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Inverted Organic Solar Cells with ZnO Thin

Films Prepared by SolGel Method
Article in Journal of Nanoelectronics and Optoelectronics August 2010
DOI: 10.1166/jno.2010.1079

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Copyright 2010 American Scientic Publishers

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Printed in the United States of America

Journal of
Nanoelectronics and Optoelectronics
Vol. 5, 14, 2010

Inverted Organic Solar Cells with ZnO

Thin Films Prepared by SolGel Method
Hye-Jeong Park1 , Kang-Hyuck Lee1 , Brijesh Kumar1 , Kyung-Sik Shin1 ,
Soon-Wook Jeong2
, and Sang-Woo Kim1
3

1

School of Advanced Materials Science and Engineering, Sungkyunkwan University,

Suwon 440-746, Republic of Korea
2
School of Advanced Materials and System Engineering, Kumoh National Institute of Technology,
Gumi 730-701, Republic of Korea
3
SKKU Advanced Institute of Nanotechnology (SAINT) and Center for Human Interface Nanotechnology (HINT),
Sungkyunkwan University, Suwon 440-746, Republic of Korea

Keywords: Inverted Organic Solar Cell, ZnO Thin Films, Buffer Layer, SolGel Method.

1. INTRODUCTION
Inverted organic solar cells (IOSCs) that are based on bulkheterojunction (BHJ) have attracted substantial attention
due to their low cost, light-weight materials, compatibility
with exible plastic substrates, and ease of fabrication.13
However organic materials have the small excitons diffusion length and low carrier mobility. This causes the IOSCs
to reduce the efciency. An approach to reduce the problem
is to insert a buffer layer between the metal and active layers as a path for photo-generated carriers to collect at the
electrode. This buffer layer can also solve another problem
with prolonged exposure to air that can lead to oxidation
of the electrode and degradation of the active layer from
oxygen and moisture.35
The zinc oxide (ZnO) buffer layer, among metal oxide
semiconductor lms, has been widely studied in recent
years. ZnO is a good candidate for this application due to
its high electron mobility and high transparency in visiblewavelength range. Additionally, zinc oxide have interesting properties such as excellent chemical and thermal

Authors to whom correspondence should be addressed.

J. Nanoelectron. Optoelectron. 2010, Vol. 5, No. 2

stability in different environments, non-toxicity, excellent

substrate adherence, and they are inexpensive.68 A wide
variety of techniques for the deposit method of high quality ZnO thin lms have been reported, such as metalorganic chemical vapor deposition (MOCVD),9 pulsed
laser deposition (PLD),10 solgel,11
12 sputtering,13 and
electrochemical deposition.14 Among them, ZnO thin lms
on exible substrate can be deposited by easily using
the solgel method. The general advantage of the solgel
method is that it can be used for large area deposition and
processed at a low temperature. In addition, this method is
easy in its composition control, it has a low cost and it provides uniformity of the lms thickness.1517 Many recent
studies have focused on the control of the preferential orientation of ZnO thin lms in IOSCs by using a relatively
tractable solgel method. However, studies on the thickness
of ZnO thin lms have rarely been carried out.
Therefore, in this paper, we used the solgel method to
study the thickness of ZnO buffer layer in IOSCs. We studied the morphology-dependent inuences of ZnO buffer
layer on the photovoltaic performances in IOSCs, and the
thickness effect of ZnO buffer layer was explored and optimized for the IOSCs.
1555-130X/2010/5/001/004

doi:10.1166/jno.2010.1079

RESEARCH ARTICLE

The inuences of buffer layers on the performance of hybrid solar cells that are fabricated with
an active layer blend of poly (3-hexylthiophene) (P3HT) and [6, 6]-phenyl-C61-buytyric acid methyl
ester (PCBM), were investigated. The ZnO thin lms were used as an electron transport layer
in solar cells to improve the photovoltaic performances. To explore the effects of ZnO lm thickness, ZnO thin lms were deposited as an electron transport layer by spin coating them one
to four times at 4000 rpm using zinc acetate dehydrate that was dissolved in a mixed solution of 2-methoxyethanol and ethanolamine. We fabricated IOSCs on PES substrate, consist of
Au/MoO3 /PCBM:P3HT/ZnO/ITO. The optical property of the ZnO buffer layers was investigated.
Furthermore, we found the optimum ZnO buffer layer by using the solgel method to enhance the
performance of the solar cells.

