Article

pubs.acs.org/JPCC

Inverted Type Polymer Solar Cells with Self-Assembled Monolayer

Treated ZnO
Ye Eun Ha, Mi Young Jo, Juyun Park, Yong-Cheol Kang, Seong Il Yoo, and Joo Hyun Kim*,

Department of Polymer Engineering and Department of Chemistry, Pukyong National University, Busan 608-739, Korea
ABSTRACT: The work function and surface property of ZnO can be
simply tuned by the self-assembled monolayer (SAM) molecules derived
from benzoic acid such as 4-methoxybenzoic acid (MBA), 4-tertbutylbenzoic acid (BBA), and 4-uorobenzoic acid (FBA), which have
dierent dipole orientation and magnitude. MBA, BBA, and FBA treated
ZnO layers were used as an electron injection/transporting layer for
inverted type polymer solar cells (PSCs) with a structure of ITO/SAM
treated ZnO/active layer (P3HT:PC61BM)/MoO3/Ag. The power
conversion eciency (PCE) of PSCs based on MBA and BBA treated
ZnO reaches 3.34 and 2.94%, respectively, while the PCE of the device
based on untreated ZnO is 2.47%. In contrary, the PCE of the device
with FBA treated ZnO is 1.81%. The open circuit voltage (Voc) of the
device with MBA, BBA, and FBA treated ZnO is 0.63 and 0.62 V,
respectively, while the Voc of PSC with untreated ZnO is 0.60 V.
Contrarily, the Voc of the device with FBA treated ZnO is 0.53 V. The PCE and Voc of PSCs based on MBA and BBA treated
ZnO are better than those of the other devices. This seems to be related with the direction of dipole moment of benzoic acid
derivatives. Also, the morphology of the active layer seems to be aected by the substituent on the 4-position of benzoic acid.
The active layer on MBA treated ZnO shows optimized morphology, and its device shows the best performances. We
demonstrate that the work function and morphology of the active layer can be controlled by SAM treatment of the ZnO surface
with dierent dipole orientation and a substituent on the 4-position of benzoic acid. These are very simple and eective methods
for improving the performances of PSCs. The results provide an alternative strategy to improve the interface property between
inorganic and organic materials in organic electronic devices.

1. INTRODUCTION
Polymer solar cells (PSCs) based on -conjugated polymers are
considered as an energy source because they can be fabricated
by a cost-eective, large area printing and coating process on
exible substrates.14 The bulk heterojunction (BHJ) solar cells
based on -conjugated polymer and fullerene derivative blend
layers sandwiched between a transparent conducting electrode
and a low work function metal electrode are eective structures
of polymer solar cells.57 In the past few years, tremendous
results have been reported to improve the performances of
PSCs by the development of new materials 811 and
optimization of morphologies by processing methods.1215
The photoinduced charge separation, transporting, and
collection properties are very important factors for inuencing
the performances of PSCs. Thus, the interfacial properties
between the active layer and the cathode or anode are a crucial
factor for governing performances as well16 because series
resistance (Rs) of PSCs is an important parameter for
performances of PSCs and determined by the electrical
resistivity of each layer and the contact resistance between
layers. The charge collections from the active layer to each
electrode are one of the fundamental steps, which are strongly
related with the contact resistance. A thin layer of poly(3,4ethylenedioxylenethiophene):poly(styrenesulfonic acid) (PEDOT:PSS)17 on ITO, cross-linkable arylamine derivatives1822
2013 American Chemical Society

on ITO, and self-assembled monolayers (SAMs) modied on

ITO23,24 are mainly used for improving the interface properties
between ITO and the active layer. As for the cathode,
introducing a thin layer of LiF,2527 poly(ethyleneoxide),28
water-soluble -conjugated polymers,2931 alcohol-soluble
neutral conjugated polymers,32 and water-soluble nonconjugated polyelectrolyte based on viologen33 between the active
layer and metal cathode has been used for decreasing the work
function of the cathode. These improve the device performances through the formation of a favorable interface dipole
across the junction. In addition, TiOx3436 and ZnO3743
prepared by the solgel process between the active layer and
metal cathode have been used for improving the device
performance. The surface property of a thin lm of ZnO can be
easily tuned by SAMs.44 By using this advantage, the contact
properties between ZnO/cathode and ZnO/active layer can be
modied by SAMs. The direction of the interface dipole
between ZnO/metal can be modied by the conjugated
carboxylic acid derivatives.12 To control contact properties
between ZnO and the TiO2/active layer in inverted type PSC
(ITO/ZnO/active/MoO3/Ag), mixed SAMs with a dierent
Received: November 10, 2012
Revised: January 2, 2013
Published: January 21, 2013
2646

