ARTICLE IN PRESS
Solar Energy Materials & Solar Cells 94 (2010) 11521156
Contents lists available at ScienceDirect
Solar Energy Materials & Solar Cells
journal homepage: www.elsevier.com/locate/solmat
Improved photovoltaic effect of polymer solar cells with nanoscale
interfacial layers
Young In Lee a, Mina Kim a, Yoon Ho Huh a, J.S. Lim b, Sung Cheol Yoon b, Byoungchoo Park a,
a
b
Department of Electrophysics, Kwangwoon University, Wolgye-Dong, Nowon-gu, Seoul 139-701, Republic of Korea
Advanced Materials Division, Korea Research Institute of Chemical Technology (KRICT), Republic of Korea
a r t i c l e in f o
a b s t r a c t
Article history:
Received 3 November 2009
Received in revised form
26 February 2010
Accepted 28 February 2010
Available online 21 March 2010
In poly(3-hexylthiophene):methanofullerene bulk-heterojunction polymer photovoltaic (PV) cells, we
introduced nanoscale interfacial layers between the PV layer and the cathode. The nanoscale interfacial
layers were made of ultrathin poly(oxyethylene tridecyl ether) surfactant and low-work-function alloy
metal of Al:Li layers. It was found that the nanoscale interfacial layers increase the photovoltaic
performance: increasing short-circuit current density with ll factor and improving device stability. For
PV cells with the nanoscale interfacial layers, an increase in power conversion efciency of 4.18 70.24%
was achieved, compared to that of the control devices (3.89 7 0.08%).
& 2010 Elsevier B.V. All rights reserved.
Keywords:
Polymer
Photovoltaic
Interfacial layers
Nanomaterials
1. Introduction
Recently, important research has been conducted on the
development of polymer solar cells (PSCs) for realizing high
efciency in generating electrical power by absorbing light [15].
Among the desired developments, an interesting one for the
efcient photoinduced charge generation of the photovoltaic (PV)
layer is the bulk heterojunction PSC structure [2,3], which is
composed of a conjugated polymer and fullerene composite layer.
Using the bulk heterojunction structure together with pre- or
post-thermal annealing of PV layers of poly(3-hexylthiophene)
(P3HT) and phenyl C61-butyric acid methyl ester (PCBM), PSCs
with a power conversion efciency (PCE) of 34% were demonstrated [4,5]. More recently, it was reported that the efciency can
be increased dramatically up to 6:77% by using a low-band gap
polymer cell [6]. The use of these PSC technologies should result
in much lower costs for high-speed solution-coating processes,
such as the roll-to-roll process (abbreviated R2R) [7,8]. However,
for practical applications, the efciency of PSCs needs to be
improved further with good environmental stability. In order to
achieve this goal, the electrical contact at the interfaces between
the PV layer and the electrodes also has to be optimized. To achieve
better electrical contact, it has been common practice to modify the
electrodes. At the indium tin oxide (ITO) anode side, a buffer layer
of poly(3,4-ethylene dioxylene thiophene):poly(styrene sulfonic
acid) (PEDOT:PSS) [9] or self-assembled monolayers [10],
Corresponding author. Tel.: + 82 2 940 5237; fax: +82 2 943 3208.