Inverted Organic Solar Cells with ZnO Thin Films Prepared by SolGel Method

RESEARCH ARTICLE

2. EXPERIMENTAL DETAILS
We rst prepared ZnO sol using zinc acetate
(Zn(CH3 COO)2 ) as a source, 2-methoxy ethanol (C3 H8 O2 
as a solvent, monoethanolamine (C2 H7 NO) as a stabilizing
agent. These were stirred for one hour at 60  C. The molar
concentration of zinc acetate in the solution was 0.05 M.
The ZnO thin lms were deposited using spin coating at
4000 rpm for 50 seconds on exible substrate (ITO/PES).
The deposited lms were thermally treated at 150  C for
30 minutes in each deposition. Secondly, we prepared a
P3HT:PCBM-blended solution for active layer deposition
by spin coating it at 2000 rpm for 120 seconds. Poly(3hexylthiophene) (P3HT), used as a p-type material, and
[6,6]-phenyl C61 butyric acid methyl ester (PCBM), used as
an n-type material, were dissolved into chlorobenzene in a
weight ratio of 1:1 for one day, this making P3HT:PCBM
blended in chlorobenzene. After annealing an active layer
for 30 minutes at a temperature of 150  C, an MoO3
layer of 20 nm as a hole-elective layer2 and a 100 nm Au
layer were deposited by thermal evaporation through a
shadow mask. The structure of the IOSC was PES/indiumtin-oxide (ITO)/ZnO/P3HT: PCBM/MoO3 /Au stacked
from bottom to top, as shown in Figure 1.
The optical transmittance spectra were recorded by using
an UV-VIS spectrophotometer (Shimadza UV-3600). The
thickness and microstructures of ZnO thin lms were measured by scanning electron microscopy (SEM). Moreover,
we measured the photovoltaic performance.

3. RESULTS AND DISCUSSION

The cross section FE-SEM images of the ZnO thin lms
with the depositions from one to four (14) times are

Fig. 1. Device structure of the exible inverted OSCs. including the

short circuit current density (Jsc ), open circuit voltage (Voc ), ll factor
(FF), power conversion efciency (PCE) and series resistance (Rs ) by
AM 1.5G, 100 mW/cm2 solar simulator.

Park et al.

shown in Figure 2. The thickness of the ZnO thin lms

were estimated to be 53100 nm, 93107 nm, 120
127 nm, and 133 nm as shown in Figures 2(a)(d), respectively. The structure observed from the one-time deposit
ZnO lms had small wrinkles as shown in Figure 2(a).
The thickness of this ZnO lms was approximately 53 nm
except for the wrinkles and approximately 100 nm with
wrinkles. The thickness of the one-deposit ZnO lms on
the sample was a minimum of approximately 93 nm as
shown in Figure 2(b). This value is similar with measuring
value of thickness with wrinkles in Figure 2(a). The thickness error range of the two-deposit ZnO thin lms was
large due to a little curvature of the surface. The thickness
error range of three-deposit ZnO thin lms was reduced
to deposit a littler curvature of the surface, as shown in
Figure 2(c). The samples of the four-deposit ZnO thin
lms were measured at 133 nm of uniform thickness.
Figure 3 shows the UV-visible optical transmittance
spectra of the ZnO lms between 300 and 800 nm wavelengths. All of the ZnO lms were highly transparent in
the UV-VIS region of 400 nm to 800 nm and a sharp
fall in transmittance was observed below 400 nm due to
bandgap absorption.18 All of the lms had a higher transmittance than the ITO/PES substrate. Transmittance from
the one-deposit ZnO thin lms improved approximately
10% more than the ITO/PES substrate. The transmittance
considerably improved up to three times deposition. Furthermore, the transmittance of the four-deposit ZnO thin
lms slightly decreased as shown in Figure 3. Compared
to the surface of the ITO and ZnO thin lms, the surface
of ZnO thin lms was relatively of higher roughness than
the surface of the ITO/PES.
We performed an X-ray diffraction (XRD) measurement of an ITO/PES substrate and a ZnO lm-deposited
ITO/PES substrate. A weak feature of indium oxide
In2 O3 was observed from the ZnO-deposited lm on the
ITO/PES sample. However, we could not observe an In2 O3
peak from the ITO/PES substrate. From the XRD result,
we suggest that a few of the indium sites were present in
the ITO. It was interrupting the light to transmit through
the ITO-coated substrate. These indium sites transformed
into In2 O3 (wide bandgap semiconductor) during ZnO
lm deposition on the ITO/PES substrate, which allowed
the transmission of the visible light through the ZnOdeposited ITO/PES sample, hence higher transmittance
was observed.
We fabricated IOSCs to conrm the solar power performances based on various thickness of the ZnO buffer
layer. J V measurements were extracted using a solar simulator under an AM 1.5G solar illumination. The J V
characteristics are summarized in Figure 4 and Table I,
respectively. There was almost no change in the open circuit voltage (Voc  of these devices. The short circuit current (Jsc  increased when the thickness of ZnO thin lms
was increased. The Jsc ranges varied from 6.51 mA/cm2
J. Nanoelectron. Optoelectron. 5, 14, 2010

Park et al.

