Solar Energy Materials & Solar Cells 143 (2015) 250259

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Solar Energy Materials & Solar Cells

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

Graphene quantum dots decorated electrospun TiO2 nanobers as an

effective photoanode for dye sensitized solar cells
Zaahir Salam a, E. Vijayakumar a, A. Subramania a,n, N. Sivasankar b, Sudhanshu Mallick b
a
Electrochemical Energy Research Lab, Centre for Nanoscience and Technology, Pondicherry University, Puducherry 605 014, India
b
Department of Metallurgical Engineering & Materials Science, Indian Institute of Technology-Bombay, Mumbai 400076, India

art ic l e i nf o a b s t r a c t

Article history: In this study, graphene quantum dots (GQDs) are prepared with an average size of
15 nm by a top
Received 16 March 2015 down approach using carbon nanobers (CNFs) to improve the photovoltaic performance of DSSCs. The
Received in revised form titanium isopropoxide (Ti(OPr)4)/PVP precursor solution is used to get TiO2 NFs by electrospinning
5 June 2015
technique and then they are decorated with the prepared GQDs. First, the prepared GQDs are conrmed
Accepted 1 July 2015
by XRD, Raman, TRPL, DLS, UVvis, and PL Spectroscopy. The presence of GQDs onto TiO2 NFs is also
Available online 23 July 2015
conrmed by XRD, Raman spectroscopy and EDX studies. The surface morphology and the presence of
Keywords: GQDs onto TiO2 NFs are conrmed by SEM and TEM analysis. The optical properties of GQDsTiO2 NFs
Electrospinning are studied by UVvis and PL spectroscopy. Finally, the dye sensitized solar cell is fabricated using GQDs
Dye sensitized solar cell
decorated TiO2 nanobers as the photoanode and standard Pt (Dyesol Ltd.) as the counter electrode and
Graphene quantum dots
0.5 M 1-butyl-3-methylimidazolium iodide, 0.5 M LiI, 0.05 M I2, 0.5 M 4-tertbutylpyridine, in acetonitrile
Carbon nanobers
Titania nanobers as the electrolyte. A dye-sensitized solar cell (DSSC) with a photoanode based on GQDsTiO2 NFs
exhibited a high energy conversion efciency of 6.22%, than the DSSC based on pure TiO2 NFs photo-
electrode (4.81%), accompanied by an increment in both short-circuit photocurrent density and open-
circuit voltage. The overall improvement in PCE is
29.31% for GQDs decorated TiO2 NFs which is higher
than other reported systems. The better photogenerated electron transfer ability, reduced charge
recombination, increased dye adsorption, and an effective harvesting of visible light, which together
added to an improvement in PCE. The stability test is performed for the DSSCs over a period of 30 days
(720 h) under one sun soaking, where GQDs decorated TiO2 NFs DSSCs is seen to retain
99% of its initial
normalized efciency, thereby making it a viable option for practical applications.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction nanostructured networks inside the photoanode. Such a random

Dye sensitized solar cell (DSSC) was rst reported by O'regan
and Gratzel, which attracted the world to the light to electricity
conversion, because of its low cost, easy fabrication, environ-
mental friendly than other conventional solar cells [1]. The per-
formance of DSSC depends mostly on photoanode material; since,
it inuences both photocurrent and photovoltage of the solar cell.
TiO2 is a wide band gap semiconductor material (3.2 eV) that is
commonly used as photoanode material in DSSC, which helps in
anchoring of dye molecules, acceptance of electron from the dye
and transport of these electrons to the conductive base. The major
bottleneck in yielding higher efciency is ascribed to a fact that the
photogenerated electrons encounter huge amounts of grain
boundaries among nanoparticles as they travel through these 3-D
n
Corresponding author. Tel.: 91 413 2654980; fax: 91 413 2655348.
E-mail address: a.subramania@gmail.com (A. Subramania).
walk mode can lead to retardation in electron transit and increases
their probability to recombine with oxidized dye molecules and
electron acceptor in electrolyte. To overcome this problem, pho-
toanode is prepared in the 1-D nanostructured mode. The recent
developments in electrospinning technique provide a simple and
low cost approach for producing 1-D nanobers with a broad
range of diameters ranging from a few nanometers to micro-
meters. For a typical TiO2 photoanode based DSSC, the high charge
collection efciency of photogenerated electrons that are trans-
ported through mesoporous TiO2 lm to electrode is needed to
avoid any recombination with the reduced redox species. To
improve the charge collection efciency of these photogenerated
electrons, one of the promising solution is to introduce electrically
high conductive carbon materials such as fullerene, CNTs and
graphene into TiO2 nanostructures [24]. Among these carbon
materials, graphene onto TiO2 NFs is seen to enhance the perfor-
mance of DSSC due to its low resistance, excellent optical