0927-0248/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.solmat.2010.02.045
has been used to tune the electrical contact of the ITO. At the
cathode side, an ultrathin LiF [11] or poly(ethylene oxide) [12]
layer has been placed between the PV layer and the cathode to
form a favorable dipole layer, which results in improved electron
collection. As a representative example, an efciency of 3:3%
was reported for PSCs with a LiF interfacial layer [11]. Recently,
instead of a LiF interfacial layer, a multifunctional inorganic layer
of TiOx [13] or ZnO [14] was provided as a hole-blocking barrier,
an optical spacer, and oxygen barrier. The use of these inorganic
lms resulted in signicantly improved device efciency and
stability. A PCE of 4.2% was reported when using ZnO lm with
the dipolar layer [14]. However, the electrical properties of
inorganic lms depend strongly on the conditions of processing
and their fabrication is complex. These may be limiting factors for
fabricating highly efcient devices. Thus, the improvements made
so far with respect to the efcient transfer of electrons in PSCs
remain inadequate. Hence, to improve PSCs further, we initiated
work related to the interfacial layer. In this study, to improve the
collection of electrons at the cathode side, we used nanoscale
interfacial layers, which consisted of (i) a ultrathin surfactant of
poly(oxyethylene tridecyl ether) (PTE) and (ii) a low-workfunction metal alloy (Al:Li) layer, as shown in Fig. 1. Because of
the low highest-occupied-molecular-orbital (HOMO) ( 8.1 eV)
and high lowest-unoccupied-molecular-orbital (LUMO) ( 2.1 eV)
levels of PTE [15], it may be surmised that the nanoscale
interfacial layers of (PTE/Al:Li) can modify the charge carrier
injection and transport at the electrode interface. In previous
work, nanoscale double interfacial layers (DILs) were also used to
improve the performance of organic light-emitting diodes [15].
ARTICLE IN PRESS
Y.I. Lee et al. / Solar Energy Materials & Solar Cells 94 (2010) 11521156
2.1
Al:Li (1 nm) / Al
A
V
PTE
PTE (1~2 nm)
P3HT:PCBM PV Layer
PEDOT:PSS
ITO
Glass substrate
ITO
4.4
~
4.7
3.0
3.1
3.7
Al:Li
12
HO (
PEDOT:PSS
1153
Al
4.2
P3HT
4.9
5.1
~
5.4
PCBM
6.1
PTE
8.1
Fig. 1. (Left) Device structure and (right) energy band diagram for the studied polymer solar cells with nanoscale interfacial layers.
2. Experimental details
For the experiments, P3HT (Aldrich, regiospecic ratio Z99:5%),
as the electron donor and PCBM (Rieke Metals, Inc.), as the electron
acceptor were used as received. The chemical structures of P3HT and
PCBM are shown in elsewhere [4,5]. P3HT (1.20 wt%) and PCBM
(0.88 wt%) were added to a solvent of 1, 2-dichlorobenzene to blend
a PV solution [16]. An ITO layer (80 nm, 30 O=square) on glass
substrate was used as an anode, as shown in Fig. 1. After routine
cleaning of the substrate using ultraviolet-ozone treatment, the
blended PV solution was spin-coated on top of the ITO, precoated
with PEDOT:PSS buffer layers. The PV layer was about 85 nm thick.
In order to form the rst ultrathin interfacial layer of PTE (C13H27
(OCH2 CH2)12OH, Aldrich), a PTE solution (0.1 wt% in distilled water)
was further spin-coated (12 nm) on top of the underlying PV layer.
(Details of the thickness of the PTE layer will be reported elsewhere.)
After spin-coating, all coated lms were baked at 120 1C for 3 min.
For the second interfacial layer, a 1 nm thick Al:Li alloy
(Li: 0.1 wt%) layer was formed on the PTE layer via thermal
deposition (0.5 nm/s) at a base pressure below 2 10 6 Torr.
Finally, a pure Al ( 50 nm thick) cathode layer was formed on the
interfacial layers under vacuum. Thus, the sample PSC device
fabricated has the structure of ITO/PEDOT:PSS/P3HT:PCBM/PTE
(12 nm)/Al:Li (1 nm)/Al with active area of 3 3 mm2. For
comparison, we also fabricated a control device without the PTE
interfacial layer, i.e. ITO/PEDOT:PSS/P3HT:PCBM/Al:Li (1 nm)/Al.
