Journal of Alloys and Compounds 793 (2019) 400e409

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Hydrothermally synthesized self-assembled multi-dimensional TiO2/

Graphene oxide composites with efficient charge transfer kinetics
fabricated as novel photoanode for dye sensitized solar cell
V.S Manikandan*, A.K. Palai, S. Mohanty, S.K. Nayak
Laboratory for Advanced Research in Polymeric Materials, Central Institute of Plastic Engineering & Technology, Bhubaneswar, Odisha 751 024, India

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

Article history: The proposed work suggests the fabrication of hybrid TiO2/reduced graphene oxide composites with self-
Received 10 January 2019 assembled multidimensional structure. The two step facile alkaline hydrothermal route is implemented
Received in revised form using variable wt% of GO for the successful synthesis of multidimensional reduced graphene oxide TiO2
29 March 2019
composites structure (MGTS). In the first step, TiO2 aggregates (TNA) were prepared by low temperature
Accepted 3 April 2019
hydrothermal process. Subsequently, growth of multidimensional TiO2 on hGO sheet, as well as simul-
Available online 13 April 2019
taneous reduction of GO is done and the as prepared MGTS is applied for dye sensitized solar cell (DSSC).
Structural and surface morphology of the developed samples were investigated by X-ray diffraction
Keywords:
Multidimensional reduced graphene oxide
(XRD) and field emission scanning electron microscopy (FESEM) techniques. The X-ray photoelectron
TiO2 composites structure (MGTS) spectroscopy studies monitored the chemical composition and surface binding energy of TNA and MGTS
Hydrothermal route samples. The current-voltage (J-V) and electrochemical impedance studies evaluates the performance of
TNA (TiO2 aggregates) the TNA and MGTSs photoanodes in DSSC. The finest loading of GO in the TiO2 matrix assisted the
Hierarchical structure accelerated electron transport channel within the TiO2 matrix resulting in superior photo conversion
Dye sensitized solar cell efficiency of 8.62% as compared with neat TiO2 which has an efficiency of 6.3%.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction DSSC. The nanocrystalline spherical particle has relatively lower

Dye-sensitized solar cell (DSSC) draws extensive attention
owing to their cost effectiveness and reliable power conversion
efficiency in comparison with traditional silicon based solar cells
from the last two decades [1]. DSSC is comprised of wide band
semiconductor based photoanode, redox couple electrolyte and Pt
based photocathode. The up-to-date exploration in this arena
revealed an achievement of about 14.3% photo-conversion effi-
ciency with the mesoporous TiO2 film encompassed with mono-
layer of co-photosensitizer as a photo-anode [2]. However, the
attained power conversion efficiency does not meet up with the
commercialized silicon based solar cells; since DSSC with photo-
anode have undesirable processes such as back charge carrier
transfer between the interfacial components [3]. Therefore, a
plethora of efforts have been commenced on semiconductor film
(wide band gap of nanocrystalline TiO2 particle) and also the
photosensitizer to boost up the power conversion efficiency of the
* Corresponding author.
E-mail address: manikandasiva88@gmail.com (V.S Manikandan).
probability of producing the internal electric field (poor light
scattering ability) within TiO2 film resulting in reduced short circuit
current density [4,5]. Consequently, the short circuit current can be
enhanced by either modifying the surface morphology or
substituting metals such as (TiO2eZnO and TiO2eSnO2) Mg, F, Zr,
Co, Fe with TiO2 for TiO2 nanocomposites [6e11]. In addition,
improving the charge injection efficiency and electron trans-
portation are inevitable properties for a better photoanode in DSSC.
Thus, TiO2 matrix in combination with a thin conducting layer
which can reduce reversible charge carrier loss and can improve
rapid charge separation is utilized as photoanode. In this respect,
the carbon allotropes mainly graphene oxide (GO) or reduced
graphene oxide (rGO) are receiving huge research interest [12].
Moreover, the excellent electronic properties of graphene with a
Fermi velocity of 106 ms
1, layer structured carbon atom with sp2
hybridisation and specific contact resistivity 3.3  10
6 U cm2 are
extensively utilized as functional materials in a numerous fields
such as energy storage, energy conversion and in electronic devices
too [13]. Furthermore, the reduced graphene oxide has an excellent
electrical conductivity (200,000 cm2/V s) at ambient temperature.