http://dx.doi.org/10.1016/j.solmat.2015.07.001
0927-0248/& 2015 Elsevier B.V. All rights reserved.
 Z. Salam et al. / Solar Energy Materials & Solar Cells 143 (2015) 250259
transmittance and high electron transport [5]. To facilitate further
the applications of graphene and to tune its band gap, one of the
approaches is to convert the 2-D graphene sheets into zero
dimensional (0-D) graphene quantum dots (GQDs) which have
unique electron transportation properties, and show new phe-
nomenon that arises due to quantum connement and edge
effects [6,7]. The development of these type of QDs will help to
control the fundamental properties of materials through size/
shape effects, in turn to help in the development of new devices
with extraordinary properties and functions. A lot of methods have
been used to develop GQDs by fragmentation or cutting of gra-
phene sheets (top down approach) [8] and synthesizing graphene
like molecules from organic molecules (bottom up approach)
[9,10]. GQDs are large-band-gap semiconductor with distinctive
physical properties of high chemical stability, large surface area,
and huge exciton binding energies.
Till date, there are only very few reports on GQDs decorated
TiO2 nanoparticles (NPs) as photoanode for the enhancement of
photovoltaic performance of DSSC [1114]. But, there is no report
on the effect of GQDs onto TiO2 NFs as photoanode for DSSCs.
Hence, in the present investigation, we prepared GQDs by a top
down approach using CNFs as the precursor and the prepared
GQDs are decorated onto electrospun TiO2 NFs at the rst time and
their effect on the photovoltaic performance of DSSC are studied in
detail.
2. Experimental
2.1. Materials used
Carbon nanobers are procured from Sigma Aldrich, and are
pyrolitically stripped platelets with 498% carbon basic, Diame-
ter  Length 100 nm  20200 mm with a M.Wt. of 12.01 g/mol,
Titanium (IV) isopropoxide (98%), polyvinylpyrrolidone and Dia-
lysis bag (Retained M.wt: 2000 Da) were procured from Sigma-
Aldrich. Conc. H2SO4, Conc. HNO3, ammonia solution, ethanol and
acetic acid were procured from Merck India Ltd. All these chemi-
cals are analytical grade and used as received without any further
purication.
2.2. Synthesis of GQDs
Carbon nanobers (0.30 g) were added into a mixture of conc.
H2SO4 (60 mL) and HNO3 (20 mL). The solution was ultra sonicated
for 2 h and reuxed with stirring for 24 h at 100 C. The mixture
was then cooled and diluted with deionized water (800 mL). The
pH was adjusted to 7 with NH4OH solution. The resultant solution
was further dialyzed in a dialysis bag (Retained M.Wt.: 2000 Da)
for 3 days to get GQDs (Fig. 1).
2.3. Preparation of GQDs decorated TiO2 NFs
The TiO2 NFs were prepared as per our earlier report [15]. GQDs
were decorated using electrophoretic lling [16]. Before the
deposition, the GQDs were converted into negatively charged one
by tuning the pH of the suspension into 8 with NH4OH. Then, a
positive bias potential of 6 V was applied to the TiO2 NFs, directing
the negatively charged GQDs to move towards the TiO2 NFs and
tightly attach to the positively charged surface of the TiO2 NFs with
sonication for 10 min followed by removal of excess diluting agent
under reduced atmospheric pressure at 25 C using a rotary eva-
porator, which led to a proper decoration and a strong attachment
of GQDs onto TiO2 NFs.
251
Fig. 1. Schematic representation of the processes for the preparation of GQDs by a
top down approach using CNFs as precursor.
2.4. Characterization
The various properties of synthesized GQDs and the GQDs
decorated TiO2 NFs are studied individually in detail for clear
understanding and quality maintenance.
First the structural properties of GQDs prepared from CNFs are
characterized by X-ray diffraction studies (Rigaku, Ultima IV) over
a range of 2 angles from 10 to 80. The quality of GQDs is
characterized by Raman Spectroscopy (Renishaw). Viability of
GQDs for optoelectronics applications are characterized by Time
resolved photoluminescence (TRPL) using a time-correlated single
photon counting technique with Fluorolog-spectrometer (Model
no. FL-1057). The average size of GQDs are characterized by
Dynamic Light Spectroscopy and various optical properties char-
acterized by UVvis and PL Spectroscopy.
The structural properties of GQDs decorated TiO2 NFs are also
characterized by X-ray diffraction studies over a range of 2 angles
from 10 to 80. Raman Spectroscopy is done to know the presence
of GQDs in TiO2 NFs using a 514 nm laser for excitation. The
scanning electron microscopy (Hitachi, Model: S-4200) coupled
with EDS (Energy dispersive X-ray spectroscopy) employed to
study surface morphology and the composition of TiO2 NFs
respectively. The morphology of GQDs decorated TiO2 NFs was also
probed by eld emission-transmission electron microscope (FE-
TEM, JSM-7600F). The absorption spectra was recorded by UVvis
spectrophotometer (Perkin Elmer, Model: L-650) to study the
inuence of GQDs decorated TiO2 NFs on the adsorption of N719
dye. Photoluminescence characterization was done using a lumi-
nescence spectrometer (Nanolog, HORIBA, JobinYvon) with Xenon
lamp as the source of excitation. Time resolved photoluminescence
(TRPL) using a time-correlated single photon counting technique
with Fluorolog-spectrometer (Model no. FL-1057) was used to
know about decay time of GQDs decorated TiO2 NFs.
2.5. Fabrication of DSSC
FTO glass plates were cleaned with a detergent solution in an
ultrasonic bath for 5 min, followed by cleaning in de-ionized
water, acetone, and ethanol for 5 min each, and then dried with
hot air. The pure TiO2 NFs and GQDs decorated TiO2 NFs were
coated with 1012 m thick on FTO glass plates by the doctor
blade technique and then annealed at 450 C for 30 min. After
252 Z. Salam et al. / Solar Energy Materials & Solar Cells 143 (2015) 250259

