Solar Energy Materials and Solar Cells 183 (2018) 211–219

Contents lists available at ScienceDirect

Solar Energy Materials and Solar Cells

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

Exploration of graphene oxide nanoribbons as excellent electron conducting T

network for third generation solar cells
⁎
J. Kusuma, R. Geetha Balakrishna , Siddappa Patil, M.S. Jyothi, H.R. Chandan, R. Shwetharani
Centre for Nano and Material Sciences, Jain Global Campus, Jain University, Kanakapura, Bangalore 562112, Karnataka, India

A R T I C L E I N F O A B S T R A C T

Keywords: The future of third generation Quantum dot sensitized solar cells (QDSSCs) can be optimistic if concerns of
Graphene nanoribbons charge recombination and stability of cells can be worked upon. In this work, we report the role of Graphene
Conducting edges materials in its different dimension in overcoming recombination and enhancing power conversion efficiency
Band gap (PCE). Composite of Graphene oxide nanoribbons (GNRs) synthesized by oxidative unzipping of multi walled
SILAR-QDSSC
carbon nanotubes (MWCNTs) was used as an effective electron transport layer with TiO2 as photo anode in
Carbon nanotubes
1D quasi structure
QDSSCs. The best performing TiO2-GNR showed a significant enhancement in PCE of 3.7% for CdS based
quantum dots, apart from increased efficiency reported earlier. Investigation of design of anode material reveals
that the enhanced surface area and active sites of partially conducting GNRs facilitated uniform deposition of
Titania particles (TiO2) with less aggregation, excellent mobility, presence of organic functional group for anchor
of TiO2, its 1D quasi structure add to enhanced electron transport (less resistance).

1. Introduction for photovoltaic applications [6–8].

Graphene oxide (GO) are two dimensional sheets in morphology,
The third generation quantum dot sensitized solar cells (QDSSCs) possessing less or no conductivity. Rolling these sheets results in one
have drawn a lot of attention over last decade due to their unique dimensional tubes called carbon nanotubes (CNTs), and are well known
properties like tunability of band gap for broad light absorption, mul- for their strong mechanical property, high thermal conductivity and
tiple exciton generation, narrow emission, easy processing, low cost, optoelectronic properties [9]. Moulding sheets into single (metallic or
high efficiency and its use as flexible panels [1,2]. Over this short span semiconducting) or multi-walled tubes (metallic) imparts them dif-
of time, QDSSCs have yielded an efficiency of 11.6% for Zn-Cu-In-Se ferent optical properties [10]. One dimensional strip of these unzipped
quantum dot cells [3] and 13.7% for lead halide quantum dot based CNTs are known as Graphene oxide nanoribbons (GNRs). Unzipping of
perovskites cells [4] which tops the current certified efficiency by CNTs forms ribbons of few nanometers to hundred nanometers in width
NREL. The existing challenges of QDSSCs namely the recombination of with different edge configurations namely arm chair and zig-zag. The
exciton and degradation of counter electrode on long exposure to cor- angle of chirality of carbon atoms at the edges decides the semi-
rosive electrolytes has limited them from commercialization. Although conducting (arm chair) and metallic (zig-zag) property respectively of
TiO2 is one of the promising wide band gap metal oxide semiconductor GNRs [11]. The flat edge states in case of zigzag configuration allows
(because of its photo catalytic activity, stability and favorable energy high density of states to be located at the edges for greater reactivity
alignments) recombination is one major concern as it forms an as- [12] and lateral confinement of charge carriers in ribbons allows them
sembly of colloidal particles with higher grain boundaries that increases to possess band gap, which decreases with increase in the width of
the charge carrier recombination [5]. Incorporation of Graphene ma- ribbons [13]. The exceptional property of tuning GNRs to form a
terials into TiO2 has been an established concept for photocatalytic semiconductor (unlike insulating in GO), can be a very promising
applications. Graphene materials can render unique functionalities on candidate for next-generation semiconductor materials. Since these
incorporating into wide band gap semiconductor like extension of light graphitic structures are finite in dimension compared to infinite GO
absorption, sufficing continuous network for transport of electrons due sheets, they possess edge boundaries which have higher aspect ratio
to their morphology, excellent charge carrier mobility and its ability in [14] and also the three non-coordinated atoms at edges impart excep-
separation of exciton for quick transfer of photo injected electrons to tional properties that control the electric and magnetic properties. Also
overcome recombination. Hence Graphene can be a promising material wrinkling of strips leads to a number of fold lines enhancing electrical

⁎
Corresponding author.
E-mail address: [email protected] (R.G. Balakrishna).

https://doi.org/10.1016/j.solmat.2018.01.039
Received 6 September 2017; Received in revised form 24 January 2018; Accepted 26 January 2018
Available online 06 March 2018
0927-0248/ © 2018 Elsevier B.V. All rights reserved.
J. Kusuma et al. Solar Energy Materials and Solar Cells 183 (2018) 211–219

the diol groups.