https://doi.org/10.1016/j.jallcom.2019.04.050
0925-8388/© 2019 Elsevier B.V. All rights reserved.
 V.S Manikandan et al. / Journal of Alloys and Compounds 793 (2019) 400e409
On the other hand, the four outer orbital electrons of rGO creates
three sigma bonds at an angle of 120 in the identical plane permits
the fourth electron to move freely, like realistic particles without
altering the crystal mismatch or lattice distortion, which comple-
ments the improved charge separation in DSSC [14,15]. In addition,
the incorporation of rGO into TiO2 matrix can enhance the specific
surface area which assists in dye loading onto TiO2 surface that
eventually intensifies the charge collection (number of photo
induced electron) [16]. Nonetheless, conduction band of the
anatase TiO2 is higher than the Fermi level of graphene that could
meant for the effective electron transfer from TiO2 to graphene
resulting in the improved charge transport efficiency [17]. TiO2-
graphene hierarchical sphere on Ti thread based fiber shaped DSSC
fabricated by Zhen et al. probed for remarkable enhancement in the
photoconversion efficiency [18]. Hence, composites of reduced
graphene oxide (rGO) and TiO2 has a ballistic charge transport as
well as inhibition of high intrinsic electron recombination due to
the excited electron transfer from the conduction band of TiO2 to
thin conducting layer of graphene, subsequently increased the
charge separation. The downside in the fabrication of graphene
oxide-TiO2 composite is the non-homogeneity generated from the
particle aggregation persisting after the ultrasonic treatment im-
pedes the device performance. Hence, techniques such as sol-
vothermal, electro spinning and hydrothermal techniques to
synthesize nano or micro Graphene-TiO2 3D hierarchical structures
are being scrutinized [19]. Among them, several research interests
have been concentrated on self-assembled hydrothermal process
for applications such as batteries, super capacitor etc. Menghua
et al. have investigated the photo electrochemical properties of the
TiO2-GO hybrid nanostructure by using hydrothermal method [20].
Maradi et al. have achieved higher efficiency with the randomly
aligned inclined TiO2 nanorod on the zero-dimensional particles
[21]. Recently, Wang et al. reported the higher short circuit current
and open circuit voltage with TiO2-graphene oxide composite
structure [22]. Wang et al. mends the removal of organic dye from
water with TiO2/graphene oxide composite which was designed in
a flower like structure [23].
The present work deploys facile two step hydrothermal process
for the fabrication of TiO2- hGO nanocomposites with self-
assembled multidimensional structure. Initially, TiO2 aggregates
(TNA) are produced by low temperature hydrothermal route with
cetyl trimethyl ammonium bromide as a shape factor. Subse-
quently, graphene based multidimensional TiO2 hierarchical com-
posite structure (MGTS) were prepared by facile hydrothermal
method. Afterwards, TiO2 aggregates were grown on the hGO
sheets under hydrothermal condition. The growth mechanism via
electron microscopic probing has also been proposed for the
fabricated TiO2 aggregates and TiO2-rGO flowered structure. The
MGTS based photoanode fabricated for DSSC was examined for
power conversion and a comparison with the bare TiO2 aggregates
(TNA) photoanode was explored.
2. Experimental section
2.1. Materials and reagents
Commercial TiO2 (P25) nanoparticles, graphite flakes, were
purchased from M/s Sigma Aldrich, India. Anhydrous Lithium Io-
dide (LiI) and Iodine (I2) was provided by M/s Thermo Fisher sci-
entific, India. Cetyl trimethyl ammonium bromides (CTAB) were
purchased from M/s TCI chemicals, India. Di-
tetrabutylammoniumcis-bis (isothiocyanato) bis (2,20 -bipyridyl-
4,40 - dicarboxylato) ruthenium(II) N719 dye was procured from M/s
Greatcell Solar Australia Pvt Ltd. Common chemical reagents such
401
as sodium hydroxide (NaOH) (99%), Hydrochloric acid (HCl) were
obtained from M/s Himedia, India and FTO glass substrate (Rsh<
15 U) was supplied by M/s Shilpa Enterprises, India.
2.2. Synthesis of TNA
TNA was prepared by using 1.5 g of P25 nanoparticles which was
well dispersed in 30 mL millipore water, sonicated and then the
solution was allowed to stir for 30 min. Then, 2 g of CTAB was added
to above solution and further stirred for a period of 1 h. The mixed
colloidal solution was then transferred to 100 mL autoclave and
sealed well for maintaining the pressure at 120  C for 6 h in electric
oven. Subsequently, the autoclave was kept for cooling to the
ambient temperature. The sediments of solid products were
centrifuged and washed a number of times with water, ethanol and
acetone. Finally, the prepared sample was dried in an oven at 60  C
for 1hr and then annealing has been done at 450  C for 30 min at
the rate of 5  C in a tubular furnace.
2.3. Synthesis of MGTS nanostructure
Graphene oxide is prepared according to the method adopted in
the previous article [24]. Facile hydrothermal method was chosen
for the synthesis of graphene composite; multidimensional TiO2-
hGO hierarchical structure (MGTS). Different weight ratio of GO
powder was added to TiO2. Firstly, a minuscule amount of GO
powder was dispersed in 30 mL distilled water which was soni-
cated to obtain clear solution. Then, the prepared TNA was added
slowly to the above suspension and was stirred continuously for 1 h
to ensure complete mixing of TiO2/GO. 10 g of NaOH was added to
the above-mixed solution, which was then transferred to 100 mL
Teflon-lined autoclave. The autoclave was upheld at 180  C for 24 h
followed by natural cooling, resulting in a grey coloured gel. The
obtained gel was washed with 0.1 M HCl and agitated continuously
for overnight. Finally, the greyish coloured gel precipitate was
washed and centrifuged with DI water and ethanol. Subsequently,
drying the precipitate at 80  C removes the solvent and finally
annealed at 300  C for 60 min. The preparation of reduced gra-
phene oxide follows a similar procedure without the addition of
TiO2 for obtaining the product named as hGO (hydrothermally
reduced graphene oxide). The prepared TiO2 composite samples
were labelled as MGTS-1, MGTS-2 and MGTS-3 (0.25, 0.5, 1.0 mg of
GO powder).
2.3.1. Fabrication of DSSC
The TiO2 and TiO2/hGO thin film on fluorine-doped tin oxide
(FTO) glass substrate were fabricated by screen printing method.
About 0.1 g of TiO2 nanoparticles was dissolved in 30 mL ethanol
solution under stirring for 1 h in order to attain proper dispersion.
Then, 3 g terpineol, 0.5 g of ethyl cellulose, 0.3 mL of acetic acid and
0.5 mL distilled water were added to the above suspension. After,
that mixed solution was stirred continuously for 6 h to obtain semi
viscous colloidal paste. It is kept for the evaporation of solvent in an
electric oven. The FTO glass (sheet resistance of Rsh < 15 U/cm2) was
sonicated individually in acetone, ethanol and distilled water for
15 min to eliminate the remnants of any contaminant from the
substrate. Then the colloidal paste was screen printed on the pre-
cleaned FTO and the process was repeated for 10 times to main-
tain the optimum thickness. Finally, TiO2 film was calcined at 450  C
for 30 min at a ramp rate of 5  C, cooled to 80  C and was finally
dipped in 0.3 mM N-719 dye/ethanol solution for 24 h at room
temperature. The sensitized electrode was finally rinsed with
ethanol to remove the unadsorbed dye molecules. Platinum
counter electrode was developed by using chloroplatinic acid drop-
casted on FTO glass followed by sintering at 350  C for 30 min. Then
402 V.S Manikandan et al. / Journal of Alloys and Compounds 793 (2019) 400e409

