Organic Electronics 11 (2010) 1864–1869

Contents lists available at ScienceDirect

Organic Electronics
journal homepage: www.elsevier.com/locate/orgel

Efficient bulk-heterojunction photovoltaic cells with transparent

multi-layer graphene electrodes
Minhyeok Choe a,1, Byoung Hoon Lee a,1, Gunho Jo a, June Park c, Woojin Park a, Sangchul Lee b,
Woong-Ki Hong a,2, Maeng-Je Seong c, Yung Ho Kahng a, Kwanghee Lee a,b,⇑, Takhee Lee a,b,⇑⇑
a
Department of Materials Science and Engineering, Gwangju Institute of Science and Technology, Gwangju 500-712, Republic of Korea
b
Department of Nanobio Materials and Electronics, Gwangju Institute of Science and Technology, Gwangju 500-712, Republic of Korea
c
Department of Physics, Chung-Ang University, Seoul 156-756, Republic of Korea

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

Article history: We present the results of applying multi-layer graphene (MLG) films as transparent con-
Received 9 August 2010 ductive electrodes in organic photovoltaic devices (OPVs). The MLG films synthesized at
Received in revised form 29 August 2010 different growth temperatures by chemical vapor deposition were applied to OPVs. The
Accepted 30 August 2010
performance of OPVs with 1000 °C-grown MLG films was found to be the best with a power
Available online 9 September 2010
conversion efficiency (PCE) of 1.3%. The PCE was further enhanced when a hole-blocking
TiOX layer was inserted in the device structure, resulting in a PCE of 2.6% which is a sig-
Keywords:
nificantly higher efficiency compared to other previously reported graphene-adopted pho-
Graphene
Photovoltaics
tovoltaic cells. Our demonstration of the PCE-increase in the graphene-electrode OPVs may
Transparent electrode foster the application of the fast-progressing graphene technology toward more practical
TiOX OPV technology.
Chemical vapor deposition Ó 2010 Elsevier B.V. All rights reserved.

1. Introduction mechanical exfoliation of graphite crystals, reduction of

graphene oxide films, and growth by chemical vapor depo-
Graphene, a two-dimensional sheet of covalently sition (CVD) [6–11]. In this study, we used the CVD method
bonded carbon atoms, has been attracting great attention for graphene production. This method offers several advan-
in the field of optoelectronics of organic and inorganic tages, including the capability to grow large and continuous
materials. This is because of its outstanding electronic, opti- uniform films with low sheet resistances, transferability to
cal, and mechanical properties, such as quantum electronic arbitrary substrates, and controllability of the synthesized
transport properties, transparency, mechanical and chemi- film properties. It has been reported that the graphene films
cal stability, stretchability, and flexibility [1–6]. Currently, produced by CVD typically have sheet resistances of 300–
graphene films that can be deposited on arbitrary sub- 1000 X/h and mobilities of 300–4000 cm2/V s [4,8,9].
strates are prepared by various techniques, including In this work, our focus is on the application of graphene
films as the electrodes in organic photovoltaic cells. In the
⇑ Corresponding author at: Department of Materials Science and optoelectronics, the need for a noble material to replace in-
Engineering, Gwangju Institute of Science and Technology, Gwangju dium tin oxide (ITO) that can be produced cheaply while
500-712, Republic of Korea. Tel.: +82 62 715 2325; fax: +82 62 715 2304. providing high transparency and conductivity has emerged
⇑⇑ Corresponding author at: Department of Materials Science and [12,13]. Graphene films potentially fulfill all of these re-
Engineering, Gwangju Institute of Science and Technology, Gwangju quired properties and are therefore currently being vigor-
500-712, Republic of Korea. Tel.: +82 62 715 2313; fax: +82 62 715 2304.
ously researched [4,5,10,11,14–23]. Wang et al. [11] first
E-mail addresses: klee@gist.ac.kr (K. Lee), tlee@gist.ac.kr (T. Lee).
1
These authors contributed equally to this work.
reported the application of graphene films in dye-sensi-
2
Present address: Nanoscience Centre, University of Cambridge, tized photovoltaic cells and obtained a power conversion
Cambridge CB3 0FF, UK. efficiency (PCE) of 0.26%. A number of reports followed.