Nomenclature

2.3. Synthesis of graphene composites

QDSSCs Quantum dot sensitized solar cells
GNRs Graphene oxide nanoribbons
The composites of TiO2-GNR was prepared by solvothermal method
MWCNTs Multi-walled carbon nanotubes
as described in protocol by Wang et al. [9] with slight modification of
GO Graphene oxide
using di-methyl formamide (DMF) as the solvent, because of better
ETL electron transport layer
dispersion of Graphene. 0.1 g of TiO2 and different wt% of GNRs
(0.04 wt%, 0.08 wt%, 0.12 wt% and 0.16 wt%) were mixed and soni-
cated for 30 min with DMF. The mixture was placed in autoclave and
conductivity in GNRs [14]. These outstanding electronic properties add
was maintained at 180º C for 6 h. The obtained mixture was given water
to the performance wings of electronic devices as an alternative to CNTs
and ethanol wash followed by vacuum drying overnight. The same was
and GO sheets. It has been incorporated in some of the major applica-
followed for other graphene composites.
tions like field effect transistors (FETs), sensors, super capacitors and
energy based devices. To mention few, Liu et al. reported ribbons based
2.4. Fabrication of solar cells
meshes as wearable devices for sensor applications and it showed an
excellent recoverable stability sensitive to different tensile strains [15].
Cells were fabricated according to standard protocol [22]. In brief,
Pachfule et al. investigated its usage in electrochemical storage and
fluorine doped tin oxide (FTO) glass substrates were sequentially
demonstrated an excellent electrochemical capacitive properties in a
cleaned by ultra-sonicating in surfactant, deionized water, and ethanol
steady state as well as in the galvanostatic charge–discharge measure-
for impurity free substrates. Paste of TiO2 was prepared by grinding
ments [16]. Arnold et al. reported direct growth of GNRs onto Ger-
0.25 g of TiO2 with 0.5 ml of acetic acid for 20 min. 1:3 mixture of
manium semiconducting wafer on a large scale for its use in hybrid
deionized water and ethanol were added drop wise in intervals to the
integrated circuits making them feasible for industrial applications.
above paste for better suspension of particles and were further grinded
This not only promises to boost the performance of next-generation
by adding Triton-X (0.5 ml) as binder for 20 min to get a homogenous
electronic devices significantly but it is going to be very useful material
paste and for better adhesion on the substrate. The same was followed
in industrial and military applications, such as sensors and photonic
to prepare the composites. FTO glasses were sintered at 70 ºC in oven
devices which manipulates light [17]. Ghosh et al. reported GNRs
by immersing the electrode in 40 mM solution of TiCl4 for 30 min to get
composite with copper sulphide as counter electrode to boost the per-
a compact layer, as this can enhance the short circuit current [23]. The
formance owing to its electrical conductivity and is the only literature
prepared paste was coated on to the FTO substrate by doctor blade
available for its use in photovoltaic devices [18]. The present paper
technique. The final TiO2 coated films were sintered at 500 ºC for
focuses on study of GNRs and its role in third generation solar cells with
30 min to stabilize the films and as well to remove if any organic im-
comparison to two dimensional GO sheets and one dimensional
purities were present. Sintering brings out better electrical connection
MWCNTs. This work hence gains significance in providing efficient
between nanoparticles. It was then allowed to cool at room tempera-
GNRs as an alternate to CNTs and GO in applications that need quick