both the electrodes were sandwiched together with a binder clip 3. Results and discussion
for further studies.
3.1. Structural and morphological properties
2.3.2. Characterization and measurement
Fig. 1 shows that flow chart for the preparation of TNA and hGO-
X-ray diffraction (XRD), Field Emission Scanning Electron Mi-
TNA nanocomposites. Fig. 2(A) represents the XRD pattern of
croscopy (FESEM), Raman spectroscopy (RAMAN), X-ray photo-
graphite, GO, hGO, and Fig. 2(B) for TNA, MGTS-1, MGTS-2, MGTS-3
electron spectroscopy (XPS), UV-VIS absorption spectroscopy (UV)
respectively. It can be seen in Fig. 2(A) (top), the appearance of
and Photoluminescence spectroscopy (PL) are employed to reveal
strong diffraction peaks at 2q ¼ 21.6 . In the case of GO, the existing
the TiO2 aggregates and multidimensional TiO2@graphene com-
small and broad peaks were moved to a lower angle at 2q ¼ 10.6 as
posites structure. XRD studies were conducted on an X-ray powder
shown in Fig. 2(A) (middle). This indicates the fact that the oxygen-
diffraction instrument with (Shimadzu, Japan using CuKa radiation,
containing functional group are binded with each side of the
l ¼ 1.54 Å) 2q range value from 10 to 90 at a scan rate of 2 s
1.
graphite flakes which contributes defects (sp3 bonding) in the
Microscopical images were probed by Field emission electron mi-
graphite structure. The appearance of broad peak with higher angle
croscope (TESCAN, MIRA3) functioning at acceleration potential of
of 2q ¼ 24.5 in Fig. 2(A) (bottom) corresponds to the (002) plane in
3 kV. HRTEM image and SAED patterns were performed on a Jeol/
the hGO diffractgram confirms the exfoliation of GO the hydro-
JEM 2100 electron microscopy operating at an acceleration poten-
thermal condition [25,26]. The XRD pattern [Fig. 2(B) (a)] of the
tial of 200 kV. Raman spectra were carried out on a confocal Raman
pure TNA aggregate exhibits the typical (101), (004), (200), (105),
microscope (WI Tec GmbH Alpha 300 RA AFM & RAMAN) using
(211), (204), (116), (220), and (215) reflection revealed the distinct
532 nm around 70 mW. X-ray photoelectron spectroscope was
anatase phase of TiO2 (JCPDS PDF: 00-021-1272). It was confirmed
done by using AXIS-NOVA C109 spectroscopy system for deter-
that after the hydrothermal process rutile phase totally vanished
mining the elemental composition and surface interaction of the as
with respect to P25 nanoparticles shown in inset Fig. 2(B). Further,
synthesized product. The absorption analysis of the material was
anatase phase is highly stable compared to the all three phases such
measured at room temperature by using UVeVis absorption spec-
as rutile and brookite. Moreover, the anatase phases are favoured
trometer (Shimadzu-2450). The dye loading was measured by
for the solar cell. However, similar information can also be observed
immersing dye loaded film in 0.1 M NaOH solution containing
for MGTS [Fig. 2(B) (b-d)] nanocomposites. The distinctive peaks of
ethanol by UVevisible spectrometer. Photoluminescence (PL)
hGO cannot be isolated from the diffraction pattern of MGTS-1,
spectroscopy was performed with spectroflurophotometer (Shi-
MGTS-2, MGTS-3 due to low amount of GO and the proximity of
madzu RF-5000). Electrical conductivity of TiO2 and composite
anatase (101) at 25.1.
sample were determined by using keithley source meter (model-no
The crystalline phase of TNA and MGTS-2 has also been vali-
6517 B).
dated from Raman spectra shown in Fig. 3(a) and (b) respectively.
The Photocurrent-Voltage(I-V) characteristics was carried out by
There are several characteristic modes of vibration at 158 cm
1,
means of a computer controlled electrochemical workstation and
282 cm
1, 450 cm
1 and 634 cm
1 which corresponds to bands Eg1,
SAN-EI solar stimulator, 150 W Xenon lamp was used as light source
B1g(1), A1gþ, B1g(2) and Ag(2) were observed for TNA. This
with AM 1.5 G filter which has an intensity of 100 mW/cm2. The
behaviour confirms the existence of all the prominent modes of
active area of the cell used was 0.25 cm2. Electrochemical imped-
vibration in pure anatase TiO2. However, there is no rutile vibration
ance spectra studies were carryout in electrochemical workstation
mode is possible due the hydrothermal treatment which is
(ZIVE- SP2).

