-8001/& 2015 Elsevier Ltd. All rights reserved.

Among all the materials carbon materials (carbon black,

graphite, carbon nanotubes, graphene etc.) have been
studied by many researchers [814] as a promising alternatives to substitute the Pt for DSSCs due to their high
conductivity, easy fabrication and good catalytic activity. In
this work, we report the fabrication of carbon material
produced from the graphitization of glucose at high
temperature in flowing argon. Carbon slurry was made
by using produced carbon material with PVP and carbon
film was coated on FTO glass substrate by the doctor blade
technique for the fabrication of counter electrode used
in DSSCs.

2. Experimental details
2.1. Materials and methods
Carbon material was produced from the graphitization
of glucose (Glucon-D, Heinz) (5 g) at high temperature
(14001 C) in flowing argon. Carbon slurry from produced
carbon was prepared as follows, PVP (K-32, Sigma-Aldrich)
(0.12 gm) solution was prepared in ethanol (10 ml), carbon

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Fig. 1. FEG-SEM micrographs (a) at low magnification and (b) at high magnification, Raman Spectroscopy (c), XRD pattern (d) of the carbon produced from
the graphitization of glucose at 1400 1C.

(1 g) was crushed in a mortar pestle to make it finer was

added to the PVP solution and this mixture was kept on
pot mill for 48 h in order to make a homogeneous slurry
by deagglomeration of powder. To measure the particle
size of the produced carbon, carbon slurry was diluted by
ethanol to make the diluted carbon solution and put in a
sonicator for 15 min to reduce the agglomerates. Diluted
carbon solution was also used for FEG-TEM characterization. This solution was put on carbon grid and dried under
a UV lamp for characterization. Counter electrode was
made by coating the slurry on FTO-glass substrate (TEC8,
sheet resistance 89
1 Pilkington) by the doctor blade
technique. Scotch tape (3 M) was used to coat on the
desired area. The counter electrode was kept in furnace at
450 1C for 1 h in flowing argon in order to burn out the
binder. Sputter deposited platinum on FTO glass was also
used as counter electrode to fabricate the cell. Titania
slurry used for fabricating photoanodes was prepared by
roller milling TiO2 nanopowder (P25, Degussa), PEG 600
(Thomas Baker) and ethanol for 24 h. The slurry was then
coated onto the cleaned FTO-glass substrates and sintering
was carried out at 450 1C for 1 h. Then the electrodes were
cooled to 80 1C and dipped into a 0.3 mM solution of N3
(Dyesol) dye in ethanol. After 24 h, the electrodes were

taken out of the dye solution, rinsed with ethanol and

dried. An electrolyte used in the DSSCs was prepared by
mixing 1-Methyl-3-propylimidazolium iodide [PMII]
( Z98% Aldrich) (0.60 M), iodine (LR, Thomas Baker) [I2]
(0.03 M), guanidinium thiocyanate (0. 10 M) and 4-tertbutylpyridine ( 0.50 M) [TBP] (96% Aldrich) in the mixture
of acetonitrile and valeronitrile (volume ratio: 85:15). The
solution was stirred by magnetic stirring for 30 min [15].
Cell was fabricated using electrolyte, electrodes and
spacer. To seal both the electrodes together, a 25 m spacer
(SX1170-25PF, Solaronix) was used and the assembly was
heated at 115 1C for 15 min. The active area of each cell was
0.25 cm2.
2.2. Characterization
The produced carbon from the graphitization of glucose
at 1400 1C was independently characterized by FEG-SEM
(JEOL,JSM-7600F), FEG-TEM (JEOL,JEM-2100F), BET (Smart
Sorb 92/93, Smart Instruments Co.), DLS(Beckman Coulter,
Delsa Nano-C particle analyzer), XRD measurement was
performed with the scan rate of 201/min with Cu-K
source (Expert Pro, 40 kV,30 mA, Panalytical) and Raman
spectroscopy measurement was performed with the scan

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333

Fig. 2. FEG-TEM micrographs (a) at high magnification and (b) diffraction pattern of carbon produced from graphitization of glucose at 1400 1C.

rate of 2000 cm
1/min with 514 nm excitation source

(Jobin-Yvon, FranceRamnorHG-2S Spectrometer). Cyclic
voltammetry measurement was performed by using
PGSTAT (AUTOLAB 302N). Cyclic voltammetry (CV) of
counter electrodes was performed at a scan rate of
50 mV/s from
0.6 to 1.2 V using a three electrode
assembly where the carbon or platinum coated FTO-glass,
platinum wire and Ag/AgCl served as the working electrode, counter electrode and reference electrode respectively. Resistivity of the carbon film and platinum film was
measured by using four probes. DSSC performance measurements were performed by using a Keithley model
2420 source measure unit. The irradiation source was a
150 W xenon lamp on a Newport 1 sun solar simulator
with AM 1.5G.
3. Results and discussion
FEG-SEM of carbon produced by glucose (Fig. 1a)
showed flake like particles in the range of 200900 mm.
Surface area of the produced carbon was measured by BET
and was found to be 7 m2/g. The particle size of the
produced carbon was measured by DLS (Dynamic light
scattering). 10 vol% particles were having particle size less
than 463 nm while 90 vol% particles were having particle
size less than 783 nm and average particle size (d50) was
obtained around 620 nm. Higher magnification micrographs (Fig. 1b) indicated that the individual flakes were
composed of much finer particles. In Raman spectroscopy
measurement of carbon produced by glucose (Fig. 1c), we
observed a prominent band around 1341 cm
1. This band
is known as the D band and one another prominent band
was also observed at 1598 cm
1, this is known as G band.
We also observed two bands at 2683 cm
1 and 2940 cm
1
respectively. Band at 2683 cm
1 is known as 2D band or G'
band. This band is symmetry allowed and appears in the
second order Raman spectra of crystalline graphite. Band
at 2940 cm
1 is associated with a D G combination mode
and also induced by disorder [16]. The ID/IG ratio of the
produced carbon was found to be 1.18 showed graphitic
nature of the carbon and also confirmed by SAD pattern of

