Solar Energy Materials & Solar Cells 94 (2010) 2148–2153

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Solar Energy Materials & Solar Cells

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

Improving photovoltaic properties by incorporating both SPFGraphene and

functionalized multiwalled carbon nanotubes
Zhiyong Liu, Dawei He n, Yongsheng Wang n, Hongpeng Wu, Jigang Wang, Haiteng Wang
Key Laboratory of Luminescence and Optical Information, Ministry of Education, Institute of Optoelectronic Technology, Beijing Jiaotong University, Beijing 100044, PR China

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

Article history: Solution-processable functionalized graphene (SPFGraphene) and functionalized multiwalled carbon
Received 8 May 2010 nanotubes(f-MWCNTs) are introduced for heterojunction solar cell. The performance of the device has
Received in revised form improved by the incorporation of both SPFGraphene and f-MWCNTs. The open-circuit voltage (Voc),
20 June 2010
short-circuit current density (Jsc), fill factor (FF) and power conversion efficiency (Z) were 0.67 V,
Accepted 5 July 2010
4.7 mA/cm2, 32%, and 1.05%, respectively. Here, we expect that SPFGraphene acts as exciton dissociation
and provide percolation paths for electron transfer, whereas f-MWCNTs provide efficient hole
Keywords: transportation. SPFGraphene and f-MWCNTs incorporation yields better carrier mobility, easy exciton
SPFGraphene splitting, and suppression of charge recombination, thereby improving photovoltaic action.
f-MWCNTs
& 2010 Elsevier B.V. All rights reserved.
Charge

1. Introduction transport efficiently to the electrodes before recombination

occurs [9]. So far, the research effort of OPV materials has
The photovoltaic of inorganic materials based on the ZnO, TiO2, dominated on the PCBM as the electron acceptor. In addition, the
CdSe and CdS has attracted much interest of researcher all over solubility and stability of both donor and acceptor are critically
the world [1]. However, the photovoltaic devices based on important. The most successful OPV cells are based on soluble
inorganic materials offer great disadvantage because of their high poly(3-hexylthiophene) (P3HT) and poly(3-octylthiophene)
cost and environment-pollute manufacturing methods. Organic (P3OT) as the donor and PCBM as the acceptor [10,11].
photovoltaics (OPVs) are a promising low-cost alternative to Some paper had reported the external quantum efficiency (EQE)
silicon solar cells, thus a great deal of effort has been devoted to of P3HT/PCBM hybrid solar cell to be nearly 80%; the
increase the power conversion efficiency and to scale up the power conversion efficiency (PCE) of organic photovoltaic
production processes [2]. An attractive feature of the organic cells has surpassed 7.4%. The structure of devices is based on
photovoltaics based on conjugated polymers is that they can be ITO/PEDOT:PSS/PTB7: PC71BM/Ca/Al, the PTB7 acted as donor
fabricated by a coating process (e.g. spin coating or inkjet materials and the PC71BM acted as acceptor materials [11,12].
printing) to cover large areas, and may be formed on flexible However, the power conversion efficiency of these OPV devices is
plastic substrates [3]. The photovoltaic devices based on organic still low compared to conventional inorganic devices [7]. The
materials have attracted much interest of researcher including commonly accepted mechanism for the light-to-electricity con-
materials, processes and devices [4]. Some lab has reported the version process is light absorption exciton generation, exciton
manufacture of polymer solar cells using full roll-to-roll proces- diffusion, exciton dissociation and charge formation and charge
sing [5]. It has developed the full manufacture, integration and transport and charge collection [13]. The main factor of low-
demonstration of polymer solar cells [6]. Power efficiency of power efficiency compared with conventional inorganic devices is
organic photovoltaic devices is still low compared to the the absorption spectrum of P3HT. Thus, new materials for both
traditional inorganic devices [7]. The main factor is structural donor and acceptor with better HOMO/LUMO matching, stronger
traps in the form of dead ends, isolated domains and incomplete light absorption and higher charge mobility with good stability
pathways in the random percolation network [8], which has is needed. This has led to studies of other allotropic forms of
resulted in inefficient hopping charge transport and electron carbon nanomaterials, including single-walled carbon nanotubes
transport. Therefore, the challenge here is to provide continuous (SWCNTs) and multiwalled carbon nanotubes (MWNTs) as
pathways within each component and thus to allow charges to acceptors [14]. Functionalized multiwalled carbon nanotubes
(f-MWCNTs), SWCNTs and PCBM have shown better power
conversion efficiency than pristine samples without CNTs or
n
Corresponding authors. PCBM [15,16]. In such solar cells, it is suggested that MWCNTs
E-mail addresses: dwhe@bjtu.edu.cn (D. He), yshwang@bjtu.edu.cn (Y. Wang). enhance hole transport, whereas SWCNTs enhance electron