cooling to 80 C, the TiO2 electrodes were immersed into the
puried 0.3 mM N719 dye solution [Di-tetrabutyl ammonium cis-
bis(isothiocyanato) bis (2,2-bipyridyl-4,4-dicarboxylato) ruthe-
nium(II)] for 12 h at 30 [17]. After completion of the dye
adsorption, the lms were rinsed with pure ethanol to remove the
excess dye. In the counter electrode, a hole was drilled to allow the
electrolyte introduction later on and subsequently cleaned in an
ultrasonic bath with acetone and ethanol for 5 min. Then, the Pt
paste was applied by using the doctor blade technique and then
sintered in a mufe furnace at 450 C for 30 min. A 60 mm surlyn
spacer (SX 1170-60 from Solaronix) was sandwiched between the
photoelectrode and the standard platinum coated FTO counter
electrode. A drop of the prepared electrolyte solution of 0.5 M
1-butyl-3-methylimidazolium iodide, 0.5 M LiI, 0.05 M I2, 0.5 M
4-tertbutylpyridine in acetonitrile [18] was introduced inside the
cell through the hole drilled in the counter electrode. The holes
were then sealed with surlyn strip. The resultant active areas of
the cell was found to be 0.20 cm2.

Fig. 2. Various characterization studied to conrm the preparation and properties of GQDs; (a) XRD of CNFs and GQDs, (b) Raman spectra for GQDs and CNFs, (c) DLS
spectrum of GQDs solution, (d) TRPL spectrum of GQDs solution, (e) UVvis spectrum of GQDs solution, (f) PL spectra of GQDs solution. (For interpretation of the references
to color in this gure legend, the reader is referred to the web version of this article.)
 Z. Salam et al. / Solar Energy Materials & Solar Cells 143 (2015) 250259
2.6. Cell studies
The photovoltaic performances were measured using a com-
puter controlled digital source meter. A Xe lamp with AM 1.5 lter
(Oriel) was used to illuminate the DSSC at 100 mW cm  2. Elec-
trochemical impedance measurements were carried out at room
Fig. 3. XRD patterns of pure TiO2 NFs and GQDs decorated TiO2 NFs.
Fig. 4. Raman spectra of pure TiO2 NFs and GQDs decorated TiO2 NFs.
Fig. 5. EDS spectra of (a) Pure TiO2 NFs and (b) GQDsTiO2 NFs.
253
temperature in the frequency range of 1 mHz100 kHz with the
AC amplitude of 10 mV to determine charge transfer resistance
between the conducting oxide (FTO) and GQDs decorated TiO2 NFs
and the interface between GQDsTiO2 NFs|dye|electrolyte. The
illumination condition for the impedance measurements was the
same as that of JV measurements. To know about the effect on
harvesting of sunlight, the incident photon-to-current conversion
efciency (IPCE) of the DSSCs was measured using a photon
counting spectrouorometer (ISS PC1), equipped with a 350 W Xe
lamp and a motorized monochromator in the wavelength range of
300800 nm. Transient photocurrent curves were also obtained
using an electrochemical analyzer (Biologic-VSP, France) to know
about the charge transfer dynamics of the DSSC.
3. Results and discussion
Fig. 2 lists various characterizations done to identify the for-
mation and the quality of as prepared GQDs. Fig. 2(a) shows the
X-ray diffraction (XRD) pattern of GQDs prepared from CNFs and it
is seen that the GQDs have a broad (002) peak centered at around
21.5, while for CNFs, it is centered at 25.02 this is due to the
bigger interlayer spacing in GQDs than CNFs as oxygen containing
groups are introduced in between during the exfoliation and
oxidation of CNFs [19,20]. Fig. 2(b) shows the Raman prole of
GQDs which shows Major Raman feature with a D-band at around
1361 cm  1 and G-band at around 1584 cm  1, and the relative
intensity of the disorder D-band to the crystalline G-band (ID/IG) is
found to be 0.9 and 1.4 for GQDs & CNFs, respectively. A 2D peak
around 2703 cm  1 is seen to occur for GQDs. Fig. 2(c) shows the
dynamic light scattering (DLS) size distribution spectrum for
GQDs. It is used to know average size of synthesized GQDs and is
found to be
15 nm, which conrmed their quantum nature.
Fig. 2(d) shows the luminescence decay prole of the synthesized
GQDs and it is found that as synthesized GQDs can be used for
optoelectronic applications as the lifetime data which was very