ture. Two such layers were coated and the average thickness of the film
electron transport and efficient charge separation.
was roughly around ~9 µm. The sintered FTOs were sensitized by
cadmium sulphide (CdS) QDs by SILAR deposition. 0.1 M aqueous so-
2. Experimental lution of cadmium nitrate (Cd (NO3)2) and sodium sulphide (Na2S) was
used as cationic and anionic source respectively. FTO substrates were
2.1. Materials and methods first dipped in (Cd (NO3)2) solution for three minutes and later in
(Na2S) for 30 s and in between rinsing the electrodes with the distilled
TiCl4 (99.5%) was used as a titanium source for the preparation of water to remove excess or unanchored particles for uniform deposition.
the electron transport layer (ETL) procured from spectrochem and the This completes one SILAR cycle. Eight such SILAR cycles were carried
others include the solvent ethanol, ammonium hydroxide, potassium out to get sensitized electrodes. Later it was passivated with inorganic
nitrate, hydrochloric acid, ether, hydrogen peroxide, sulphuric acid, layer (ZnS) of 4 cycles by SILAR deposition with Zn (NO3)2 and Na2S as
potassium permanganate, acetic acid from Merck. Fluorine doped tin respective cationic and anionic source in between rinsing with the
oxide (FTO) glass, triton X-100, graphite powder, MWCNTs, zinc nitrate distilled water. This inorganic layer acts as a barrier avoiding chemical
hexahydrate (Zn (NO3)2·6H2O, 98%), cadmium sulphide powder (100 corrosion of QDs and prevents the photo degradation of CdS to CdSO4
mesh 99.5%) sodium sulphide non hydrate (Na2S·9H2O, 98%), sulphur as they are more prone to undergo oxidation in ambient conditions.
and Copper sulphide were procured from Sigma Aldrich. Polysulphide electrolyte was prepared using 1 M solution of Na2S and
Sulphur which acts as a redox couple or hole transporter with CuS as
2.2. Synthesis of ETL, GO and GNRs counter electrode obtained by sonicating CuS with ethanol and drop
casting them on conducting side of FTO.
Sol–gel technique was adopted to prepare TiO2 (ETL) nano particles
[19]. Briefly TiCl4 was hydrolyzed with water and sulphuric acid. 3. Characterization techniques
Ammonium hydroxide was used for gel to crystalline conversion at
appropriate pH of 8 followed by drying and annealing for 6 h at 600 °C The Crystal structure and phase identification of these nanomater-
to obtain anatase phase of TiO2 nanoparticles. ials were done using Rigaku XRD using Cu Kα radiation (scan rate of
Graphene oxide was synthesized by Hummer’s method [20]. Briefly 3° min−1). The functional groups were analyzed using Bruker ATR-IR
Graphite with H2SO4 was cleaved into Graphene sheets with the use of spectroscopic analyzer. The absorption spectrum of samples were re-
KMnO4 as strong oxidizing agent. The sheets were allowed for complete corded using a Shimadzu 1700 PC UV−visible spectrophotometer, the
oxidation in presence of hydrogen peroxide and were given acid and absorbance wavelength was recorded and the band gap was calculated
water wash for purification. using Eg = hc/λ at the absorbance band edges wavelength.
GNRs was synthesized by unzipping of MWCNTs with almost 90% Photoluminescence were recorded using Shimadzu RF 5301 PC spectra
yield as reported by Higginbotham et al. [21] by an efficient chemical fluorometer using Xenon lamp. Surface morphology was carried by JSM
oxidation process with phosphoric acid as second acid along with 7100F JEOL FESEM and HR-TEM was carried out using JEOL/JEM
KMnO4 and H2SO4 to control the vacancies created in GNRs by masking 2100 at an accelerating voltage of 200 kV. The Brunauer-Emmett-Teller