0927-0248/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.solmat.2010.07.001
 Z. Liu et al. / Solar Energy Materials & Solar Cells 94 (2010) 2148–2153 2149

transport. However, practically, the solubility and stability of both

donor and acceptor are critically important.
Graphene, as a very recent rising star in materials science with
two-dimensional (2D) structure consisting of sp2-hybridized car-
bon, exhibits remarkable electronic and mechanical properties that
qualify it for application in future optoelectronic devices [17]. It is a
gapless semiconductor with unique electronic properties and its
electron mobility reaches 200,000 cm2/V s at room temperature
[18]. Its one-atom thickness and large 2D plane lead to a large
specific area, and therefore, very large interfaces can form when it
was added to a polymer matrix. A conducting film and a transparent
anode for PV device applications have also been developed [19,20].
The unique structure and excellent electronic properties, particu-
larly its high mobility, and the ready availability of solution-
processable functionalized graphene (SPFGraphene), render it a
competitive alternative as the electron-accepting material in PV
device applications [21]. In this paper, the SPFGraphene not only
acts as electron acceptors, but also provide high field at the
Fig. 1. (a) Schematic of the devices with P3HT/f-MWCNT-SPFGraphene as the
polymer/SPFGraphene interfaces for exciton dissociation.
active layer. (b) The chemical structure of SPFGraphene.