well tted to a triple exponential function reveled the life time
decay to be in nanoseconds 1 3.04 ns, 2 1.00 ns, 3 6.65 ns,
which means that they will allow a faster transfer of the electron
through them. Fig. 2(e) shows the UV absorption for GQDs where
peak absorption is seen to occur at approximately 294 nm which is
attributed to * transition of aromatic sp2 domains in GQDs, the
peak is small because of low intensity of very small size of the sp2
domain of the carbon skeleton in GQDs [21,22]. In the inset of
Fig. 2(e) the photographs of GQDs under normal and UV light
254 Z. Salam et al. / Solar Energy Materials & Solar Cells 143 (2015) 250259
(365 nm) are shown. The blue PL of GQDs is strong enough to be
seen easily with naked eye. The blue color is due to the effect of
size and surface functional groups. Fig. 2(f) shows strongest pho-
toluminescence (PL) emission occurred at 498 nm with a Stokes
shift of 26 nm by the change in excitation wavelength from 365 to
440 nm[23].
Fig. 3 shows XRD proles of pure TiO2 and GQDs decorated TiO2
NFs calcinated at 500 C. It shows a dominance of pure anatase
phase. The diffraction peaks corresponding to anatase phase are
represented by the crystal planes (101), (004), (200), (105), (211),
(204), (116), (220) and (215), which have good agreement with
JCPDS data (Card no. 89-4921). It shows that there is no change in
phase with decoration of GQDs. The peak appear at 21.5 conrms
the presence of GQDs onto TiO2 NFs. The crystallite size of GQDs
decorated TiO2 NFs increased from 13.1 nm to 14.8 nm than pure
TiO2 NFs. This is due to the penetration of some GQDs into the
pores of TiO2 NF during sonication, which is calculated using
Bragg's equation:
n GQDs decorated TiO2 NFs. It can be seen that the GQDs of size
d=
cos ( )
where, n 0.9 (Scherer's constant), 1.54 A, Full width
half maximum, Bragg's diffraction angle.
Fig. 4 shows Raman spectra for pure TiO2 NFs and GQDs
decorated TiO2 NFs. The main characteristic peak of anatase TiO2
appeared at 155 cm  1 is attributed to the main Eg(1) anatase
vibration mode. Moreover, the presence of crystalline TiO2 is
conrmed by the vibration peaks at 100 cm  1 for B1g(1), 516 cm  1
for A1g(1) B1g(2) and 639 cm  1 for Eg(2) [24,25]. The two typical
bands at around 1343 cm  1 (D-band) and 1570 cm  1 (G-band)
correspond to presence of GQDs. The D-band is ascribed to edges,
defects, and disordered carbon, whereas the G-band arises from
the zone center E2g mode, corresponding to ordered sp2-bonded
carbon atoms. The presence of D and G bands in GQDs decorated
TiO2 NFs, highlight a strong interaction between GQDs and anatase
Table 1
Energy dispersive X-ray spectra showing the distribution of. Ti, C, and O atoms in
pure TiO2 NFs and GQDs decorated TiO2 NFs.
Photoanode Titanium (wt%) Carbon (wt%) Oxygen (wt%)
Pure TiO2 NFs 62.20 0.00 37.80
GQDsTiO2 NFs 60.80 2.94 36.26
Fig. 6. SEM images of (a) Pure TiO2 NFs and (b) GQDs decorated TiO2 NFs.
TiO2 NFs which means that they can work in unison to effectively
inuence the conduction of charge carriers through them.
Fig. 5 shows the EDS spectrum of pure TiO2 NFs and GQDs
decorated TiO2 NFs. It is used to conrm the weight percentage of
various elemental composition of pure TiO2 NFs and GQDs deco-
rated TiO2 NFs as summarized in Table 1. It is observed that the
amount of GQDs decorated onto TiO2 NFs is
3 wt% within
10 min, which is an effective method to improve the performance
of the DSSC without the need of going for doping of GQDs onto
TiO2 NFs that can hamper the actual structure of TiO2 NFs and
sometimes lead to introduction of defects, thereby inducing elec-
tronhole recombination.
SEM micrographs suggest that there is no change in the mor-
phology of TiO2 NFs with the decoration of GQDs is shown in
Fig. 6. Both these NFs have an average diameter of
83 nm. The
presence of GQDs onto TiO2 NFs is not seen because of the low
phase contrast as well as the concentration in the matrix. To
analyze further the microstructure of GQDs decorated TiO2 NFs,
the FE-TEM is used. Fig. 7(a) shows the typical FE-TEM image of