Inverted Organic Solar Cells with ZnO Thin Films Prepared by SolGel Method

(a)

(b)

(c)

(d)

Fig. 2. FE-SEM images of ZnO thin lms derived from different number of deposition: (a) 1 time, (b) 2 times, (c) 3 times, and (d) 4 times. Red and
green bar means ZnO layer and ITO layer, respectively.

Fig. 3. The transmission spectra of ZnO thin lms for four different
depositions. ZnO thin lms of A, B, C, and D were derived from 1, 2,
3, and 4 depositions.

J. Nanoelectron. Optoelectron. 5, 14, 2010

the maximum absorption is for P3HT:PCBM21 could produce a larger number of excitons, which resulted in a large
photocurrent. The highest PCE, 2.2% with Jsc and Voc of
8.6 mA/cm2 and 0.55 V, respectively, was obtained by
three-deposit ZnO thin lms. These results suggest that
photovoltaic PCE of IOSCs is affected by the optimum
thick and transparent of the ZnO buffer layer.
Figure 5 shows the J V curve in a dark condition.
The value of the sheet resistance (Rs ) increases by the

Fig. 4. The J V characteristics of the ZnO thin lms derives from a

different number of deposition under simulated solar irradiation of AM
1.5G normalized 100 mW/cm2 . ZnO thin lms of A, B, C, and D were
derived from 1, 2, 3, and 4 depositions.

RESEARCH ARTICLE

to 8.85 mA/cm2 depending on the thickness and transmittance of the ZnO thin lms. This trend could be the result
of the formation of more percolation pathways of the ZnO
buffer layer that increase the photocurrent and improve
the transport of electrons. The FF ranged from 38.6% to
45.4% depending on the thickness of ZnO thin lms. The
FF of IOSC fabricated with ZnO thin lms at three-deposit
ZnO buffer layers is higher. The ZnO buffer layer revealed
an enhancement in PCE from 1.1% to 2.2%. The enhanced
photovoltaic performance was attributed to a higher transmittance in the visible wavelength around 550 nm, where

Inverted Organic Solar Cells with ZnO Thin Films Prepared by SolGel Method
Table I. Summary of device performance.

Device
A
B
C
D

Deposition
number

Thickness
(nm)

Jsc
(mA/cm2 )

Voc
(V)

FF
(%)

PCE
(%)

1
2
3
4

53100
93107
120127
133

6.551
7.801
8.857
6.612

0.465
0.534
0.548
0.554

38.656
41.363
45.478
41.159

1.177
1.724
2.207
1.508

Park et al.

Acknowledgments: This paper was supported by the

Research Fund of Green Energy System Education Center,
Kumoh National Institute of Technology (2009-130-012)
and by the Basic Science Research Program through the
NRF funded by the Ministry of Education, Science and
Technology (2010-0015035).

References and Notes

RESEARCH ARTICLE

Fig. 5. In a condition, the J V curve of the ZnO thin lm devices from

different numbers of depositions. ZnO thin lms of A, B, C, and D were
derived from 1, 2, 3, and 4 depositions.

increasing deposition number from two times to four

times. The curve of sample A was unexpectedly in the
middle of B and C. This could be due to the highest surface roughness of sample A and fairly large wrinkles as
shown in Figure 2(a). This high surface roughness was
also the reason why Jsc was lower in sample A.

4. CONCLUSIONS
In this paper, surface morphologies and optical qualities of
ZnO thin lms that were prepared by the solgel method
were investigated and optimized for inverted inorganic
organic solar cell structures. The transmittance from onedeposit ZnO thin lms improved approximately 10% more
than the ITO/PES substrate. The transmittance improved
approximately 10% more with up to three times deposit.
We found the optimum thickness and deposited transparent ZnO buffer layer using the solgel method. The ZnO
buffer layer inuenced Jsc of the IOSCs due to the combined factors of electron mobility and light harvesting.

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Received: 30 April 2010. Accepted: 16 June 2010.

J. Nanoelectron. Optoelectron. 5, 14, 2010