For post-thermal annealing, the fabricated PSC was annealed
at 150 1C for 10 min to induce the crystallization of the PV layer
[4,5]. It should be noted that, except for the PTE interfacial layer,
the control device was fabricated in exactly the same way as the
sample cell. The optical properties of the PV layers were
investigated via UV-vis spectrometry at room temperature with a
Cary 1E (Varian) UVvis spectrometer. The performance of the PSCs
was measured under an illumination intensity of 100 mW/cm2
generated by an AM1.5 light source (Newport, 96000 Solar
Simulator). The photocurrentvoltage (J V) characteristics were
measured with a source meter (Keithley 2400) and calibrated by
using a reference cell (Bunkoh-keiki, BS-520). The incident photonto-current collection efciency(IPCE) spectra were measured using
an IPCE measurement system (Titan Electro-optics Co.,
QE-IPCE 3000).
3. Results and discussion
First, the optical characteristics of the PV layers were observed
by UVvis absorption spectroscopy. Fig. 2 shows the normalized
absorption spectra of PV layers after thermal annealing at 150 1C
for 10 min. It is clear from the gure that the P3HT:PCBM PV lm
Fig. 2. Normalized UVvis absorption spectra of PV layers of P3HT:PCBM without
(black dotted curve) and with (blue solid curve) a PTE interfacial layer after
heating treatment at 150 1C for 10 min.
shows strong absorption spectra with absorption peak centered at
around 507 nm with the pronounced three vibronic absorption
peaks at ca. 600 nm. This absorption in the visible region is
attributed mainly to the P3HT polymer because PCBM shows
strong absorption in the UV region. It is noted that the
improvement in the ordering of P3HT polymer with thermal
annealing can be conrmed from the pronounced three vibronic
absorption peaks. As shown in the gure, these results are almost
identical to those of the P3HT:PCBM PV lm with the PTE
interfacial layer. Thus, it indicates that the PTE interfacial layer
does not alter the optical absorption characteristics of the PV layer
of P3HT:PCBM.
Next, the effect of the interfacial layers on the performance of
the current versus voltage (J V) characteristics for the PSCs was
investigated, as shown in Fig. 3. Fig. 3(a) shows the dark current
characteristics of the PSCs under study. Both of the devices that
we tested show an excellent rectication ratio and thus good
coverage for the organic layers. However, as shown in the gure,
the tested PSCs show a small but clear difference in current ow,
which implies that there is a clear difference in the extraction of
charge carriers through the interfacial layers. Thus, to see the PV
effect of the studied devices, J V curves under illumination were
also observed, as shown in Fig. 3(b). For the case of the control PSC
devices without the PTE interfacial layer, fairly good performance
was observed with an open-circuit voltage (VOC) of 0.6170.01 V
and a short-circuit current density (JSC) of 11.1170.17 mA/cm2
ARTICLE IN PRESS
1154
Y.I. Lee et al. / Solar Energy Materials & Solar Cells 94 (2010) 11521156
Fig. 4. IPCE spectra of P3HT:PCBM solar cells without (dotted curve) and with
(solid curve) the PTE interfacial layer.
Fig. 3. The J V characteristics of the PSCs with different interface layer structures
(a) in the dark and (b) under light illumination. (c) The J V curves of the
illuminated photocurrent for extended reverse bias. The linear lines represent
linear ts.
with a ll factor (FF) of 57.34 71.11%. This corresponds to a PCE
of 3.8970.08%, which is comparable to that reported in previous
studies [4]. By contrast, for the sample cells with nanoscale
interfacial layers comprised of (PTE/Al:Li), the VOC was
0.6370.01 V and the JSC increased to 11.22 70.29 mA/cm2 with
a FF of 59.7771.09%. Thus, the efciency of the sample solar cells
with interfacial layers comprised of (PTE/Al:Li) increases to
4.1870.24%. These values are the averages and standard
deviations of four to ve individual PSCs on independent
substrates for both device congurations. From these results,
one can see that the device with the nanoscale interfacial layers
yields increases in JSC and FF. These increases lead to an
improvement of PCE by up to 107%. Note that, for the
nanoscale interfacial layers, when the thickness of each layer,
i.e., the PTE layer and Al:Li layer, changes from 122 nm the
efciency begin to decrease. We also focused on losses of charges
by recombination, which has a critical inuence on the charge
separation and transport. The losses in the JSC that are due to
monomolecular recombination were estimated from the
dependence of the current on negative voltage [17], as shown in
Fig. 3(c). For the control device and the sample cells with
(PTE/Al:Li) interfacial layers, the losses in the JSC were estimated
at 3.48 71.47% and 2.6072.50%, respectively. These losses of JSC
are relatively small, which indicates that little monomolecular
recombination occurred in both devices. This yields evidence that
there is no signicant difference in recombination mechanisms
between the studied PSC devices.