dx.doi.org/10.1021/jp311148d | J. Phys. Chem. C 2013, 117, 26462652

The Journal of Physical Chemistry C

Article

Figure 1. Schematic illustration of polymer solar cells with SAM modied ZnO and schematic energy level diagram of the devices with SAM
modied ZnO. For ZnO/FBA, the interfacial dipole directed toward ZnO. As for ZnO/BBA and ZnO/MBA, the interfacial dipole directed away
from ZnO. There is no net interfacial dipole for ZnO without SAM.

molecular species were applied to the ZnO surface;45 carboxylic

acid derived from a fullerene SAM was applied to the ZnO
surface;24 and various materials were applied to ZnO or TiO2
surfaces.46,47 The optimum surface energy for the optimum
BHJ morphology can be controlled by the mixed SAM without
sacricing the work function of ZnO. The performances of
inverted type PSCs are improved by insertion of ultrathin layers
of TiO2 (<3 nm) between ZnO and the active layer. TiO2
layers act as a barrier for electron collection and reduce
recombination of electrons and holes at ZnO surfaces by the
thin layer of TiO2.47 Bruening et al. report that the surface
potential of the inorganic semiconductor such as CdTe and
CdSe can be controlled by the adsorption of a series of 4substituted benzoic acid derivatives on the semiconductor
surface. The surface potential is directly proportional to the
eective work function. Also, the surface potential and work
function of the semiconductor are decreased by the strong
electron-donating substituent on benzoic acid.4850
In this research, we introduce SAMs derived from benzoic
acid (BA) such as 4-methoxybenzoic acid (MBA), 4-tertbutylbenzoic acid (BBA), and 4-uorobenzoic acid (FBA) and
between ZnO and the active layer. We refer to MBA treated
ZnO, BBA treated ZnO, and FBA treated ZnO as ZnO/MBA,
ZnO/BBA, and ZnO/FBA, respectively. As illustrated in Figure
1, the work function of ZnO will be changed by the SAM
treatment with dierent magnitude and direction of the
permanent dipole moment of BA derivatives. FBA, BBA, and
MBA have dierent dipole moments, which are 1.55, 0.55,
and 1.45 D, respectively.4850 The performances of PSCs will
depend on SAMs with dierent substituent on BA derivatives

modied with ZnO. Moreover, the morphology of the active

layer will be changed by the surface property of ZnO, which
will be depend on the chemical structure of SAM molecules.
Here, we report the photovoltaic and physical properties of the
inverted type PSC with SAM modied ZnO as the electron
injection/transporting layer.

2. EXPERIMENTAL SECTION
Materials. 4-Fluorobenzoic acid, 4-tert-butylbenzoic acid, 4methoxybenzoic acid, zinc acetate dihydrate, triethanol amine,
and methoxyethanol were purchased from Alfa Aesar and used
as received unless otherwise described. Regioregular poly(3hexylthiophene) (P3HT) and (6,6)-phenyl-C61-butyric acid
methyl ester (PCBM) were purchased from Rieke Metals Inc.
and nano-C Inc., respectively.
Measurements. The thickness of the lm was measured by
an Alpha-Step IQ surface proler (KLA-Tencor Co.).
Elemental analysis of before and after SAM treatment by the
benzoic acid derivatives was performed using (THERMO VG
SCIENTIFIC (UK), MultiLab2000) X-ray photoelectron
spectroscopy (XPS) and recorded using Al K X-ray line (15
kV, 300 W). The surface energy () of the ZnO layer before
and after SAM treatment was evaluated by the measurements of
the static advancing contact angle with deionized water and
diiodomethane. The contact angles (KRUSS, Model DSA 100)
were entered in the Wu model (harmonic mean) for the
calculation of the dispersive and polar components of the
surface energy. The eective work function was obtained by
Kelvin probe (KP) measurements (McAllister Technical
Services, KP 6500) of the contact potential dierence between
2647