15 nm is uniformly decorated onto TiO2 NFs. The TiO2 NFs
morphology remains unchanged with the decoration of GQDs. The
interface between anatase TiO2 and GQDs can be observed from
the FE-TEM. The selected area electron diffraction (SAED) pattern
of GQDs decorated TiO2 NFs is shown Fig. 7(b). The rst four rings
are assigned to the (101), (004), (200) and (005) conrms the
anatase TiO2 phase. The SAED studies has good agreement with
the XRD measurements Fig. 7(c). The TEMEDX pattern of GQDs
decorated TiO2 NFs is shown in Fig. 7(d). It further conrms the
amount of GQDs onto TiO2 NFs.
Fig. 8 shows UVvis absorption spectra of pure TiO2 NFs and
GQDs decorated TiO2 NFs on adsorption of N719 dye. The pure
TiO2 NFs and GQDs decorated TiO2 pastes are prepared and used to
prepare photoanodes. The pastes are prepared by the following
method, which help to maintain a proper density of two nanos-
tructures for effective comparison. Both the pure TiO2 NFs and
GQDs decorated TiO2 NFs (0.15 g each) are mixed separately with
PVP and then stirred vigorously for 15 min followed by the addi-
tion of 2 mL ethanol and 0.3 mL acetyl acetone to avoid aggrega-
tion. Subsequently, 0.2 mL acetic acid is added. Finally 4-octyl
phenol polyethoxylate (Triton X-100) is added as a dispensing
agent followed by 1 mL ethanol. PVP is used to increase the visc-
osity and adhesion property of the paste and easily decomposed at
450 C during sintering. The pastes are coated separately with a
constant thickness of
15 m on FTO glass plates by the doctor
 Z. Salam et al. / Solar Energy Materials & Solar Cells 143 (2015) 250259
Fig. 7. TEM images of GQDs decorated TiO2 NFs; (a) Bright eld image; (b) High resolution image; (c) SAED pattern and (d) TEMEDX image.
Fig. 8. UVvis spectra of pure TiO2 NFs and GQDs decorated TiO2 NFs lm after dye
(N719) dipping.
blade technique using adhesive tape as a frame and spacer [15].
The active area of the cell is found to be 0.2 cm2. Hence, the
density of nanostructures have been controlled uniformly in both
pure TiO2 NFs and GQDs decorated TiO2 coated glass substrates.
They are kept in air for 1 h and placed in mufe furnace for 30 min
at 450 C. The glass substrates with pure TiO2 NFs and GQDs
decorated TiO2 NFs are placed separately in N719 dye bath for
24 h. The excess dye is removed by rinsing the surface of each
glass substrate with ethanol. UVvis spectral studies are per-
formed in solid mode rather than NaOH/ethanol solution method
due to the leaching of GQDs when ethanol is used, to check the dye
uptake for pure TiO2 NFs and GQDs decorated TiO2 NFs. It is seen
that the amount of dye adsorbed by GQDs decorated TiO2 NFs is
more than for Pure TiO2 NFs, is due to the increase in the
255
Fig. 9. PL spectra of pure TiO2 NFs and GQDs decorated TiO2 NFs lm after N719
dye dipping.
roughness factor and amorphous nature of GQDsTiO2 NFs than
pure TiO2 NFs. A bathochromic shift [26] in adsorption band of
about 15 nm is observed in the absorption edge of GQDs decorated
TiO2 NFs with respect to the pure TiO2 NFs due to the enhanced
donor (dye molecules) semi acceptor interactions
(photoanode-TiO2 NFs) by the incorporation of auxiliary electron
acceptor (GQDs), and also the increase in the surface stress asso-
ciated with surface state energy of TiO2 NFs.
Fig. 9 shows the PL spectra of pure TiO2 and GQDs decorated
TiO2 NFs. It can be seen that the PL peaked around a region of
375 nm for both TiO2 NFs and GQDs decorated TiO2 NFs. However,
the quantum yield for GQDs decorated TiO2 NFs region got
reduced as compaired to pure TiO2 NFs. It is seen that the PL
intensity for GQDs decorated TiO2 NFs is quenched by
43% with
respect to pure TiO2 NFs suggesting a high charge extraction due
256 Z. Salam et al. / Solar Energy Materials & Solar Cells 143 (2015) 250259