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(BET) specific surface area of the materials was obtained from N2 ad- MWCNTs with inner tube diameter ranging between 7 nm and 15 nm.
sorption/desorption isotherms recorded on model BELSORP- max MWCNTs unzipped to form GNRs is as shown in Fig. 2(d) which has
(Japan) at 77 K. Time resolved PL measurements were carried out using varying ribbon width from 80 to 300 nm. Ribbon lengths appear shorter
Horiba fluorescence photometer at 345 nm excitation source. than tubes but contribute efficiently to increase the aspect ratio.
Composite analysis was carried out using surface measurements by X- Figs. 2(b) and 2(f) shows the composites of TiO2-MWCNT and TiO2-
ray photoelectron spectra with Al Kα (1486.6 eV) as the X-ray source GNR respectively. The entanglement or intercalation of tubes in
set at 150 W and a pass energy of 50 eV. Photovoltaic performance of MWCNTs tend to trap the TiO2 nanoparticles restricting the flow,
QDSSCs were measured by integrated I–V Test station (PVIV-211 V) whereas in case of GNR composite the ribbons/strips provides a large
with Keithley 2420 source meter and 94023A Oriel Sol3A, class AAA surface area for TiO2 nanoparticles with less grain boundaries for better
Solar Simulator (power output: 100 mW/cm2, lamp power: 450 W), transport. Also the high reactive edge sites with carboxylic, epoxy and
equipped with an AM 1.5 filter. IQE measurements were carried out –OH groups allows better bonding with TiO2 than metallic nanotubes. It
using Oriel using Hg lamp (450 W, Oriel) and a monochromator with a could be possible that TiO2 spheres can act as pillars between the strips,
bandwidth of 5 nm. Impedance analysis was carried out using electro- separating the ribbons from each other due to its high active edge sites.
chemical station in Impedance mode using CHI660D model in the fre- It also allows to carry the electrons across more quickly and this could
quency range of 1 MHz to 1 Hz. For AFM, a solution of nano crystals be the reason for better quenching (observed from PL). The HR-TEM
(dispersed in DMF) were dropped on Mica sheet for imaging in air using image of nanotubes and GNR composites are shown in Fig. 2(c) and (g).
Bruker Dimension Icon AFM equipped with a Nano scope V SPM con- Inclusion of graphene materials into TiO2 via thermal treatment tend to
troller in contact mode and TUNA was used for conductivity measure- form a strong chemical interaction giving rise to new Ti-O-C bonds
ments. (confirmed from XPS and IR- Fig S5 in SI), resulting in changes in the
lattice spacing. The changes in the lattice structure brings out changes
4. Results and discussions in the lattice parameters reflecting the changes in d-spacing as well
from 0.39 nm to 0.42 nm (GNRs) and from 0.35 nm to 0.32 nm (TiO2).
4.1. X-ray diffraction studies (XRD) SAED diffraction fringes are presented in Fig. 2(d) and (h) for MWCNT
and GNR composites. It clearly depicts the material on a whole to be
Structural studies of graphene and composite materials were carried perfectly crystalline and also the lattice plane reflections match with
out using XRD as shown in Fig. 1. Peaks at ~10.8°, 11.7° and 25.7° the XRD data.
(JCPDS no 75-1621) with d-spacing of 8.1 Å, 8.9 Å and 3.4 Å (Fig. 1a)
indicate the synthesized GO [20], GNRs [21] and MWCNTs [24] re-
spectively. The appearance of (001) reflection in GNRs at 11.7° is an 4.3. Brunauer-Emmett-Teller (BET)
indication of successful unzipping of MWCNT (at 2θ = 26°) and ex-
foliation [24]. TiO2 and its composite with GNR is shown in Fig. 1(b). N2 adsorption and desorption isotherms were carried out to find the
TiO2 is in anatase phase and peaks at 2θ values of 25.5°, 37.8°, 47.9° surface area of graphene materials and their composites as listed in
and 53.9° are assigned to the crystal planes of (101), (004), (200) and Table 1 below. The highest surface area is observed for unzipped GNRs
(105) of the body-centred tetragonal TiO2 (JCPDS 21-1272). The strong (399.3 m2 g−1), which is 1.8 times higher than MWCNTs (213.7 m2
interaction caused during composite formation results in changes in the g−1) showing maximum unzipping of MWCNTs. The isotherm curve for
crystalline phase of TiO2 particles. Since the amount of dispersed GNRs (Fig S1 of SI) suggest a type IV isotherm of irreversible desorption
carbon material is less, there is no significant peak of GNRs in the patterns with H3-hysteresis loop [25], and average pore size around
composite and hence exhibit similar XRD patterns [8]. HR-TEM, IR and 1.9 nm (micro porous structure) [26]. Tri-distribution mesoporous
XPS has been further used to confirm the Ti-O-C bond formation in nature (3, 8 and 14 nm) with higher pore diameter and volume has been
composites. obtained for MWCNTs. Also TiO2-GNR has comparatively greater sur-
face area and narrow pore size distribution (Fig S2 of SI) with TiO2
nanoparticles being uniformly spread throughout (as evidenced by
4.2. Transmission electron microscopy (TEM)
EDAX mapping in Fig S3 of SI). This predicts that GNRs could serve as a
conducting floor for deposition of TiO2 particles because of its high
TEM (Fig. 2) has been further used to evidence the unzipping of
surface area and microporous structure.
MWCNTs and as well to confirm the network of graphene materials
with TiO2 as composites. Fig. 2(a) represents the entangled network of