Fig. 1. Flow chart of for preparation of TNA and hGO/TNA nanocomposites.

 V.S Manikandan et al. / Journal of Alloys and Compounds 793 (2019) 400e409
Fig. 2. XRD Pattern of (A) Graphite, GO, hGO and (B) TNA (a), MGTS-1 (b), MGTS-2 (c), MGTS-3 (d) respectively. XRD pattern of commercial P25 (inset).
Fig. 3. Raman spectra of (a) TNA (b) MGTS-2. (inset) corresponds to the enlarged view
of Raman spectra (a) TNA (b) MGTS-2.
consistent with the XRD results discussed in the earlier sections. In
the case of MGTS-2, the presence of new peaks at 1330 cm
1 and
1572 cm
1 corresponding to the D and G band can be ascribed to
the vibration of hGO in Fig. 3(a) inset. Usually, D bands are exhibited
due to the vibration of optical E2g phonon mode of sp2 carbon
atoms whereas; the G bands are due to the planar vibration mode
of the carbon rings [27]. In addition to it, D bands indicate the local
defects and disorders in the carbon ring. However, the D to G band
(ID/IG) ratio of TiO2-hGO composites structure (MGTS-2) was rela-
tively lower in contrast to the previous reports of GO, suggesting
the reduction of GO during the hydrothermal process which can be
correlated with the XPS and XRD findings.
3.2. Morphology of GO and MGTS nanocomposites
FESEM analysis has been done to characterize the morphology
of the prepared samples; MGTS-1 and MGTS-2. The GO was
reduced to a folded layer of graphene which appeared as a sheet
like structure, depicted in Fig. S1. The TiO2 particles are formed due
to the aggregation of several spherical grains that is clearly
403
noticeable like microsphere or aggregates structure with an
average diameter of 0.12 mme0.2 mm [Fig. 4(a)]. FESEM micrographs
displayed in Fig. 4(b) and (c) were corresponds to MGTS-1 and
MGTS-2 samples respectively. It is distinct that MGTS-1 depicts as a
flower like morphology. Furthermore, presence of densely aligned
tubular structures conceals the surface of hGO that are more
favourable for the electron transport channel in DSSC. On the other
hand, MGTS-2 clearly shows 3D micro flower structure wherein the
micro-flowers are constructed by the self-organization of
numerous thin sheets that can act as structural units contributing
to formation of flower like structure on the surface of hGO sheet
[Fig. 4(c) and (d)]. The cross section images of the MGTS-2 coated
on FTO substrate exposed in Fig. 4(e and f) and the thickness of
coated sample is found to be around 13 mm. To scrutinize the suc-
cessful growth of MTS (multidimensional TiO2 structure) on the
hGO layer TEM analysis has also been performed. The TEM image of
hGO appears a sheet like morphology as shown in Fig. S2, postu-
lates that GO is effectively reduced by hydrothermal treatment that
is consistent with the FESEM and XRD results. Fig. 5(aec) shows the
TEM images of MGTS-2 sample with a tube like morphology,
exhibiting an average inner diameter of 10e12 nm and length of
98 nm, which can be probably due to the mono dispersed TiO2 on
graphene oxide sheet that helps in the in situ growth of TiO2
nanotubes on the surface of hGO sheet in hydrothermal condition
[28]. Interestingly, the observation of spherical particles with
50 nm diameter attached with the tube is clearly shown in Fig. 5(a)
provides the supplementary support for the efficacious dye loading
to influence the light harvesting and light scattering in DSSC. The
high magnification TEM image in Fig. 5(c) indicates that the titania
tubes are connected to the sheet with an individual sheet diameter
of 17 nm. These findings are consistent with the FESEM micro-
graphs given in Fig. 4(f). It can be seen that the GO got reduced and
simultaneously TiO2 hierarchical structure was grown on hGO
surface by hydrothermal condition; TiO2 circumvents GO after the
reduction process without restacking in hGO layer structure. The
HRTEM images MGTS-2 is shown in Fig. S3, show a lattice space of
0.35 nm corresponding to the crystalline plane (101) in the anatase
phase of TiO2. The selected area diffraction pattern of MGTS-2 is
depicted in Fig. 5(d) displays the polycrystalline nature of MGTS-2