2. Experimental lene dioxythiophene) doped with polystyrene sulfonic acid

(PEDOT:PSS) was spin-coated on the indium tin oxide (ITO)
2.1. Synthesis of functionalized multiwalled carbon nanotubes coated glass substrate. Then PEDOT:PSS-coated substrate was
(f-MWCNTs) annealed for 20 min at 120 1C in vacuum. And then spin coating a
solution of 15 mg/ml poly(3-hexylthiophene-1,3-diyl) (P3HT) in
In this work, we aimed to study the role of incorporation of both chlorobenzene with various SPFGraphene contents (0, 1, 2.5, 5, 10,
f-MWCNTs and graphene with conducting polymer to make 12.5 and 15 wt%) and 2% f-MWCNTs content onto indium tin
heterojunction photovoltaic device. Purified MWCNTs was sus- oxide (ITO) glass substrate. Then the devices annealed for 10 min
pended in mixture of concentrated H2SO4/HNO3 (H2SO4:HNO3 is at 180 1C in vacuum. LiF and Al were vapor deposited on the
3:1) and sonicated in a water bath for a few hours. The suspension active layer. Fig. 1a shows the schematic of the devices with
is diluted by deionized water. A functionalized multiwalled carbon P3HT/SPFGraphene as the active layer.
nanotube (0.1 mg) is dispersed in chloroform solvent (1 ml) [14]. The current–voltage (J–V) was determined using a Keithley 2410
source measure unit. A 150 W xenon lamp acted as a broadband
light source and the intensity of incident light is 100 mW/cm2. The
2.2. Synthesis of solution-processable functionalized graphene
photoluminescence been measured using a Fluolog-3fluoresvent
(SPFGraphene)
spectrometer. The absorption spectra been measured using a
Shimadzu UV-3101 PC spectrometer. All measurements were at
In this paper, SPFGraphene is been prepared by exfoliated
atmospheric pressure and room temperature.
graphene oxide sheets. The first step is the preparation of graphite
oxide by the modified hummer method [21]. Five grams of
crystalline flake graphite, 30 g KMnO4 and 15 g of NaNO3 (purity
3. Results and discussion
99%) were placed in a flask. Then, 300 ml of H2SO4 (purity 98%)
was added, a stirrer chip was placed in the mixture, and the
The power conversion efficiency (Z) was calculated according to
mixture was stirred while being cooled in an ice water bath. The
liquid added to 1000 cm3 of deionized water over about 1 h of Voc Isc FF
Z¼
stirring. Then, 30 ml of H2O2 (30% aqueous solution) was added to Pin
the above liquid and the mixture was stirred for 2 h.
where Voc, Jsc, Pin and FF are the open-circuit voltage, the short-
In order to remove Mn2 + , the resultant liquid purified by repeating
circuit current density, the incident light power and the fill factor
the following procedure: centrifugation, removal of the supernatant
(FF), respectively. The fill factor (FF) of definition is
liquid, addition of a mixed aqueous solution of 0.5% H2O2, and shaking
to disperse. The procedure was cycled using aqueous HCl solution Vmax Imax
FF ¼
(5%) and using H2O, and then drying process in vacuum. The Voc Isc
molecular structure of graphite oxide been shown in Fig. 1b.
The FF measures the quality of solar cell as a power source and is
Isocyanate functionalization of graphene oxide: dried graphite
defined as the ratio between the maximum power delivered to an
oxide (200 mg) was suspended in deionized water (20 ml), and
external circuit and the potential power. Vmax and Imax are,
treated with phenyl isocyanate (20 g) for 24 h and the impurities
respectively, the values of the voltage and current densities for
were removed, and finally the isocyanate-treated graphene oxide
maximizing for the product of I–V curve in the fourth quadrant,
was obtained [9]. The second step is to exfoliate graphite oxide
where the device operates as an electrical power source.
ultrasonically. Then a phenyl isocyanate treatment resulted in
After functionalization, the SPFGraphene sheet and multi-
SPFGraphene that can dissolve in organic solvent [22].
walled carbon nanotubes introduced many functional groups and
the structure been partly isolated by the functional groups.
2.3. Fabrication and characterization of optoelectronic devices Therefore, the organic functional groups decrease charge trans-
port properties and mobility of the SPFGraphene sheets and
The organic photovoltaic (OPV) was made using a common f-MWCNTs. This will limit the performance of the above P3HT/
fabrication process. The hole-injections buffer layer of (polyethy- SPFGraphene-f-MWCNTs based device. In view that the functional
2150 Z. Liu et al. / Solar Energy Materials & Solar Cells 94 (2010) 2148–2153

groups can be removed from the SPFGraphene sheet and

f-MWCNTs in an elevated temperature under vacuum, the
conductivity of the SPFGraphene sheet and f-MWCNTs can be
recovered [14,23]. The other affect of introduced functional
groups is band gap. Graphene has zero band gap; some paper
has reported that the solution-processable functionalized of
graphene band gap is 0.4 eV [24]. Clearly, improvement of the
overall photovoltaic performance is due to annealing process.
Therefore, we will anneal all the optoelectronic devices.
For study on absorption spectra of P3HT/SPFGraphene compo-
site film, mixed solution of P3HT/f-MWCNTs, P3HT/f-MWCNTs-
SPFGraphene (P3HT: 1 mg/ml, SPFGraphene content: 5%) and P3HT
dissolved in chlorobenzene was used. Fig. 2 shows the absorption Fig. 3. Energy band diagram of the fabricated device showing band alignment for
spectra of P3HT/f-MWCNTs, P3HT/f-MWCNTs-SPFGraphene, as well SPFGraphene.
as the reference solution of P3HT in chlorobenzene. The absorption
characteristics of P3HT in the range of 300–800 nm, the original
absorption of P3HT centred at 550 nm. However, the absorption 1.0
spectra of P3HT/f-MWCNTs, P3HT/f-MWCNTs-SPFGraphene mixed SPFGraphene content 12%
0.9 SPFGraphene content 8%
solution is almost the same as the scope and absorption peaks, but
the absorption peak of the P3HT/f-MWCNTs-SPFGraphene slightly 0.8 SPFGraphene content 5%
SPFGraphene content 0%
increases, and enhanced absorption ranging from 340 to 550 nm. 0.7