1566-1199/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.orgel.2010.08.018
 M. Choe et al. / Organic Electronics 11 (2010) 1864–1869 1865

Tung et al. [5] reported organic bulk-heterojunction (BHJ) was rapidly cooled to room temperature (>200 °C/min ini-
photovoltaic cells with modified graphene films compos- tially and slower later) to suppress excessive precipitation
ited with carbon nanotubes and demonstrated a 0.85% of carbon atoms. Finally, the graphene film was released
PCE. More recently, Wang et al. [14] used functionalized from the Ni substrate by etching Ni in an aqueous solution
graphene films in organic BHJ photovoltaic cells and re- of iron chloride (FeCl3) [4]. The CVD-synthesized MLG film
ported an improved PCE of 1.71%. Overall, BHJ photovoltaic was transferred onto a glass substrate to form the
cells with graphene electrodes have exhibited PCEs below anode for OPV. Before a poly(3,4-ethylenedioxythiophene)
2% to date [5,11,14–17]. These PCEs are only proof-of- poly(styrenesulfonate) (PEDOT:PSS) layer was spin coated
concept and are far below the best performance obtained on top of the graphene film, the graphene film was under-
from organic solar cells made with ITO electrodes. Values gone an ozone treatment to produce the hydrophilic sur-
of 6.1% [24], with a BHJ structure, and 6.5% [25], with a face, which was a necessary step to increase the coating
tandem cells structure, have both been reported by the efficiency of PEDOT:PSS on graphene. Next, the photo-
research group of Heeger and Lee, one of co-authors of this active BHJ composite of poly(3-hexylthiophene) (P3HT)
paper. Recently, a PCE of 6.7% has been reported from an and [6,6]-phenyl-C61 butyric acid methyl ester (PCBM)
organic BHJ structure with low bandgap polymers having was spin coated on top of the PEDOT:PSS layer. Then, a
an enhanced open-circuit voltage [26,27]. On the contrary, TiOX film was spin coated for some devices. Finally,
the poor performance of photovoltaic cells incorporating aluminum was thermally evaporated to form the cathode.
graphene electrodes is apparently due to the poor quality A cross-sectional high-resolution transmission electron
of graphene films: high sheet resistances and interfacing microscopy (HRTEM) image of a prepared photovoltaic cell
problems with the active layers. (Fig. 1(b)) clearly shows that the individual layers were
In this paper, we report an application of CVD-synthe- nicely formed with distinctive interfaces; the TiOX film
sized multi-layer graphene (MLG) films incorporated as and MLG film are shown in the upper and lower inset of
transparent and conductive electrodes of organic BHJ pho- Fig. 1(b), respectively.
tovoltaic cells (OPVs). Particularly, the growth temperature
of the graphene films was studied as a control paramter on
the PCE of the graphene-OPVs. Overall, the MLG films 3. Results and discussion
showed good performance as electrodes for OPVs, and
among tested graphene-OPVs the1000 °C-grown MLG 3.1. Characteristics of multi-layer graphene films
films were found to yield the best PCE. Furthermore, when
a thin sol–gel processed titanium sub-oxide (TiOX) layer Before applying the MLG films in photovoltaic cells, we
was inserted in the cell, the PCE was further increased to investigated the properties of these films using various
2.60%. Our results show the control of the graphene film techniques. To determine the morphological features and
quality and the cell structure optimization with a TiOX thicknesses of the MLG films, we used an atomic force
layer can increase the performance of OPVs beyond the microscope (AFM) to image a transferred MLG film on a
proof-of-concept level. 300-nm-thick SiO2 layer on a Si substrate, as shown in
Fig 2(a). The thinnest part measured on our graphene film
is 1.13 nm, as shown in the cross-sectional profile in
2. Experimental Fig. 2(b). This thickness corresponds to the thickness of a
monolayer; due to the chemical contrast between graph-
The device structure of a photovoltaic cell with graph- ene and substrate, the monolayer thickness has been mea-
ene as a transparent and conducting electrode is shown sured as 1 nm by AFM [7,9,28–30]. Fig. 2(c) shows the
in Fig. 1(a). To synthesize graphene films, 300 nm thick TEM images for a graphene film. Our graphene films con-
Ni-deposited substrates were placed into the CVD chamber sisted of mono to multi-layer regions and contained rip-
and heated to 800, 900, or 1000 °C under the flow of a 4% pled regions, as marked by a square in the lower image.
H2 in Ar gas mixture. Then, a graphene film was grown By counting the number and the distance of the bright
by adding CH4 gas to the flow. After growth, the substrate and dark stripes in the rippled region, the number of