to the decoration of GQDs onto TiO2 NFs [27], which allows NFs photoanode based DSSC as compared to GQDs decorated TiO2
maximum number of photoelectrons from N719 dye to reach the NFs based DSSC where the transfer of electrons is so quick that the
conductance band (CB) of TiO2 NFs, as the threshold ionization electrons do not get the time to go to the deep state, thereby
potential of GQDs is
5.3 eV (below vacuum level). It matches reducing the recombination of photoelectrons with the oxidized
well with the band levels of TiO2 NFs and the reduction potential dye (D ) or the oxidized component of the electrolyte (I3  ) [30].
of I3  /I  [28]. This TiO2 NFs provide less resistance to ow of The Jsc starts to fall when the switch is turned off and it is seen
charges due to presence of less grain boundaries between them as that there is a slow decay associated with electron detrapping for
compaired to TiO2 NPs and the presence of an extra electron pure TiO2 NFs in comparison to GQDs decorated TiO2 NFs, because
transport medium further facilitates the improvement in this a lot of electrons in case of pure TiO2 NFs are present in the deep
extraction. To verify the improvement in charge extraction tran- surface state which are hard to be extracted as shown in the inset
sient photoluminescence decay for the DSSC made of the pure of the Fig. 11. The mechanism need to be further investigated by
TiO2 NFs and GQDs decorated TiO2 NFs samples are recorded and theoretical studies. Here, it is believed that the presence of GQDs
the curves are well tted using a bi-exponential function, where provides a highly conductive medium for electrons to travel easily
the relationship with fast and slow time constant is given by Eq. from dye to TiO2 NFs photoanode as also veried by the TRPL
(1): studies (Fig. 10), thereby reducing the back recombination and
improving the Jsc of the DSSC.
t t
R (t ) = A1 exp + A2 exp The Nyquist plots for DSSC fabricated using pure TiO2 NFs and
1 2 (1) GQDs decorated TiO2 NFs as photoanodes are shown in Fig. 12 and
their corresponding impedance parameter values are given in
Where, 1 and 2 are the time constants of the fast and slow
Table 2. The Nyquist plots consist of two semicircles, which cor-
radiative decay, respectively. Similarly, A1 and A2 are the constants
respond to the charge transport resistance of counter electrode/
which determine the contributions of the fast and slow decay
electrolyte (Rct1) at higher frequency and the electrical contacts
components, respectively. The life time parameters upon excita-
between FTO/TiO2 NFs or among TiO2 NFs. The larger semicircles
tion at 530 nm are summarized in Table 5. It is seen that the
at lower frequency corresponds to charge transfer resistance of
electron extraction in case of GQDs decorated TiO2 NFs (125.4 ps)
GQDsTiO2 NFs/dye/electrolyte interface (Rct2) and the Warburg
was much faster than for pure TiO2 NFs (350.7 ps).
diffusion process of I  /I3- redox couple in electrolyte (Zw) at open
To further verify the effect of GQDs decoration on the e  /h
circuit voltage under dark condition [3133]. Though Zw is vir-
recombination rate and enhancement in electron transport, the
tually overlapped by Rct2 and cannot be seen in the plot. The
transient photocurrent analysis of DSSC fabricated using GQDs
identical semicircles at higher frequency suggest that the decora-
decorated TiO2 NFs based photoanode was performed. Fig. 11,
tion of GQDs onto TiO2 NFs does not affect the charge transfer at
shows the rise and fall of Jsc during several onoff cycles upon
illumination at 100 mW cm  2. It is observed that the rise time for
GQDs decorated TiO2 NFs based DSSC was much faster than pure
TiO2 NFs based DSSC. There exist two states on TiO2 lm namely
shallow surface state and the deep surface state were the
traping and detraping of photo-generated electrons takes place
[29]. The shallow surface state lies closer to the CB of TiO2 and the
electrons from this surface state are released constantly and
retrapped into deep surface state. The deep states lie in the
middle of the bandgap of TiO2 and the transfer of photoelectrons
from this state to the CB of TiO2 photoanode is much slower than
the transfer of the photoelectrons trapped in shallow surface state.
During irradiation, the shallow surface states are lled rst by the
electrons, and then these trapped electrons move progressively
down to the deep surface state. A large portion of photoelectrons
get trapped in these deep states and are not able to reach TiO2
photoanode which is a cause of this slow rise of Jsc for pure TiO2 Fig. 11. Transient photocurrent curves of DSSCs based on dye adsorbed pure TiO2
NFs and GQDs decorated TiO2 NFs as photoanodes.