PL intensity (a.u.)
This may explain the absorption of P3HT/f-MWCNTs-SPFGraphene
0.6
composite film. Despite the SPFGraphene content of 5%, the
absorption spectra of P3HT/f-MWCNTs-SPFGraphene did not show 0.5
significant changes. This should be the result of P3HT/f-MWCNTs- 0.4
SPFGraphene mixed in solution, with no significant ground state
0.3
interaction between the two materials. Therefore, there is no charge
transfer in the ground state of P3HT/SPFGraphene composite [21]. 0.2
SPFGraphene could also exhibit strong donor/acceptor interac- 0.1
tions for the conjugated polymers. We will investigate the character
0.0
of electron acceptor between SPFGraphene and P3HT by photo-
luminescence (PL). Thus, we will investigate the PL spectra that -0.1
P3HT/SPFGraphene (P3HT: 5 mg/ml, SPFGraphene content: 0%, 5%, 500 550 600 650 700 750 800
8% and 10%) mixture solution in chlorobenzene and P3HT (5 mg/ml) Wavelength (nm)
solution in chlorobenzene. From Fig. 4 we can see that the pure
Fig. 4. PL spectra of P3HT and P3HT/SPFGraphene (SPFGraphene contents: 0%, 5%,
P3HT solution shows strong photoluminescence between 525 8% and 12%) composite films at an excitation wavelength of 422 nm.
and 750 nm, with excitation at 422 nm. However, introduction of
SPFGraphene into the P3HT has remarkably reduced the
photoluminescence intensity. It has shown efficient charge/energy P3HT/SPFGraphene configuration. These results show that the
transfer along the P3HT/SPFGraphene interface. This efficient quench of fluorophore is due to the electronic interactions at the
quenching of PL emission is due to the efficient electron transfer P3HT/SPFGraphene interfaces. The relative position of donor LUMO
from P3HT to SPFGraphene. The trend of reduction in PL intensity and acceptor LUMO is crucial for the aimed charge transfer. Fig. 3
along with an increase in SPFGraphene content has shown that the shows that there is a difference between LUMO of P3HT and work
efficiency of charge separation has improved in the roughened function of SPFGraphene. Energy band diagram favored the
photoexcited P3HT to transfer electron to SPFGraphene molecule.
Therefore, P3HT acted as electron donor and SPFGraphene acted as
P3HT/f-MWCNT-SPFGraphene electron acceptor to prepare donor/acceptor solar cells. The
1.0 P3HT/f-MWCNT quenching of PL of an appropriate donor polymer by a suitable
P3HT acceptor gives an indication of an effective donor–acceptor charge
0.8 transfer from the donor to the acceptor, as described by Sariciftci
et al. [25] for composites of p-conducting polymers and
Absorption (a.u.)

SPFGraphene derivatives. The other reason is the increased

0.6 interfacial areas that facilitate charge separation within the bulk
instead of just at the planar interface for the bilayer structure. By
0.4 referring to previous work with PCBM and carbon nanotubes
[26,27], this efficient reduction in PL intensity shows that
SPFGraphene expected to be an effective electron acceptor
0.2 material for organic photovoltaic applications.
Fig. 5 shows the current–voltage (J–V) of photovoltaic devices
0.0 in the dark and AM 1.5 100 mW simulated solar radiation for P3HT/
f-MWCNTs and P3HT/f-MWCNTs-SPFGraphene (SPFGraphene con-
300 400 500 600 700 tent is 5%) devices. There is no reaction in the dark of P3HT/
f-MWCNTs and P3HT/f-MWCNTs-SPFGraphene (SPFGraphene
Wavelength (nm)
content is 5%) devices. Under simulated 100 mW AM 1.5 G
Fig. 2. Absorption spectra of P3HT, P3HT/f-MWCNT and P3HT/f-MWCNT- illumination, open-circuit voltage (Voc) of P3HT/f-MWCNTs active
SPFGraphene. layer is 0.65 V, short-circuit current density (Jsc) of P3HT/f-MWCNTs
 Z. Liu et al. / Solar Energy Materials & Solar Cells 94 (2010) 2148–2153 2151