(a) (b) Al TiOX

TiOX

10 nm
P3HT:PCBM

50 nm
Graphene
PEDOT:PSS
PEDOT:PSS Graphene
Graphene 10 nm
Glass

Fig. 1. (a) Schematic diagram of the photovoltaic device structure with MLG electrodes and a hole-blocking TiOX layer. (b) TEM cross-sectional image of a
photovoltaic device. The insets show HRTEM images near the TiOX layer (top) and near the MLG films (bottom).
1866 M. Choe et al. / Organic Electronics 11 (2010) 1864–1869

grown at three different temperatures (Fig. 3). Raman

(a) spectroscopy is a non-destructive analysis tool which pro-
vides high-throughput and unambiguous identification of
SiO2 Graphene the properties of graphene films with three most intense
peaks: D peak at 1350 cm 1, G peak at 1580 cm 1,
and 2D peak at 2700 cm 1 [32–34]. Our CVD-grown
graphene films typically showed multi-layer-type Raman
features (i.e., G-peak intensity > 2D-peak intensity) and
small D peaks that were related to defects on MLG. The
integrated intensity ratios of the observed Raman peaks
are shown in Fig. 3(b) and (c). The ratios of the G-peak
intensity to the 2D-peak intensity (IG/I2D) shown in Fig
500 nm 3(b) indicate that the average thickness of the graphene
film increased as the growth temperature increased since
the higher ratio corresponds to the thicker graphene film.
The ratios of the D-peak intensity to the G-peak intensity
(ID/IG) shown in Fig. 3(c) correspond with the average den-
(b) sity of defects [33–35], and these ratios indicate that the
3 defect density decreased as the growth temperature in-
2.43 nm
creased. From the comparison of Raman peak ratios, we
conclude that the growth temperature significantly affects
Height (nm)

2 the properties of the graphene in terms of the film thick-

1.13 nm ness and defect density.
Furthermore, the film property that is directly relevant
1
to the performance of the organic photovoltaics was inves-
tigated: the optical transmittances and the sheet resis-
0 tances of the MLG films synthesized at three different
growth temperatures. Results are summarized in Fig. 4.
0 1 2 Fig. 4(a) shows the representative transmittances of MLG
Distance (μm) films prepared at different growth temperatures and the
inset shows the transmittance of 90.7 ± 1.5, 88.8 ± 2.2,
and 86.9 ± 1.2% at 515 nm wavelength according to the
(c) growth temperatures of 800, 900, and 1000 °C, respec-
tively. The plot of mobility versus resistance, shown in
Fig. 4(b), was obtained by taking the statistical means
and standard deviations of 8–10 synthesized-MLG films
at each growth temperature. As expected from Raman
10nm analysis, higher temperature grown thicker MLG films
yielded less transparency and lower sheet resistance. Spe-
Multi layer cifically, MLG films prepared at growth temperatures of
800, 900, and 1000 °C showed the sheet resistances of
Graphene 1730 ± 600, 990 ± 400, and 610 ± 140 X/h, and the mobil-
Ripple ity of 660 ± 270, 1030 ± 440, and 1180 ± 260 cm2/V s
respectively. Furthermore, we measured the work function
100 nm of the MLG films by using a Kelvin probe measurement
system. As shown in Fig. S2(b) in Supplementary material,
Fig. 2. (a) AFM image of a MLG film showing the edge of the MLG layers
the work function of the graphene films was 4.45 ± 0.04 eV
(dashed) on a SiO2 substrate. (b) Topographic height profiles across the and did not change significantly with the growth tempera-
solid line indicated in (a). (c) TEM image of a region of MLG. The insets ture change.
show an HRTEM image of the rippled region (top left) and an electron
diffraction pattern (top right) of MLG.
3.2. Performance of the organic photovoltaic cells with
graphene electrode
graphene layers (15) and the interlayer distance
(3.5 ± 0.1 Å) were obtained; the results were found consis- Fig. 5(a) shows the representative current density–volt-
tent with values reported previously [9,31]. The electron age (J–V) data of the fabricated OPVs without TiOX layers
diffraction (ED) pattern (upper right inset, Fig. 2(c)) taken under AM 1.5 G irradiation by a solar simulator with an
on a monolayer region shows a hexagonal spot pattern, irradiation intensity of 100 mW/cm2. The three different
confirming the threefold symmetry of the arrangement of MLG films prepared at different growth temperatures
carbon atoms in the graphene film. (800, 900, and 1000 °C) were used to compare the perfor-
Raman spectroscopy using the 514 nm line of an Ar+ mance as electrodes in OPVs. The best performance was
laser was used to analyze the properties of MLG films achieved from the devices using MLG films that were
 M. Choe et al. / Organic Electronics 11 (2010) 1864–1869 1867

(a) 514 nm
G

Intens ity (a.u.)