The performance of the interfacial layers was also evaluated by
measuring the IPCE spectra. The observed IPCE spectra of the PSC
devices are shown in Fig. 4. Both PSCs shows the well-known
spectral response of its BHJ composite and are in good agreement
with the absorption spectra of the PV composites (Fig. 2). As
shown in Fig. 4, the PSC device structure of ITO / PEDOT:PSS/
P3HT:PCBM/PTE/Al:Li/Al has the higher IPCE with a maximum of
ca. 64.1% at 480 nm than that of ca. 62.8% for the control device.
This interesting result is the substantial contribution to the IPCE
of the PTE interfacial layer on the PV layer. Given that the UVVis
absorption results (Fig. 2) show no signicant differences between
the sample and control device structures, this increased IPCE can
be attributed to the improvement of the carrier injection and
transport at the electrode interface. By coating PTE interfacial
layer on the PV layer, the oriented dipole effect [14] of the dipolar
OH groups in the PTE molecules along normal to the surface may
contribute to the efcient carrier injection and transport at the
interface via the reduction of the potential barrier between the PV
layer and the Al cathode.
Next, in order to understand the electrical performance of the
PTE interfacial layer, the owing current density versus applied
electric eld (J E) characteristics for hole-only and electron-only
devices with the PTE interfacial layers were investigated
at T 300 1K, as shown in Fig. 5. For hole-only devices, we
used a (ITO/PEDOT:PSS/P3HT:PCBM/Au) structure and a
ARTICLE IN PRESS
Y.I. Lee et al. / Solar Energy Materials & Solar Cells 94 (2010) 11521156
1155
Fig. 6. 3-D topographical AFM images of P3HT:PCBM lms without (upper) and
with (lower) the PTE interfacial layer after annealing at 150 1C.
Fig. 5. The J E characteristics of hole-only devices (a) and electron-only devices
(b) with different interfacial layers.
(ITO/PEDOT:PSS/P3HT:PCBM/PTE/Au) structure. As shown in
Fig. 5(a), the hole-only device with the PTE interfacial layer
shows a greatly reduced hole-current ow, which conrms that
the presence of the PTE interfacial layer on the PV layer can block
the hole current efciently. In order to estimate the electron
transfer, we also tested electron-only devices with structures of
(Al/P3HT:PCBM/Al:Li/Al) and (Al/P3HT:PCBM/PTE/Al:Li/Al). As
shown in Fig. 5(b), the electron-only device with the PTE
interfacial layer shows an increased electron-current ow. Thus,
charge carriers can be selectively transported through the PTE
interfacial layer, blocking the holes and transporting the
electrons. Thus, these electric effects of the PTE layer at the
interface between the PV layer and the cathode can contribute to
the collection of electrons, thereby improving PSC performance.
Next, we also observed atomic force microscopy (AFM)
topographic images of the surfaces for the PV layers formed on
at glass substrates by scanning in the static force mode. Fig. 6
shows the AFM surface images for the spin-coated P3HT:PCBM
layer (upper gure) and the P3HT:PCBM layer after coating the
PTE interfacial layer (lower gure). Compared with the smooth
surface of the P3HT:PCBM layer, which has roughness at the
nanoscale, it is clear that a fairly smooth surface with the
nonoscale roughness was also formed on the P3HT:PCBM layer
coated with a PTE surfactant layer. This is in contrast to that
Fig. 7. Comparison of the relative PCE as a function of the storage time for the PSCs
with (open circles) and without (closed circles) the PTE interfacial layer. The
dotted and solid curves are least-squares ts of the stretched exponential decays.
which was observed by AFM with respect to the behavior of PTE
surfactant on polymer lm [18]; there was no spike orientation of
PTE on the PV lm in this study due to the difference in surface
interactions. Thus, it is also easy to judge that, coating the PV layer
with the PTE surfactant does not change the surface quality of the
P3HT:PCBM PV layer.