Fig. 10. TRPL spectra of pure TiO2 NFs and GQDs decorated TiO2 NFs based DSSCs Fig. 12. Nyquist Plots of DSSCs based on dye adsorbed pure TiO2 NFs and GQDs
tted using bi-exponential equation. decorated TiO2 NFs as photo anodes.
 Z. Salam et al. / Solar Energy Materials & Solar Cells 143 (2015) 250259 257

Table 2 counter electrode/electrolyte interface. The change in Rct2 value is

Impedance parameter values of DSSCs fabricated using pure TiO2 NFs and GQDs in accordance with the results of TRPL (Fig. 10) and PL (Fig. 9) of
decorated TiO2 NFs as photoanodes.
GQDs decorated TiO2 NFs with respect to pure TiO2 NFs. The
Photoanode Rs Rct1 ( cm  2) Rct2 ( cm  2) presence of GQDs provides an easy and fast transport medium to
charge carriers, which led to a decrease of
21.25% in Rct2 value.
DSSC with pure TiO2 NFs 14.41 7.07 24.28 The current densityvoltage (JV) characteristics of the DSSC
DSSC with GQDsTiO2 NFs 14.01 6.97 19.12
fabricated using pure TiO2 NFs and GQDs decorated TiO2 NFs as
photoanodes are shown in Fig. 13 and their corresponding cell
parameter values are summarized in Table 3. The incident photon-
to-electron conversion efciency (IPCE) as a function of incident
wavelength for DSSCs is also recorded in the wavelength range
from 300 to 800 nm and is shown in Fig. 14. The GQDs decorated
TiO2 NFs photoanode based DSSCs showed an improvement of

10% in the incident photon to electron efciency (IPCE 80%) in
comparison to pure TiO2 NFs (IPCE
70%). The IPCE spectrum data
for the DSSCs based on GQDs decorated TiO2 NFs is in good
agreement with their absorption spectra (Fig. 8) and the value of
Jsc for the DSSCs obtained from JV measurements (Fig. 13). The
DSSC fabricated using GQDs decorated TiO2 NFs showed an
improved power conversion efciency (PCE) of 29.31% ( 6.22%)
with respect to the DSSC fabricated using pure TiO2 NFs
( 4.81%). It is much higher than GQDs/graphene decorated TiO2
NPs based reported systems (Table 4). The current density (Jsc) of
Fig. 13. Photocurrent densityvoltage characteristics of DSSCs based on dye
11.72 mA/cm2, open-circuit voltage (Voc) of 0.68 V and an ef-
adsorbed pure TiO2 NFs and GQDs decorated TiO2 NFs as photoanodes. ciency () of 6.22% with a ll factor (FF) of 78 is obtained for DSSC
fabricated using GQDs decorated TiO2 NFs as photoanode. The high
Table 3 efciency of the cell is due to the following factors; (i) Highly
Photovoltaic parameter values of DSSCs fabricated using pure TiO2 NFs and GQDs porous nature of TiO2 NFs with the addition of GQDs increased the
decorated TiO2 NFs as photoanodes. roughness factor thereby allowing more dye molecules to get
adsorbed leading to generation of more number of photoelectrons
Photoanode Jsc (mA cm  2) Voc (V) FF (%)
which increase the value of Jsc of the cell as veried by IPCE stu-
Pure TiO2 NFs 10.30 0.64 73 4.81 dies; (ii) faster transport of photo generated electrons from dye to
GQDsTiO2 NFs 11.72 0.68 78 6.22 CB of TiO2 due to presence of GQDs onto TiO2 NFs as shown by the
PL and TRPL studies; (iii) Reduction in back carrier recombination's
due to the highly conductive nature of GQDs onto TiO2 NFs which
does not allow the photo generated electrons to go into deep state
as veried by transient photocurrent and impedance studies. So
overall all the above factors contributed to increase in both the Jsc
and FF of the cell and thereby PCE of the DSSC gets improved.
To know about the reliability of the fabricated device, stability
test is performed for both DSSC fabricated with GQDs decorated
TiO2 NFs and pure TiO2 NFs as photoanodes. The JV curves of the
DSSCs employing afore mentioned photoanodes is recorded over a

Table 5
Parameters of the transient absorption data obtained by using bi exponential
equation.