which is in concordant with the XRD data. Nonetheless, the
resulted graphene with multidimensional hierarchical structure
composed of tubular and sphere morphology can also induce the
charge collection and charge transport in DSSC which has been
discussed in the forthcoming section.
404 V.S Manikandan et al. / Journal of Alloys and Compounds 793 (2019) 400e409
Fig. 4. FESEM micrographs of (a) TNA (scale bar: 400 nm) and (b) MGTS-1(scale bar: 200 nm), (ced) MGTS-2(scale bar 1 mm and 500 nm respectively) and (eef) MGTS2 cross section
image (scale bar: 10 mm as per scale etc.).
Fig. 5. TEM images of (a) MGTS-2 (scale bar: 50 nm) and HRTEM images (b) and (c)
MGTS2 (scale bar: 10 nm, 5 nm respectively) and (d) selected area diffraction pattern of
MGTS-2.
3.3. XPS analysis
Information about the chemical composition and chemical
environment in the TNA and MGTS-2 structures were analysed by
XPS studies and the outcomes are depicted in Fig. 6. Fig. 6(a) dis-
plays the XPS survey spectra of elements O1s, Ti2p and C1s corre-
sponding to the TNA and MGTS-2 with no impurities. XPS spectra of
MGTS-2 sample displays a peaks at Ti2p, O1s and C1s which
correspond to their binding energies of 497.7 eV, 565.38 eV and
366.37 eV respectively [29]. In C1s spectra of high-resolution
deconvoluted pristine TNA, two peaks were obtained with high
intensity centred at 284.2 eV (CeC bonds) corresponds to the sp3
hybridised carbon. The peak at 286.4 eV is due to the appearance
of oxygen in covalently bonded CeOH linkage is depicted in
Fig. 6(b). Similarly, in C1s spectra hybrid structure of MGTS-2
revealed peaks at 285.1, 287.2 and 288.7 eV in which high intense
peak is related to the CeC sp3 hybridisation and the small signals
were assigned to CeO, CeC and COOH functional moieties
respectively [30]. However, the evidence of p
p* interaction be-
tween the layer of carbon ring at 288e292 eV was also noticed
wherein, the overlapping with the OeC]O region nullifies the
visibility. The peak intensity at 287.2 eV and 288.7 eV was very low
compared to the previously reported C1s spectra of GO implying
the reduction of GO after hydrothermal process which is in good
agreement with XRD and Raman results [31,32]. Meanwhile, in high
resolution Ti2p XPS spectrum of TNA, two peaks centred at 458.2 eV
and 463.7 eV were assigned to the characteristic peaks of Ti 2p3/2
and Ti 2p1/2 spin orbit splitting photo electrons that occurred from
the Ti4þ anatase crystal structure of TiO2 [33]. The deconvoluted
O1s spectra of TiO2 illustrated in Fig. S4 demonstrates two peaks at
529.2 and 531.2 eV indicate the oxygen containing group attached
with Ti4þ and TieOeTi respectively. However, after the incorpora-
tion of GO, primary peak along with new additional peak at
532.5 eV was assigned to CeO group in Fig. S5.
4. Optical characterizations
4.1. UVevisible analysis
The optical properties of TNA, MGTS-1, MGTS-2 and MGTS-3 are
examined through the UVevisible spectra at room temperature and
the same has been depicted in Fig. 7(A). The high intense absorp-
tion was exhibited at 375 nm by the pristine TNA. However, after
the incorporation of hGO into the TiO2 matrix (MGTS-1, MGTS- 2,
MGTS-3), the absorption intensity increased with a small shift to-
wards the visible region in contrast to pristine TNA [Fig. 7(A) (a)].
On the other hand, this visualization favours the utilization of solar
spectrum with the additional continuum for efficacious separation
of photogenarated charge carriers from DSSC. This behaviour
indicated a strong chemical interaction between titanium ions and
oxygen groups (TieOeC) in MGTS based hierarchical structure
[34,35]. The band gap energy of MGTS was found to be reduced
with respect to pure TNA, which was evaluated by using Tauc plots
depicted in Fig. 7(B). The narrowed band gap also indicates the
charge carrier transfer of MTS to GO (multidimensional TiO2 hier-
archical structure) from MGTS hierarchical structure [36].
Generally, a PL spectrum is employed to analyse the surface
 V.S Manikandan et al. / Journal of Alloys and Compounds 793 (2019) 400e409 405