Fig. 1. XRD graphs of (a) Graphene materials and (b) Composite of GNR.

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Fig. 2. TEM micrograph of (a) MWCNTs (b), (c) and (d) TEM, HR-TEM and SAED OF TiO2-MWCNT, (e) GNRs, (f), (g) and (h) TEM, HR-TEM and SAED OF TiO2-MWCNT.

4.4. Field Emission Scanning Electron Microscopy (FESEM)

Table 1
BET surface area, pore volume and pore diameter. Surface morphology of the samples were examined using FESEM
(Fig. 3). Fig. 3(a) and (d) depicts the entangled nature of MWCNTs and
Nanomaterials Surface area Pore volume Pore diameter its composite respectively in which the TiO2 nanoparticles are trapped
[m2 g−1] [cm3 g−1] [nm]
within the network of tubes allowing maximum aggregation on nano-
TiO2 94.7 0.12 5.02 tubes. Porous honeycomb like architecture with curvy and wrinkled
MWCNTs 213.7 0.36 6.78 sheets curled at the edges (Fig. 3b) is observed for GNRs. Also these
GNRs 399.3 0.19 1.91 ribbons are more likely aligned next to each other due to strong surface
TiO2–MWCNT 79.5 0.17 8.56
energy present at the edges substantially forming huge ribbons of dia-
TiO2–GNR 84.1 0.10 5.07
meter (up to 300 nm confirmed from AFM and TEM). In case of com-
posite of GNR (Fig. 3e), ribbons surface looks smoother with reduction

Fig. 3. Surface morphology of: (a) MWCNTs, (b) GNRs, (c) GO, (d) TiO2-MWCNT, (e) TiO2-GNR and (f) TiO2-GO.

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of lamellar aggregation of TiO2 particles. Fig. 3(c) shows two dimen- Table 2
sional stacked infinite nanosheets of Graphene oxide and its composite Parameters of radiative and non-radiative lifetime of exciton.
(Fig. 3f) represents uniform deposition of TiO2 spherical particles on
Sample A1 τ1(ns) A2 τ2(ns) τavg (ns)
nanosheets [27,28] with average particle size of 25 nm.
TiO2 93 0.54 7 6.19 5.01
TiO2-MWCNT 98 0.46 2 6.25 5.11
4.5. Photoluminescence studies (PL) TiO2-GO 99 0.45 1 8.01 6.42
TiO2-GNR 99 0.46 1 6.78 4.22
PL spectroscopy was employed to follow the fate of photo-excited
charge carriers in composite materials. The irradiation of TiO2 results in
emission of photons at specific wavelength associated with direct band network to form Ti-O-C linkages (also confirmed from ATR-IR shown in
gap or defect mediated recombination [29,30]. Composites of graphene Fig S5 of SI). Also decrease of electron density around Ti atom results in
materials with TiO2 show quenching in PL intensity (Fig. 4a) suggesting increase in its binding energy because of greater electro negativity of
electron transfer from conduction band of TiO2 to Graphene materials carbon than Ti. However no Ti 3+ peaks were detected.
efficiently while reducing radiative recombination. Among all the
composites, TiO2-GNR shows better quenching due to the enhanced 4.7. Atomic Force Microscopy (AFM)
charge separation (reflected from higher Jsc in IPCE) [31]. Also peaks
of composites have slightly shifted. This could be preferably due to the AFM was used to analyze the structure, height (no. of layers), width
reduction in the dimension of the material. CNTs/GNRs are one di- and conductivity of the ribbons. Fig. 6(a) shows the topography on
mensional in nature whose absorbance are slightly blue shifted and red micron scale wherein the ribbons looks separated forming strips of
shifted for GO composites for its plane dimension (as observed in graphene. Fig. 6(b) shows the height profile of GNRs varying from 3 nm
UV–Visible spectroscopy). Further PL emission as a function of time to 7 nm (combination of bilayer to few layers) of ribbons [37]. Widths
(Time resolved photoluminescence spectra) was carried out for probing of the ribbons were observed to extend up to 300 nm which are in
the recombination dynamics in the excited states. insert 'full stop' after agreement with the results obtained from TEM. The oxidized edges and
excited state. The kinetics can be analyzed using bi-exponential decay disruption of π network allows GNRs to gain partial conductivity and
which involves modelling the data and fitting the curve into bi-ex- was confirmed with the AFM TUNA conductivity measurements. The
ponential decay (y = y0 + A1e −x / t1+ A2e −x / t2 ) [32] as shown below in measurements were carried out at many places and results showed the
Fig. 4(b) and parameters being tabulated in Table 2. The decreasing combination of both semiconducting and metallic nature of the mate-
trend in average lifetime from TiO2 to GNR is in par with PL emmision rial suggesting ribbons to be in arm chair and zigzag configurations
decay. The average lifetime in case of GNR composites suggests the respectively. Fig. 6(c) is IV curve for biased voltage of ± 4 V. The curve
greater electron transfer rate across the interface substantiating better tends to saturate beyond 3 V biased voltage suggesting GNRs being
quenching in PL emission decay. transformed into a semiconducting material [37]. This also sub-
stantiates the band gap of GNRs (~3.45 eV) obtained by band edge of
4.6. X-ray photoelectron spectroscopy (XPS) UUV–Visble spectroscopy (Fig S4 in SI).