Photoanode A1 1 (ps) A2

Pure TiO2 NFs 0.568 350.7 0.394

Fig. 14. IPCE Spectra of DSSCs based on dye sensitized pure TiO2 NFs and GQDs
GQDsTiO2 NFs 0.398 125.4 0.308
decorated TiO2 NFs as photo anodes.

Table 4
Comparison for the photovoltaic performances of DSSCs fabricated using Graphene quantum dots (GQDs)/Graphene (G)/Graphene oxide (GO) decorated TiO2 nanoparticles
(NPs)/TiO2 nanobers (NFs) based photoanodes.

Photoanode Method of photoanode synthesis Voc (V) Jsc (mA cm  2) FF (%) Improvement in PCE (%) Ref.

Ref. cell Final cell

GTiO2 NFs Electrospinning method 0.71 16.20 66 6.30 7.60 20.63 [5]
GQDsTiO2 NPs Spin coated method 0.77 15.20 75 7.28 7.95 9.20 [13]
GQDsTiO2 NPs Dip coating method 0.66 14.07 59 5.10 6.10 19.60 [14]
GOTiO2 NPs Dispersion of GO in TiO2 0.72 13.00 63 5.34 5.95 11.40 [36]
GTiO2 NS Hydrothermal method 0.60 16.80 57 4.61 5.77 25.16 [37]
GTiO2 NPs Dip coating method 0.68 13.35 65 5.46 7.02 28.57 [38]
GQDsTiO2 NFs Electrospinning & electrophoretic deposition 0.68 11.72 78 4.81 6.22 29.31 Present study
258 Z. Salam et al. / Solar Energy Materials & Solar Cells 143 (2015) 250259
Fig. 15. Normalized light-to electricity conversion efciency characteristics of
DSSCs based on dye sensitized pure TiO2 NFs and GQDs decorated TiO2 NFs as
photoanodes.
period of 30 days (720 h). The variations in light to electricity
conversion efciency of the two DSSCs are shown in Fig. 15. The
cell efciency is recorded after an equal time interval of 48 h for a
span of 30 days storing the device in the dark at 30 C. The nor-
malized efciency of the DSSC containing the pure TiO2 NFs as
photoanode decreased gradually and retained
96% of its initial
value after 30 days, whereas the DSSC based on the GQDs deco-
rated TiO2 NFs photoanode was seen to retain a
99% of its initial
value. This slight variation occurred due to the further inltration
of electrolyte into highly porous TiO2 NFs. The reason being that
the GQDs offers a unique electron dynamics like long hot electron
lifetimes upto hundreds of picoseconds [34], and ultrafast hot
electron extraction from the GQDs to TiO2 interface within o15 fs
[35] which does not allow the hot electron to combine with the
oxidized dye molecules (D ) or the electrolyte (I3  ). So the pos-
sible reason of retaining this high efciency is the reduction in the
charge recombination which has led to the increase in overall
stability of the cell, but the mechanism for the same need to be
studied further in detail. This slight variation in the efciency
indirectly means that the attachment of these synthesized GQDs
over TiO2 NFs remains intact without any kind of detachment as
that would have led to tremendous fall of efciency over this time
period.
4. Conclusions
GQDs were synthesized effectively with an average size of

15 nm by a top down approach using CNFs as a precursor. The
XRD and Raman results suggested a strong interaction or attach-
ment of these GQDs on TiO2 NFs without affecting the integrity of
TiO2 NFs. The UVVis spectral analysis suggested an improvement
in dye uptake meaning more electrons will be photogenerated
thereby inuencing the Jsc of the cell. The PL and TRPL spectral
studies suggested that due to presence of GQDs in conjugation
with 1D TiO2 NFs, a fast transfer of photogenerated electron scan
occurs. Incident photon to current conversion efciency is seen to
improve by
10%, in the wavelength range from 370 to 800 nm
meaning an effective utilization of visible light which can be
achieved by the decoration of GQDs onto TiO2 NFs. The Impedance
spectroscopy suggested a decrease in the charge transfer resis-
tance between TiO2 NFs/dye/electrolyte (Rct2) of 21.25% with the
decoration of GQDs onto TiO2 NFs inuencing the better transfer of
photogenerated electrons to the TiO2 NFs which was also con-
rmed using transient photocurrent study, thereby reducing the
charge recombination. Finally the DSSC fabricated using GQDs
decorated electrospun TiO2 NFs showed an improved PCE of
29.31% ( 6.22%) with respect to the DSSC fabricated using pure
TiO2 NFs, better stability making it practically realizable as a better
photoanode for future use.
Acknowledgments
One of the authors, Dr. A.S. gratefully acknowledge the Pondi-
cherry University for providing the nancial support under Start-
up Research Grant (Ref.PU/PC/Start-up/No. 19/2011-12) and the CIF
of Pondicherry University for extending the instrumentation
facilities.
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