active layer is 0.27 mA/cm2, FF of P3HT/f-MWCNTs active layer is polymer and the Voc principally determined by the work function
0.27 and power conversion efficiency (Z) of P3HT/f-MWCNTs active difference between the two metal electrodes. The configuration of
layer is 0.65%. In contrast, Voc of P3HT/f-MWCNTs-SPFGraphene organic photovoltaic devices is the electrode–insulator–metal
(SPFGraphene content is 5%) has increased to 0.67 V, Jsc has (MIM) model [29], i.e, ITO–active layer–Al. However, the P3HT/f-
increased to 3.2 mA/cm2, FF has increased to 0.32 and power MWCNTs-SPFGraphene has a BHJ structure, the MIM model is not
conversion efficiency (Z) of P3HT/f-MWCNTs-SPFGraphene active applicable and Fermi level pinning is the main factor [30].
layer is 0.9%. Improvement of the overall photovoltaic performance Therefore, the upper limit of Voc can determine by the difference
can be attributed to an increase in SPFGraphene. between the work function of SPFGraphene and f-MWCNTs. Some
Then we will study the optical and electrical properties of paper has reported that the work function of as-prepared
different SPFGraphene contents (0%, 1%, 5%, 8%, 10% and 12%) SPFGraphene is 4.5 eV. The work function of MWCNTs ranges from
based on P3HT/f-MWCNTs-SPFGraphene composite, as shown in 4.6 to 5.1 eV. After acid oxidation, carboxylic acid groups were
Fig. 6. The different SPFGraphene contents (0%, 1%, 5%, 8%, 10% and introduced onto the surface of MWCNTs, which produced higher
12%) show different power conversion efficiencies (0.65%, 0.75%, work function (5.1 eV) [14,21]. Energetically favorable charge
0.9%, 1.05%, 0.82% and 0.58%), respectively. Fig. 6 shows that along transportation and band diagram are shown in Fig. 3.
with an increase in SPFGraphene content, the overall performance Increase in FF can be attributed to the introduction of
reached its peak; the best content was 8% and the power SPFGraphene in P3HT. Introduced SPFGraphene into P3HT increased
efficiency, 1.05%. the built-in electric field and field-dependent exciton dissociation
Voc of the P3HT+f-MWCNTs is 0.65 V and the Voc of composite rate. The SPFGraphene will improve the electron transport and
film P3HT/f-MWCNTs-SPFGraphene is 0.67 V. There are different balance the electron-hole pairs transport. Another reason is an
models describing the Voc of the pure P3HT [25,28]. A single improvement of the series and/or the shunt resistance. Introduced
layered organic photovoltaic cell is composed of a pure conjugated SPFGraphene into P3HT will roughen the interface and increase the
contact area between the photoactive layer and the Al, and
consequently reduce the series resistance [31].
10 Table 1 shows the J–V curve of different SPFGraphene contents
(0%, 1%, 5%, 8%, 10% and 12%). Power conversion efficiencies are
1 0.65%, 0.75%, 0.9%, 1.05%, 0.82% and 0.58%, respectively.
Current Density (mA/cm2)

SPFGraphene content of 8% has shown the best results. If the

0.1 SPFGraphene content is lower than 8%, along with an increase
in SPFGraphene content, the power conversion efficiency increases.
0.01 SPFGraphene content is the main factor improving the power