dx.doi.org/10.1021/jp311148d | J. Phys. Chem. C 2013, 117, 26462652

The Journal of Physical Chemistry C

Article

the sample and the KP tip. The KP tip work function was 5.203
0.011 eV. TEM images of the P3HT:PCBM active layer were
obtained with a JEM-2010 using an accelerating voltage of 80
kV. The active layer was delaminated from the ITO substrate
by dissolving the ZnO layer in HCl solution. The typical
thickness of delaminated lms for TEM was ca. 200 nm. The
AFM topography images were taken using a Digital Instruments (MultiMode SPM) operated in the tapping mode. The
current densityvoltage measurements under 1.0 sun (100
mW/cm2) condition from a 150 W Xe lamp with a 1.5 G lter
were performed using a KEITHLEY model 2400 sourcemeasure unit. A calibrated Si reference cell with a KG5 lter
certied by the National Institute of Advanced Industrial
Science and Technology was used to conrm 1.0 sun condition.
The incident photon to collected electron eciency (IPCE),
external quantum eciency, was calculated by

Figure 2. XPS spectra of (a) ZnO, (b) FBA treated ZnO, (c) BBA
treated ZnO, and (d) MBA treated ZnO.

IPCE (%) = 1240 JSC /

IP

indicates that the ZnO surface is fully covered by BA

derivatives.
For polymer solar cells (PSCs), the charge injection barrier is
a very important factor for improving the device performances.
As illustrated in Figure 1, the electron injection barrier can be
modied by the formation of an interface dipole between ZnO
and the active layer. The interface dipole is induced by the
SAM molecule with permanent dipole moment. To conrm the
formation of the interface dipole by SAM treatment, we
measure the eective work function of ZnO and SAM treated
ZnO surface by using Kelvin Probe Microscopy (KPM). As
shown in Figure 3, the eective work function of ZnO/FBA is

where Jsc (A/cm2) is the short circuit current density

measured at the wavelength (nm) and IP (W/m2).
Fabrication of PSCs. For fabrication of PSCs with a
structure of ITO/before and after SAM treated ZnO/active
layer/MO3/Ag, a layer of 40 nm thick ZnO lm on precleaned
and UV/O3 treated ITO (sheet resistance = 13 ohm/square)
was deposited by using the solgel process. The solgel
solution was prepared with 0.164 g of zinc acetate dihydrate
and 0.05 mL of ethanolamine dissolved in 1 mL of
methoxyethanol. The solution was stirred for 30 min at 60
C prior to deposition. The thin lm of ZnO precursor was
cured at 300 C for 10 min to partly crystallize the ZnO lm,
which is prepared by the literature procedures.44,47 To deposit
self-assembled molecules, a 1.0 mg/mL solution of benzoic acid
derivative in methanol was spin-coated on the ZnO lm at 4000
rpm for 60 s. To remove physically absorbed molecules, the
SAM treated ZnO surface was washed using pure methanol and
then dried by the stream of nitrogen. The active layer was spin
cast from the blend solution of P3HT/PCBM (20 mg of P3HT
and 20 mg of PCBM were dissolved in 1 mL of odichlorobenzene (ODCB)) at 600 rpm for 40 s and dried in
a covered Petri dish for 1 h. Prior to spin coating, the active
solution was ltered through a 0.45 m membrane lter. The
typical thickness of the active layer was 200 nm. Before
deposition of MoO3/Ag, the active layer was thermally
annealed at 150 C for 20 min in the glovebox (N 2
atmosphere). Finally, 20 nm thick MoO3 and 100 nm thick
Ag were deposited successively onto the top of the active layer
through a shadow mask with a device area of 0.13 cm2 at 2
106 Torr.

Figure 3. Eective work function (square) and the surface energy

(triangle) of ZnO/FBA, ZnO, ZnO/BBA, and ZnO/MBA.

4.31 0.04 eV, which is larger than that of ZnO (4.17 0.01
eV). The eective work functions of ZnO/BBA and ZnO/BBA
are 3.97 0.01 and 3.94 0.04 eV, which are smaller than that
of untreated ZnO. The direction of the interface dipole across
the junction depends on the permanent dipole orientation of
BA derivatives. The dipole orientation of FBA and BBA (or
MBA) is the exact opposite direction. For FBA, the interface
dipole between ZnO and the active layer is directed toward
ZnO. As for BBA and MBA, the interface dipole is directed
away from ZnO. Therefore, the eective work function of ZnO
treated with FBA is larger than that of ZnO. In contrary, the
eective work function of BBA and MBA treated ZnO is
smaller than that of untreated ZnO. It is known that the surface
potential of an inorganic semiconductor such as CdTe,
CdInSe2, CdSe, and GaAs4850 can be controlled by the
adsorption of a series of 4-substituted benzoic acid derivatives
on the semiconductor surface. The surface potential dierence