The chemical interactions in the prepared composites (TiO2- 5. Performance studies

MWCNT and TiO2-GNR) were further confirmed by XPS analysis and
the spectra is as presented below in Fig. 5. Plot (a) is wide energy Solar cell was assembled with photo anode (TiO2) sensitized by CdS
survey spectra, (b), (c) and (d) are high resolution spectra with Gaus- quantum dots, CuS counter electrode and polysulfide electrolyte.
sian curve fitting for C 1s, O 1s and Ti 2p respectively. Plot b (C 1s) Photovoltaic performance was studied under standard conditions
depicts peaks for C-C, HO-C˭O and C-OH at 285.05 eV, 288.6 eV and (100 mW/cm2 AM 1.5 G) for active area of 0.25 cm2 of cell in tripli-
286.4 eV respectively. The polar groups suggest the oxidation of cates. The current density–voltage (J–V) curves of Graphene materials
MWCNTs and GNRs that may be supportive for the nucleation of TiO2 are presented in Fig. 7(a) and the parameters are listed in Table 3.
on their surface [33,34]. –OH groups on surface of TiO2 react with C- There is a significant enhancement in Jsc (13.82 mA/cm2) for cells of
OH and COOH on GNRs through dehydration to form Ti-O-C and O˭C- GNRs with PCE inflated to 3.7%. With increase in the amount of GNRs,
O-Ti [35,36]. The binding energies of Ti4+ 2p3/2, Ti4+ 2p1/2 and O1s PCE decreases due to opacity of electrodes, as this can increase the
are all upward shifted indicating the insertion of Ti4+ cations into GNRs transport resistance of electrons at the TiO2/CdS/Polysulphide

Fig. 4. (a) Photoluminescence spectra and (b) Time-resolved photo luminescence spectra.

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Fig. 5. (a) XPS whole survey spectra of TiO2, MW-TiO2 and GNR-TiO2; (b)-(d) High resolution and Gaussian curve fitting for C, O and Ti in TiO2, TiO2-MWCNT and TiO2-GNR.