1E-3
Table 1
Performance details (Voc, Jsc, FF and Z) of the P3HT/f-MWCNT-SPFGraphene based
1E-4 P3HT/f-MWCNT dark photovoltaic devices.
P3HT/f-MWCNT-SPFGraphene dark
SPFGraphene Voc (V) Jsc (mA/ FF Z (%)
1E-5 P3HT/f-MWCNT light
content (%) cm2)
P3HT/f-MWCNT-SPFGraphene light
1E-6 0 0.65 3.7 0.27 0.65
-1.0 -0.5 0.0 0.5 1.0 1.5 1 0.66 3.9 0.29 0.75
5 0.67 4.4 0.31 0.9
Voltage (V) 8 0.67 4.7 0.32 1.05
10 0.65 4.2 0.3 0.82
Fig. 5. J–V characteristics of PV devices based in P3HT/f-MWCNT, 12 0.54 3.5 0.31 0.58
P3HT/f-MWCNT-SPFGraphene (SPFGraphene content is 5%) in the dark and light.

5.0
0.68
Power conversion efficiency (PCE)

4.8 0.32
1.0 0.66
4.6
0.64
4.4
0.62 0.30
Jsc

Voc

FF

4.2 0.8
0.60
4.0 0.58
0.28
3.8 0.56
Jsc 0.6 Voc
3.6 PCE 0.54 FF

3.4 0.52 0.26

0 2 4 6 8 10 12 0 2 4 6 8 10 12
Weight fraction of SPFGraphene on P3HT/f-MWCNTs solution (%) Weight fraction of SPFGraphene on P3HT/f-MWCNTs solution (%)

Fig. 6. (a) Dependence of the short-circuit current density and the power conversion efficiency on different SPFGraphene concentrations. (b) Dependence of the
open-circuit voltage and the FF on the different SPFGraphene concentrations.
2152 Z. Liu et al. / Solar Energy Materials & Solar Cells 94 (2010) 2148–2153

conversion efficiency. While SPFGraphene concentrations are lower, ITO/PEDOT:PSS/P3HT-f-MWCNTs-SPFGraphene/LiF/Al, P3HT acts
such as 1%, the SPFGraphene film is too small to form a continuous as the photoexcited electron donors; SPFGraphene act as electron
donor/acceptor interface and the transport pathway for the active acceptor and provide percolation paths of electron; f-MWCNTs
layer P3HT matrix. Therefore, the electron cannot effectively meet provide percolation paths of hole. When the SPFGraphene content
the donor/acceptor interface and transported smoothly through the is 8 wt%, the best Jsc has reach 4.7 mA/cm2, the best Voc has reach
active layer. However, SPFGraphene concentration further increased 0.67 V, the best FF has reach 0.32 and the power conversion
to 8%, the SPFGraphene film can form a continuous donor/acceptor efficiency is 1.05% compared to the other devices.
interface and produce a better way to transport smoothly through
P3HT matrix. This will improve the electronic transport to form the
transport pathway of LUMO–SPFGraphene–Al. The work functions Acknowledgements
of SPFGraphene are closer to the work functions of Al; this will
decrease the barrier of Al/LUMO to form the transport pathway of We gratefully acknowledge the financial support of National
LUMO–SPFGraphene–Al. In this phase, the SPFGraphene acted as Outstanding Youth Science Foundation under Contract
the percolation paths of electron. The work functions of f-MWCNTs no. 60825407, National Natural Science Fund Project under
are closer to the work functions of ITO; this will decrease the barrier Contract no. 60877025, Beijing Science and Technology Committee
of ITO/HOMO to form the transport pathway of HOMO– under Contract no. Z08000303220803, Beijing Science and Tech-
f-MWCNTs–ITO; the hole will be transported from HOMO of P3HT nology Committee under Contract no. D090803044009001 and
to f-MWCNTs, and then transported from f-MWCNTs to ITO. Beijing Natural Science Fund Project under Contract no. 2092024.
In this phase, the f-MWCNTs acted as the percolation paths of
hole. The other reason is that the SPFGraphene acted as an electron
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