Fig. 6. XPS survey spectrum of (a) TNA, MGTS-2 and corresponding high resolution spectra of (b) TNA C1s, (c) MGTS-2 c1s and (d) MGTS-2 Ti2p.

Fig. 7. (A) UV-vis (B) corresponding band gap (Tauc Plots) and (C) PL spectra of of (a) TNA, (b) MGTS-1, (c) MGTS-2, and (d) MGTS-3 respectively.
406 V.S Manikandan et al. / Journal of Alloys and Compounds 793 (2019) 400e409
structure and excited state of the semiconductor. The PL spectrum
of pristine TNA shown in Fig. 7(C) revealed three major character-
istic peaks around 370e470 nm, assigned to self-trapped exciton
which was localized on TiO6 octahedral and the surface oxygen
vacancy respectively [36e38]. There could be no variation in the
peak position of MGTS hierarchical structure; however the
remarkable quenching in peak intensity indicated the transfer of
exited electron from MTS to hGO which can reduce the charge
recombination, effecting in reduced PL intensity. Moreover, in-
creases in the concentration of GO into the titanium matrix further
quenches the PL spectrum in all the MGTS hierarchical structure
which can surplus the charge separation. These results also indi-
cated the strong interaction between hGO and MTS/(TieOeC
bonds) which is consistent with XPS data. Consequently, the MGTS
hierarchical structure errands more for the successful generation of
photoelectron for DSSC application.
4.2. Photovoltaic studies
In Fig. 8, the dye loading capacity of different semiconductor
photoanodes has been represented. The dye loading capacity of
semiconductor photoelectrode is augmented by the absorbance of
sunlight: they can induce charge collection efficiency which can be
beneficial for improved cell performance of DSSC. The absorption
capability of various photoelectrodes in dye immersion has been
displayed in Fig. 8A. It was observed that the absorption of MGTS
photoelectrode in the visible light region enhanced in contrast to
TNA signifies the dye loading capability of MGTS based photo-
electrode for boosting the power conversation of efficiency of DSSC.
To confirm the amount of dye loading, sensitized film was exam-
ined via employing dye desorption studies by immersing the film in
1 mM NaOH solution. As the observed dye loading enhanced with
the incorporation hGO in the MGTS composites on comparison
with the pristine TiO2: consistent with absorption spectra shown in
Fig. 7 (A).
The photovoltaic's performance of as prepared TNA and hier-
archical structure of MGTS was explored to evaluate the impact of
hGO content in hybrid structure fabricated for DSSC. The photo-
current density (J)-voltage (V) measurement was carried out under
one sun light condition. The characteristic I-V for evaluating the
performance of DSSC based on hierarchical MGTS photo anodes has
been depicted in Fig. 8(B) Various critical parameters of DSSC such
as; photo current density (Jsc), open circuit voltage (Voc), fill factor
(ff) and efficiency (h) are listed in Table 1. Photo current density (J) -
voltage (V) of the fabricated MGTS hybrids nanostructured DSSC
Fig. 8. (A) dye absorption of TNA and MGTS based photoanodes (B) current-voltage (JeV) characteristic curves of TNA and MGTS based photoanodes.
Table 1
Photovoltaic parameters of the TNA and MGTS based DSSC.
Photoanode Jsc (mA cm2) Voc (V) FF PCE (%) Rct 2 (Ohm)
TNA 13.3 0.82 0.58 6.32 16
MGTS-1 19.1 0.77 0.52 7.64 14
MGTS-2 20.6 0.79 0.53 8.62 13
MGTS-3 15.3 0.70 0.47 5.10 17
exhibits a power conversion efficiency of 8.62% with Jsc of 20.6 mA/
cm2, Voc of 0.79 mV and FF of 0.53. Further, a lower efficiency of
6.31% with Jsc of 15.3 mA/cm2 was obtained in the case of fabricated
TNA based DSSC device. Above results signifies, that power con-
version efficiency can be improved with the incorporation of hGO,
while the excess amount of hGO reversibly declines the power
conversion. Therefore, adequate quantity of hGO with hierarchical
MTS can enlarge the specific surface area which consequently en-
hances the dye loading capacity of overall MGTS-2 based photo-
anode. However, slight decrease in the Voc mainly depends on the
Fermi level of the TiO2 conduction band and potential of redox
electrolyte.
The photocurrent density, fill factor and open circuit voltage of
MGTS-2 based photoanode was found to be relatively higher than
the other MGTS based photoanodes. This behaviour can ease fast
charge carrier separation to accelerate the electron transport which
can reach the collector electrode in the DSSC during the operation.
Further, the addition of hGO also contribute in an increase in the
light absorption that affects the optical transparency and can act as
a recombination centre to resist the anodic reaction in dye-TiO2
interface. This in turn hampers the charge transport after light
illumination, might be resulting in a decreases in the Jsc from
MGTS-3 photoanode in DSSC devices. Ohsaki' et al. have explored
the electron life time in a nanotube which is three times higher
than that in the nanoparticles system [39,40]. Graphene
sheet along with TiO2 nanotube structure has optimum charge
carrier mobility resulting in enhanced Jsc. Further, higher Jsc value is
not only related to charge collection efficiency by more dye mole-
cules absorption from MGTS based photoanode but it can also
relate to the surface area along with crystallinity and morphology
of the material. In addition, there are some adequate factors which
can influence the enhancement in Jsc from the MGTS based pho-
toanode in the fabricated DSSC. It may be noticed that in case of the
MGTS hierarchical structure there is a microsphere coupled with
GO or hGO sheet along with a well-connected nanotube exhibiting
a multifunctional role; wherein the titania microsphere and sheet
 V.S Manikandan et al. / Journal of Alloys and Compounds 793 (2019) 400e409 407