interface. GNR composites with increased active sites red shifts the The IPCE spectra for graphene based composites are shown in the
absorption edge (as observed from UV–Visble spectroscopy), enhances Fig. 7(b), which signifies light harvesting, charge injection, and charge
the photocurrent and reduces the recombination of exciton by facil- collection in the device [47]. IPCE spectra show a superior photo re-
itating efficient charge separation [38,39]. The photovoltaic perfor- sponse between 320 and 520 nm. The Graphene composites show an
mances of these carbonaceous materials tend to show a quite significant enhancement in photocurrent compared to TiO2. The higher photo
difference in its performance because of its different chemical, optical, current observed in case of GNR composite show enhanced charge se-
electrical properties and dimensional frameworks. GO composites with paration, due to the wrinkled strips which could allow electrons to
TiO2 as photo anode has already been reported in case of DSSC [40,41]. migrate through the interconnected TiO2 nanoparticles. Though the
But GO when brought in contact with TiO2 under UV irradiation tends alignments of strips are not optimally oriented electrons can easily
to decrease the activity and PCE drops rapidly over continuous illu- channelize through these strips as they have less number of voids. Also
mination [42] unlike in the case of GNRs [43]. Though CNTs are good it allows the electrons to easily hop between the strips for which the
electron transporters the entanglement in MWCNTs can adversely affect FTO substrate creates a potential between working electrode and
(as observed in TEM) the electron transport and also suffer from in- junction driving the electrons enhancing efficiency. In case of TiO2-
tertube slipping which degrades their ability as structural reinforce- MWCNT composite, the intermingled nanotubes tends to trap electrons
ment additives [44]. But GNRs followed by unzipping is quite stable within them and possess relatively more obstruction for flow of elec-
and found to have lower electron impedance as shown in Fig. 7(c) that trons compared to GO and GNRs.
can enhance the separation of electron–hole pairs [45] (as reflected The electrical resistance and recombination dynamics are studied
from PL and IPCE). Also the high surface area of GNRs creates as many using Electron impedance spectroscopy (EIS). The measurements were
active sites for TiO2 nanoparticles and allows for intercalation with carried out in dark and the frequency was measured from 1 MHz to 1 Hz
host, facilitating quick electron transfer. The isotherm shows micro and the Nyquist plots for these cells are given in Fig. 7(c) along with
porous structure in GNRs which helps in channelizing the electrons their equivalent circuit. The series ohmic resistance (Rs) at higher fre-
through interconnected network of TiO2 nanoparticles. Also exfoliated quency contributes to the interfacial resistance between the electrical
ribbons with confined electrons tend to increase the photochemical contacts and FTO, which is the x-intercept at high frequency [29] and
activity. The work function of Graphene (−4.42 eV) is close to FTO are almost found to be around ~11 Ω. CPE is the constant phase ele-
(−4.7 eV) and hence there is no much change in the Voc for composites ment which is a constant factor for all. Rt is charge transfer at TiO2/
[46]. The enhancement of Jsc clearly indicates that GNRs are good QD/Electrolyte interface for which the values are tabulated for com-
electron transporters. posites in Table 3. The smaller radius of the semicircle with lesser Rt for

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Fig. 6. (a) AFM image of GNRs, (b) Height profile, (c) AFM TUNA measurements and (d) IV Curve from TUNA.

Fig. 7. (a) IV characteristics, (b) IPCE spectra, (c) Nyquist plot for Graphene composites and (d) Nyquist plot for different wt. ratio of GNRs.

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Table 3 helps in channelizing the electrons through interconnected network of

Photovoltaic and EIS parameters for different Graphene composites. TiO2 nanoparticles. Also exfoliated wrinkled strips/ribbons confine
electrons and tend to increase the photochemical activity, as electrons
Photo anode Jsc Voc FF PCE Rt
can easily channelize through these strips due to less number of voids.
(mA/cm2) (mV) (%) (%) (Ω) GNRs can drive electrons to the electrode as its work function is very
close to FTO, which creates a potential between working electrode and
TiO2 7.2 562 43.21 1.74 ± 0.05 63.2
junction driving the electrons and enhancing the overall efficiency. Also
TiO2-MWCNT 8.1 586 42.89 1.99 ± 0.21 39.3
TiO2-GO 9.4 574 43.04 2.36 ± 0.12 26.8
due to its conducting edges, charge carrier mobility, large surface area
TiO2-GNR 13.8 571 46.78 3.69 ± 0.16 18.5 and active sites facilitates separation of exciton when compared to
others and prove themselves to be an excellent candidate to replace
MWCNTs for optoelectronic applications.
Table 4
Photovoltaic parameters for different wt. content of GNRs. Acknowledgements
Wt. % of GNRs Jsc Voc FF PCE Rt
The authors would like to acknowledge the Nano mission project,
(mA/cm ) 2
(mV) (%) (%) (Ω) (No. SR/NM/NS-20/2014) for the financial support.

0.04 8.28 578 43.04 2.05 ± 0.14 27.5

Appendix A. Supporting information
0.08 9.58 573 42.99 2.35 ± 0.11 24.9
0.12 13.82 571 46.78 3.69 ± 0.16 18.5
0.16 10.42 563 43.20 2.53 ± 0.2 25.5 Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.solmat.2018.01.039.

TiO2-GNR in Fig. 7(c) is an indication of increase in the charge col- References

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