FEG-TEM as shown in Fig. 2(b). FEG-TEM micrograph (a)

also showed flake like particle and crystalline nature of the
produced carbon. The XRD pattern (Fig. 1d) showed two
peaks corresponding to the crystalline reflections from
(002) and (101) planes. The 2 values at which the
intensity maximum observed for (002)/(101) planes are
23.37/44.33. Carbon prepared from glucose has turbostratic graphite structure. The LD crystal size was measured by
using wavelength power law formula [16]. The LD crystal
size was found to be 14.25 nm. FEG-SEM was used to
characterize the surface morphology of the counter electrode after heat treatment at 4501 C (1 h) in flowing argon
as shown in Fig. 3. After heat treatment the surfactant
(PVP) was converted into carbon. Film appears porous in
nature and pores are homogenously disturbed within the
film. The thickness of the film was measured by FEG-SEM
as shown in Fig. 3(a) and found to be 0.98 mm. The sputter
platinum film appears dense in nature as shown in Fig. 3(c
and d). The cyclic voltammogram of platinum and carbon
electrodes are shown in Fig. 4. Fig. 4 compares cyclic
voltammograms of I2/I
system for carbon and platinum
electrode at the same electrolyte of the DSSCs. Two pairs of
redox peaks were observed in both cases. The relative
negative pair is assigned to the redox reaction (1) and the
positive one is assigned to redox reaction (2).
I3
2e
3I

3I2 2e
2I3

The redox reaction (1) that takes place at the counter

electrode of a DSSC and is vital for its operation. The redox
reaction (2) in cyclic voltammogram is due to the reduction of I2 molecules [17,18]. Thus the magnitude of current
density at counter electrode is directly proportional to the


ability of the electrode to reduce the I3 . It can be observed


that carbon shows high redox reactivity towards I3 and I2
even higher than Pt [17]. In addition to this, the reduction


peaks and hence the redox potentials of I
/I3 system is
shifted slightly toward the positive side in case of the

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R. kumar, P. Bhargava / Materials Science in Semiconductor Processing 40 (2015) 331336

Fig. 3. FEM-SEM micrographs (a) side view of the carbon film (b) upper surface of the carbon film, (c) and (d) upper surface of the sputtered platinum film.

Fig. 4. Cyclic voltammetry curves of carbon produced from graphitization of glucose and Pt counter electrodes at a scan rate of 50 mV s
1 from
0.6 to
1.2 V in 5 mM LiI, 0.5 mM I2 and 0.1 M LiClO4 acetonitrile solution. Reference electrode: Ag/Ag in acetonitrile. Auxiliary electrode: Pt/FTO.

carbon electrode. This could directly lead to higher Voc

[19].
Higher current density was observed in carbon based
counter electrode as compared to platinum. This is due to
the availability of higher catalytic sites for redox reaction
in carbon electrode than platinum. As observed from the
FEG-SEM images, carbon has highly porous structure and

hence in the carbon film higher active sites are obtained

than platinum possessing a dense film as shown in Fig. 3(c
and d). Increase in over potential towards redox reaction in
carbon electrode might be due to the higher resistance of
the film than platinum electrode. It was observed by four
probe measurement that resistivity of carbon film was
found to be 0.0067 cm while resistivity of platinum film

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335

Fig. 5. Photocurrentvoltage characteristics of the cells using carbon produced from graphitization of glucose and Pt counter electrodes.
Table 1
Photovoltaic and electrochemical parameters of DSSCs with different
counter electrodes.
Counter electrode

JSC (mA cm
2)

VOC (V)

FF

(%)