Fig. 9. (A) EIS spectra and (B) Bode pot of the TNA and MGTS respectively.

models stands for light scattering with superior dye absorbing
capability. Besides the GO sheet, the lower grain boundary of tita-
nium nanotube might have reduced the interfacial resistance that
can assist the electron transport rate during the DSSC operation
thereby resulting in higher Jsc of 20 mA/cm2 [Fig. 8.(b)].
The interfacial reaction kinetics in the DSSC was further
confirmed using the EIS result. The EIS spectra of TNA and MGTS
examined under the AM 1.5 light illuminations are depicted in
Fig. 9A. It can be seen that, all the fabricated DSSC devices revealed
three main semicircles. The first semicircle was attributed the high
frequency region relating to the electrochemical reaction occurred
in platinised counter electrode and the electrolyte interface (charge
transfer resistance Rct 1). The appearance of semicircle in the
middle frequency region is due to the electron transfer resistance
within the TiO2 film and the possible reverse reaction at TiO2/
electrolyte interface. Associated charge transfer in electrolyte
(Nernst diffusion) impacts the lower frequency region which is
evident from the third semicircle [41]. As per the EIS spectra
depicted in Fig. 9A, the diameter of second semicircle in middle
frequency region tends to reduce upon the inclusion of GO which
significantly moderates the electron transport resistance thus
contributing in higher photo current (Jsc) from the MGTS based
devices shown in Fig. 8(a). The electron life time calculated from all
the fabricated DSSC devices based on Bode plot is represented in
Fig. 9B. It could be clearly visible that in the Bode plot of all MGTS
based photoanode fabricated for DSSC, the frequency has been
shifted to higher frequency region. While, the maximum frequency
(f max) at the illumination condition is inversely related to the
electron life time ts ¼ 2 p1f [42]. The increasing order of fmax is
max
In Fig. 10 (a) depicts the electron transfer process in TNA (TiO2
aggregates) with highest light scattering capacity which is able to
generate additional photo electrons. The slower electron transfer
due to the poor interconnectivity enhances the resistance out-
comes in reduced Jsc. However, multidimensional TiO2 balances the
above issue with multiple scattering; holding the electrons within
the system and the tube can deliver electron through the transfer
channel along with the thin layer graphene, electron can easily
reach the current collector [Fig. 10 (b)]. The enhancement of Jsc is
represented in Fig. 10(c) and the corresponding schematic repre-
sentation of DSSC in Fig. 10 (d). Therefore, based on the observa-
tions it is concluded that for the better performance of DSSC,
moderate amount of GO can undoubtedly act as bridge between the
TiO2 and current collector.
The TiO2-hGO composites exhibit highest short circuit current
density (Jsc) of 20.6 mW/cm2, an open circuit voltage (Voc) of 0.79 V
with an overall photo conversion efficiency of 8.62% which is higher
than the recent reported values of TiO2-GO composites tabulated
Table 2. Majority of the literature listed in Table 2 are based on TiO2-
GO photoanode, prepared by mixing and grinding method. Lack of
proper chemical interactions between TieC after thermal annealing
is a limitation for these procedures [31]. This residue in fact acts as
recombination centre which affects the overall cell performance.
Moreover, the morphology of TiO2 particles possess grain boundary