2D
D 800oC

900oC

1000oC

1500 2000 2500 3000

Raman Shift (cm-1)

(b) 1.8 (c) 0.9

1.6
IG / I2D

ID / IG
0.8
1.4

1.2
0.7
800 900 1000 800 900 1000
Temperature (oC) Temperature (oC)

Fig. 3. (a) Raman spectra of MLG films synthesized at different growth temperatures (800, 900, and 1000 °C). (b) Integrated intensity ratios of G peak and
2D peak (IG/I2D), and (c) of D peak and G peak (ID/IG) as a function of growth temperature. These integrated intensity peaks are from the Raman spectra of
graphene films.

(a) 95
o
(b) o
800 oC 1500 800 oC
Transmittance (%)

Mobility (cm2/ Vs)

900 oC
90 1000 C 900 oC
1000 C
1000
Transmittance (%)

93 515 nm
85 90
87 500
80 84
800 900 1000 o
Temperature ( C)
0
500 750 1000 1250 500 1000 1500 2000 2500
Wavelength (nm) Sheet Resistance (Ω )

Fig. 4. (a) Transmission spectra of MLG films. The inset shows the transmittance of 90.7 ± 1.5, 88.8 ± 2.2, and 86.9 ± 1.2% at 515 nm wavelength, 800, 900,
and 1000 °C, respectively. (b) Mobility versus sheet resistance of MLG films prepared at different growth temperatures (800, 900, and 1000 °C).

(a) (b)
0 60
90
Absorption (%)
J (mA/cm2 )

IPCE (%)

40
-3 60
o
800 oC 20 30
-6 900 oC
1000 C
0 0
0.0 0.2 0.4 0.6 400 600 800
Voltage (V) Wavelength (nm)

Fig. 5. (a) J-V curves of photovoltaic cells with MLG films grown at different growth temperatures under AM 1.5 G irradiation conditions. (b) Incident
photon-to-current efficiency (IPCE) and absorption spectra of a photovoltaic device fabricated with a 1000 °C-grown MLG film.

prepared at 1000 °C. Specifically, for the case of the (FF) of 0.35. These values yielded PCE = JSCVOCFF/Pinc (here
1000 °C-graphene OPV, the representative parameters ob- Pinc is the intensity of incident light) of 1.34%. The param-
tained were short-circuit current density (JSC) of 6.25 mA/ eters for the devices with graphene films prepared at 800
cm2, open-circuit voltage (VOC) of 0.62 V, and fill factor and 900 °C are summarized in Table 1. Fig. 5(b) compares
1868 M. Choe et al. / Organic Electronics 11 (2010) 1864–1869