Finally, we also investigated the storage lifetime of the PSC
with different interfacial layers. Fig. 7 shows a linear-log plot of
the storage lifetime for the studied PSCs. Immediately after
fabrication, the tested PSCs were encapsulated in a nitrogen
glovebox ( r 2 ppm of H2O and O2) with a glass cap that was
sealed with an epoxy resin. A desiccant was incorporated inside
the package. The devices were kept in the dark under open-circuit
condition between measurements. The operational lifetimes of
ARTICLE IN PRESS
1156
Y.I. Lee et al. / Solar Energy Materials & Solar Cells 94 (2010) 11521156
the encapsulated devices were measured under intermittent
illumination (solar simulator, 100 mW/cm2, AM1.5G) at a
temperature of 26.17 2.0 1C and a relative humidity of
74.779.7%. As shown in gure, the storage lifetime of the PSC
clearly exhibits the stretched-exponential relaxation [19],
indicating a broad distribution of relaxation times. Moreover, it
is clear that the lifetime of a PSC with a PTE interfacial layer is
much longer than that of the control device, which implies that
the PTE surfactant interfacial layer may lead to increased device
stability. Because the encapsulation of the tested devices
signicantly inhibits the degradation process that is due to
oxygen and water [20,21], the degradation of the tested device
may be caused by other factors, such as diffusions of cathode
materials into the active layer. The diffusion of Al (and/or Li,
perhaps) cathode atoms and impurities into the PV active layer
may act as a recombination site and hence accelerate device
degradation [21]. Thus, the PTE surfactant interfacial layer may
protect the PV active layer effectively against the diffusion or
migration of Al (and/or Li) atoms into the PV layer through the
interaction between OH group of PTE and metal atoms (OH:Al
and/or OH:Li). The above results conrm that the device
performance due to the (PTE/Al:Li) nanoscale interfacial layers is
improved and that the fabrication of the interfacial layers may
also increase the storage lifetime of the device.
4. Conclusions
In summary, we demonstrated an efcient PSC with the
(PTE/Al:Li) nanoscale interfacial layers between the PV layer and
cathode. As an experimental result, with the interfacial layers, the
PSCs show clear improvements in power conversion efciency by
up to 107%. This improvement can be attributed to the
improved electron collection at cathode electrode. Moreover, it
was shown that the PSCs with the nanoscale interfacial layers are
more stable than the PSCs without the interfacial layers. Combining
the device reported here with the highly efcient materials
reported elsewhere will surely lead to highly efcient PSCs.
Acknowledgments
This work was supported by technology development project
of new and renewable energies of the Ministry of Knowledge
Economy of the Republic of Korea (2009). This work was
supported by the Brain Korea 21 Project 2009.
References
[1] N.S. Sariciftci, L. Smilowitz, A.J. Heeger, F. Wudl, Photoinduced electron
transfer from a conducting polymer to buckminsterfullerene, Science 258
(1992) 14741476.
[2] G. Yu, J. Gao, J.C. Hummelen, F. Wudl, A.J. Heeger, Polymer photovoltaic cells:
enhanced efciencies via a network of internal donoracceptor heterojunctions, Science 270 (1995) 17891791.
[3] C.J. Brabec, N.S. Sariciftci, J.C. Hummelen, Plastic solar cells, Adv. Funct. Mater.
11 (2001) 1526.
[4] G. Li, V. Shrotriya, Y. Yao, Y. Yang, Investigation of annealing effects and lm
thickness dependence of polymer solar cells based on poly(3-hexylthiophene), J. Appl. Phys. 98 (2005) 043704-1043704-5.