associated with the faster electron transport and the charge carrier
reaching the collector electrode; the device based on GO evidences
the enhanced photocurrent density compared to devices without
GO. Fig. S6 shows I-V characterization of the TNA and MGTS-1
MGTS-2, and MGTS-3 material. There found current values are
increased linearly with increasing the voltage. To measured room
temperature electrical conductivity (sdc) which sdc values are
enhanced with increasing GO in TiO2-GO composites conductivity
of MGTS-1 MGTS-2 corresponding to values 4.02  10
6 S/cm
8.46  10
6 S/cm higher compare to the TNA 2.47  10
7 S/cm due
to the higher conductivity of the graphene virtuous contact with
TiO2 in TiO2-RGO composites [43,44]. In addition, graphene are lead
to the charge carrier mobility when charge carrier in the electronic
vicinity of the graphene islands. There is evident higher current
density of MGTS-2 based photoanode. However more addition to
decrease the sdc it may be due to the higher restacking or affecting Fig. 10. Illustration of the electron transfer photoanode with (a) TNA and (b) MGTS. (c)
conducting path electron lower conductivity 3.47  10
7 S/cm [45]. Jsc of Photoanode with variable hGO content (d) Schematic diagram of MGTS photo-
anode based DSSC.
408 V.S Manikandan et al. / Journal of Alloys and Compounds 793 (2019) 400e409

Table 2
The table of photovoltaic parameters of DSSC in the present and previous reported works in the literature.

S. no Composite material TiO2 Structure Jsc (mA/cm2) Voc (V) Efficiency h % Ref.

1. TiO2 Sphere 13.3 0.82 6.32 Present work

2. MGTS-2 Multidimensional (particles, rod, tube) 20.6 0.79 8.62 Present work
3. TiO2 Spherical particles 13.13 0.70 5.99 Ref. [3]
4. TiO2-graphene composites Spherical 14.68 0.78 7.68 Ref [46]
5. TiO2-Graphene nanoribbon Spherical 14.2 0.724 7.18 Ref [3]
6. TiO2-graphene oxide Particles 19.5 0.68 7.83 Ref [4]
7 TiO2/RGO microsphere 16.75 0.74 7.57 Ref [47]
8 TiO2/Graphene Spherical 14.64 0.66 7.06 Ref [48]
9 Graphene integrated TiO2 Spherical 16.5 0.703 7.5 Ref [49]
10 TiO2/RGO blocking layer Spherical 15.29 0.74 7.48 Ref [50]
11 RGO incorporated TiO2 Particles 15.23 0.71 6.69 Ref [51]
12 Graphene-TiO2 nanostructure Nanorods 10.7 0.78 5.33 Ref [52]
13 Hierarchical structure TiO2-RGO Branched nanorods 13.4 0.69 4.35 Ref [53]

which affects the electron transport. Some literature prepared TiO2
nanorods which are having less surface area for lower dye loading.
Herein we report the synthesis process with two step method for
obtaining TiO2 microspheres and TiO2-GO composites with multi-
dimensional architectures (sphere, tube, and rod attached hGO
sheets) with efficient dye loading and also excellent electron
transportation with efficient charge transfer kinetics. Hence, the
photovoltaic performance is higher than the latest reported values.
The sensible amount of GO with the aforementioned multidimen-
sional attributes of TiO2 accelerates the electron transport effi-
ciency which ultimately adds on the overall DSSC performance on
comparison with the recent literature.
5. Conclusion
The designed multidimensional hierarchical TiO2-hGO com-
posite structure (MGTS) for the dye sensitized solar cell application
is prepared by using two step facile hydrothermal methods. In
addition to it, based on the performance of constructed MGTS based
photoanode in DSSC devices investigated the impact of rGO in MTS
(multidimensional TiO2 structure). The MGTS photoanode seems to
have higher light scattering, enlarged dye loading, faster electron
transport and low back electron reaction consequently aftermath
with higher photo current density. In short, the MGTS-2 based DSSC
device achieves 8.62% power conversion efficiency with a 37%
augmentation compared to the TNA based photoanode DSSC
devices.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jallcom.2019.04.050.
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