Table 1 optical spacer [36,37] and facilitates better transport of

Summary of the performance parameters of graphene-electrode organic charge carriers to each electrode as a hole-blocking layer
photovoltaic devices fabricated with graphene films that were synthesized
at different growth temperatures (800, 900, and 1000 °C) and ITO-electrode
[24,25,38,39], thereby increasing JSC. Recently, Roy et al.
devices. Short-circuit current density (JSC), open-circuit voltage (VOC), fill [37] have compared the calculated and the experimentally
factor (FF), and power conversion efficiency (PCE) are listed. The improve- measured total absorption spectra of photovoltaic devices
ment of the performance parameters by the insertion of the TiOX layer as a with and without the TiOX layer and confirmed the effect
hole-blocking layer (HBL) was compared in all the device types.
of the TiOX layer as an optical spacer. Also, Cho et al. [38]
Temp. (°C) HBL VOC (V) JSC (mA/cm2) FF PCE (%) have demonstrated the hole-blocking property of TiOX
800 – 0.62 1.11 0.25 0.17 using multilayer bipolar field-effect transistors (FETs). In
800 TiOx 0.59 6.45 0.32 1.22 their device, the TiOX layer was inserted to separate the
900 – 0.59 4.54 0.26 0.70 n-channel material and the p-channel material. Because
900 TiOx 0.62 7.57 0.46 2.13
the TiOX layer retained the injected holes within the p-
1000 – 0.62 6.25 0.35 1.34
1000 TiOx 0.60 9.03 0.48 2.60 channel material and transferred the injected electrons
ITO – 0.63 7.50 0.50 2.34 into the n-channel material, their device successfully
ITO TiOx 0.63 9.02 0.67 3.80 showed the J–V characteristics. As a result, the PCE of our
photovoltaic devices with TiOX was improved by the ef-
fects of the TiOX layer both as an optical spacer and as a
the incident photon-to-current collection efficiency (IPCE) hole-blocking layer. Moreover, the TiOX layer reduced the
spectrum and absorption spectrum of a device fabricated contact resistance between the aluminum cathode and
using MLG films prepared at 1000 °C. The graphene-elec- the P3HT:PCBM photo-active layer, consequently increas-
trode photovoltaic cell without a TiOX layer showed the ing the FF in the device. Fig. 6(b) presents detailed statisti-
typical spectral response of P3HT:PCBM composites with cal data for PCE values that were statistically determined
a maximum IPCE of approximately 57% at 515 nm. from all the measured graphene-electrode devices in com-
The performance of the graphene photovoltaic devices parison with the ITO-electrode devices, with and without
was further enhanced when a TiOX film was added be- the TiOX layers. Each statistical value in Fig. 6(b) was ex-
tween the aluminum cathode and the photo-active layer. tracted from all the measured devices shown in the Sup-
Fig. 6(a) compares the J–V curves of the photovoltaic de- plementary material (Fig. S1). For devices without the
vices with 1000 °C-grown MLG electrodes and with ITO TiOX layer, the PCEs (the mean and standard deviation) of
electrodes with and without the TiOX layer. The perfor- the photovoltaic devices were determined as 0.19 ± 0.08,
mance parameters obtained from the MLG-electrode de- 0.56 ± 0.10, and 1.38 ± 0.35% with the graphene-electrodes
vices with the TiOX layer shown in this figure are JSC of grown at 800, 900, and 1000 °C, respectively, in compari-
9.03 mA/cm2, VOC of 0.60 V, and FF, which was dramatically son to 1.20 ± 0.27, 1.79 ± 0.31, and 2.58 ± 0.45% for the de-
increased, of 0.48. The corresponding PCE was significantly vices with TiOX layer and the graphene-electrodes grown
increased to 2.60%. Such performance enhancement by at 800, 900, and 1000 °C, respectively. Also, we found that
adding a TiOX film was also observed in photovoltaic cells the PCE of the ITO-electrode photovoltaic devices without
with ITO electrodes. The representative parameters ob- TiOX was 2.53 ± 0.42% compared to 3.74 ± 0.31% of those
tained for the case of the ITO-electrode devices with the with TiOX. It can be noticed that the PCEs for ITO-electrode
TiOX layer were JSC of 9.02 mA/cm2, VOC of 0.63 V, and FF devices were higher than those for graphene-electrode de-
of 0.67, and the PCE was determined as 3.80%. The vices, partly due to higher conductivity of ITO film than
enhancement of PCE for our graphene-electrode and ITO- that of graphene films. Furthermore, the best PCE observed
electrode photovoltaic devices by inserting a TiOX layer was 3.63% from a 1000 °C-grown graphene-electrode de-
can be explained by the role of the TiOX layer that creates vice with the TiOX layer. However, this value was outside
a higher density of photo-generated charge carriers as an of the one sigma criterion, i.e., the 3.63% value was beyond

(a) (b)
ITO 4 filled symbol : pristine
0 with TiOX open symbol : with TiOX
J (mA/cm2 )

1000 oC 3
PCE (%)

-3 with TiOX
2
-6
1
-9
0
0.0 0.2 0.4 0.6 800 oC 900 oC 1000 oC ITO
Voltage (V) Device Types

Fig. 6. (a) J–V curves of photovoltaic devices with 1000 °C-grown MLG electrodes (circles) and with ITO electrodes (diamonds). The curves without the TiOX
layer (filled symbols) are compared to the ones with the TiOX layer (open symbols). (b) The PCEs for graphene-electrode photovoltaic devices in comparison
with those for the ITO-electrode photovoltaic devices with the TiOX layers and without the TiOX layers (pristine). This statistical means and standard
deviations were extracted from Supplementary material. The types of the devices are indicated on the x-axis (800, 900, and 1000 °C: graphene-electrode
devices, ITO: ITO-electrode devices).
 M. Choe et al. / Organic Electronics 11 (2010) 1864–1869 1869

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