[5] W. Ma, C. Yang, X. Gong, K. Lee, A.J. Heeger, Thermally stable, efcient
polymer solar cells with nanoscale control of the interpenetrating network
morphology, Adv. Funct. Mater. 15 (2005) 16171622.
[6] H.-Y. Chen, J. Hou, S. Zhang, Y. Liang, G. Yang, Y. Yang, L. Yu, Y. Wu, G. Li,
Polymer solar cells with enhanced open-circuit voltage and efciency, Nat.
Photon. 3 (2009) 649653.
[7] F.C. Krebs, Fabrication and processing of polymer solar cells: a review
of printing and coating techniques, Sol. Energy Mater. Sol. Cells 93 (2009)
394412.
[8] F.C. Krebs, S.A. Gevorgyan, J. Alstrup, A roll-to-roll process to exible polymer
solar cells: model studies, manufacture and operational stability studies,
J. Mater. Chem. 19 (2009) 54425451.
[9] F.L. Zhang, M. Johansson, M.R. Andersson, J.C. Hummelen, O. Inganas, Polymer
photovoltaic cells with conducting polymer anodes, Adv. Mater. 14 (2002)
662665.
[10] S. Khodabakhsh, B.M. Sanderson, J. Nelson, T.S. Jones, Using self-assembling
dipole molecules to improve charge collection in molecular solar cells, Adv.
Funct. Mater. 16 (2006) 95100.
[11] C.J. Brabec, S.E. Shaheen, C. Winder, N.S. Sariciftci, P. Denk, Effect of LiF/metal
electrodes on the performance of plastic solar cells, Appl. Phys. Lett. 80
(2002) 12881290.
[12] F. Zhang, M. Ceder, O. Inganas, Enhancing the photovoltage of polymer solar
cells by using a modied cathode, Adv. Mater. 19 (2007) 18351838.
[13] K. Lee, J.Y. Kim, S.H. Park, S.H. Kim, S. Cho, A.J. Heeger, Air-stable polymer
electronic devices, Adv. Mater. 19 (2007) 24452449.
[14] H.-L. Yip, S.K. Hau, N.S. Baek, H. Ma, A.K.-Y. Jen, Polymer solar cells that use
self- assembled-monolayer-modied ZnO/metals as cathodes, Adv. Mater. 20
(2008) 23762382.
[15] J.H. Park, S.S. Oh, S.W. Kim, E.H. Choi, B.H. Hong, Y.H. Seo, G.S. Cho, B. Park,
J. Lim, S.C. Yoon, C. Lee, Double interfacial layers for highly efcient organic
light-emitting devices, Appl. Phys. Lett. 90 (2007) 153508-1153508-3.
[16] Y. Ding, P. Lu, Q. Chen, Optimizing material properties of bulk-heterojunction
polymer lms for photovoltaic applications, Proc. SPIE 7099 (2008) 7099191709919-8.
[17] C. Waldauf, M.C. Scharber, P. Schilinsky, J.A. Hauch, C.J. Brabec, Physics of
organic bulk heterojunction devices for photovoltaic applications, J. Appl.
Phys. 99 (2006) 104503.
[18] Y.-H. Niu, H. Ma, Q. Xu, A.K.-Y. Jen, High-efciency light-emitting diodes
using neutral surfactants and aluminum cathode, Appl. Phys. Lett. 86 (2005)
083504-1083504-3.
[19] C. Fery, B. Racine, D. Vaufrey, H. Doyeux, S. Cina, Physical mechanism
responsible for the stretched exponential decay behavior of aging organic
light-emitting diodes, Appl. Phys. Lett. 87 (2005) 213502-1213502-3.
[20] K. Norrman, S.A. Gevorgyan, F.C. Krebs, Water-induced degradation of
polymer solar cells studied by H18
2 O labeling, ACS Appl. Mater. Interfaces 1
(2009) 102112.
[21] M. Jorgensen, K. Norrman, F.C. Krebs, Stability/degradation of polymer solar
cells, Sol. Energy Mater. Sol. Cells 92 (2008) 686714.