Platinum
Carbon

12.07
8.30

0.72
0.77

0.6
0.5

5.82
3.63

was found to be 0.000036 cm. JV characteristic curves

of DSSCs using carbon produced from graphitization of
glucose and Pt counter electrodes are presented in Fig. 5,
and the corresponding photovoltaic and electrochemical
performance parameters of the cells are summarized in
Table 1. The cell prepared using carbon as counter electrode displayed open circuit voltage VOC of 0.77 V, short
circuit current density JSC of 8.30 mA cm
2, fill factor (FF)
of 0.5 and conversion efficiency () of 3.63% respectively.
The cell prepared using platinum as counter electrode
displayed open circuit voltage VOC of 0.72 V, short circuit
current density JSC of 12.07 mA cm
2, fill factor (FF) of 0.6
and conversion efficiency () of 5.82% respectively. The
carbon material shows lower conversion efficiency than Pt
electrode although carbon material shows higher redox
reactivity. It is known that the Pt electrode itself at the
same time acts as a light reflector and carbon will not
reflect light [20,21]. Lower fill factor and short circuit
current density in carbon counter electrode based cell as
compared to platinum based cell is responsible for poor
efficiency. Even though higher catalytic activity was
observed in the electrode fabricated using the synthesized
carbon due to highly porous film offering higher effective
surface area for the reduction of tri-iodide species but
higher over potential towards redox reaction or resistance
of the film seems to be the dominating factor in deciding
the cell performance.
4. Conclusions
Carbon material was produced by graphitization of
glucose in flowing argon at high temperature. The

produced carbon showed flake like particles and each

flake was made of small carbon particles. The particle size
(d50) of produced carbon was measured by dynamic laser
diffraction (DLS) and was found to be around 600 nm. The
produced carbon material had graphitic nature and
showed catalytic property. The produced carbon material
was used to fabricate the counter electrode in DSSCs.
Carbon film showed porous nature and had resistivity
around 0.0067 cm. Counter electrode was fabricated
for DSSC using carbon material. The prepared cell displayed open voltage VOC of 0.77 V, short circuit current
density JSC of 8.30 mA cm
2, fill factor (FF) of 0.5 and
conversion material efficiency () of 3.63% respectively.

Acknowledgments
The authors are grateful to SAIF department IIT
Bombay.
References
[1] O ReganB, M. Grtzel, Nature 353 (1991) 737740.
[2] Y. Chiba, A. Islam, R. Komiya, N. Koide, L.Y. Han, Appl. Phys. Lett. 88
(2006) 223505223508.
[3] A. Ko, J. Oh, Y. Lee, S. Han, K. Park, Mater. Lett. 65 (2011) 22202223.
tzel, J. Electrochem. Soc. 144
[4] N. Papageorgiou, W.F. Maier, M. Gra
(1997) 876884.
[5] A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo, H. Pettersson, Chem. Rev. 110
(2010) 65956663.
[6] A. Kay, M. Grtzel, Sol. Energy Mater. Sol. Cells 44 (1996) 99117.
[7] Q. Li, J. Wu, Q. Tang, Z. Lan, P. Li, J. Lin, L. Fan, Electrochem. Commun.
10 (2008) 1299.
[8] T.N. Murakami, S. Ito, Q. Wang, M.K. Nazeeruddin, T. Bessho, I. Cesar,
P. Liska, R Humphry-Baker, P. Comte, P. Pechy, M. Gratzel, J.
Electrochem. Soc. 153 (2006) A2255.
[9] G. Veerappan, K. Bojan, S.-W. Rhee, ACS Appl. Mater. Interfaces 3
(2011) 857.
[10] T.N. Murakami, S. Ito, Q. Wang, M.K. Nazeeruddin, T. Bessho, I. Cesar,
P. Liska, R. Humphry-Baker, P. Comte, P. Pechy, M. Grtzel, J.
Electrochem. Soc. 153 (2006) A2255A2261.
[11] J. Han, H. Kim, D.Y. Kim, S.M. Jo, S.Y. Jang, ACS Nano 4 (2010) 3503.
[12] W.J. Lee, E. Ramasamy, D.Y. Lee, J.S. Song, ACS Appl. Mater. Interfaces
1 (2009) 1145.

336

R. kumar, P. Bhargava / Materials Science in Semiconductor Processing 40 (2015) 331336

[13] E. Ramasamy, W.J. Lee, D.Y. Lee, J.S. Song, Electrochem. Commun. 10
(2008) 10871089.
[14] J.D. Roy-Mayhew, D.J. Bozym, C. Punckt, I.A. Aksay, ACS Nano 4
(2010) 6203.
[15] G. Wang, W. Xing, S. Zhuo, J. Power Sources 194 (2009) 568.
[16] M.A. Pimenta, G. Dresselhaus, M.S. Dresselhaus, L.G. Cancado,
A. Jorio, R. Saito, Phys. Chem. Chem. Phys. 9 (2007) 12761291.
[17] A.I. Popov, D.H. Geske, J. Am. Chem. Soc. 80 (1958) 1340.

[18] Kohshin Takahashi Kiyoaki Imoto, Teruhisa Takahiro Yamaguchi,

Jun-ichi Komur, Kazuhiko Murata Nakamura, Sol. Energy Mater.
Sol. Cells 79 (2003) 459469.
[19] M. Durr, A. Yasuda, G. Nelles, Appl. Phys. Lett. 89 (2006) 061110.
[20] M.K. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E Mu ller,
P. Liska, N. Vlachopoulos, M. Gra tzel, J. Am. Chem. Soc. 115 (1993)
63826390.
[21] W.J. Lee, E. Ramasamy, ACS Appl. Mater. Interfaces 1 (2009)
11451149.