3. RESULTS AND DISCUSSION

Characterization of SAM Modied ZnO. XPS (X-ray
photoelectron spectroscopy) spectra were measured to conrm
covering by the SAM of the ZnO surface. As shown in Figure 2,
the oxygen peaks in XPS are asymmetric, indicating that there
are two oxygen species in the ZnO surface. The peaks at 542
and 543 eV are attributed to oxygen in ZnO (Figure 2(a)). The
peak at 542 eV is due to oxygen in the ZnO crystal lattice, and
the peak at 543 eV corresponds to chemisorbed oxygen caused
by surface hydroxyl.51 As shown in Figure 2(b)(d), the
positions of the peaks corresponding to oxygen in SAM
modied ZnO are shifted to lower binding energy. This
2648

dx.doi.org/10.1021/jp311148d | J. Phys. Chem. C 2013, 117, 26462652

The Journal of Physical Chemistry C

Article

is due to the formation of an unfavorable interface dipole

between ZnO and the active layer. The power conversion
eciency (PCE) of PSC with ZnO/MBA reaches 3.34%, which
is higher than that of the device based on ZnO/FBA (1.81%),
ZnO (2.49%), and ZnO/BBA (2.94%). As seen in Table 1 and
Figure 5(b), the Jsc and FF values of PSCs with MBA/ZnO are
higher than those of the other devices as well.
As seen in Figure 5(b) and Table 1, short circuit current (Jsc)
data of the devices with ZnO/FBA, ZnO, ZnO/BBA, and
ZnO/MBA are 7.55, 7.58, 7.88, and 8.77 mA/cm2,
respectively. The device with ZnO/MBA and ZnO/BBA shows
better Jsc data than that of the device with untreated ZnO. On
the contrary, the Jsc data of PSC with ZnO/FBA are very
comparable to that of the device based on untreated ZnO. The
ll factor (FF) data of the device with ZnO/FBA are 45.1%,
which is lower than that of the device based on untreated ZnO
(51.5%). The FFs of PSCs with ZnO/BBA and ZnO/MBA are
60.4 and 60.5%, respectively, which are higher than that of the
device based on untreated ZnO. Brabec et al. reported that the
diodes ideality factor (n) and saturation current density (Jo)
reect the performances of PSCs as well. The diodes ideality
factor (n) reects the density of donor/acceptor interfaces in
which recombination processes take place. Therefore, n is
representative of the morphology between the polymers and
the fullerenes. The saturation current density (Jo) reects the
number of charges that can overcome the barriers under reverse
bias. Therefore, Jo represents the minority charge density in the
donor/acceptor interface of bulk heterojunction solar cells.52 As
for PSCs with FBA treated ZnO, the n and J0 show the highest
values. This is presumably due to that the best performances of
PSCs with MBA treated ZnO arise from the lower ideality
factor and saturation current. However, there are still lots of
debates about the relationship between n, Jo, and the
performance of PSCs. Figure 6 shows the incident photon to
collected electron eciency (IPCE) of the PSCs in this
research, which show a maximum of IPCE at 540 nm. Among
the devices, PSC with MBA treated ZnO shows the highest
value of 65.1%, which is higher than that of PSC without SAM
(62.9%), with FBA treated ZnO (60.9%), and BBA treated
ZnO (64.7%). The IPCE results also strongly demonstrate how
the photovoltaic parameters are related to the performances of
PSCs with various SAM treated ZnO.
The series resistance (Rs) and parallel resistance (Rp) of
PSCs are important parameters of PSCs. The Rs and Rp were
calculated from the inverse slope near the high current regime
and the slope near the lower current region in the dark JV
curves (Figure 4(b)).53 As shown in Figure 5(c) and Table 1,
the Rs values of the device based on ZnO, ZnO/FBA, ZnO/
BBA, and ZnO/MBA are 13.7, 5.17, 3.15, and 2.82 cm2,
respectively. The Rs reduces in the devices with ZnO/BBA and
ZnO/MBA, while Rs is increased in the device based on ZnO/
FBA. The Rs of the device with ZnO/FBA is much higher than
the other devices. Moreover, parallel resistance (Rp) of the PSC
with FBA/ZnO is 1.03 k cm2, which is much smaller than the
PSC without SAM (2.45 k cm2), with BBA treated ZnO (6.22
k cm2) and with MBA treated ZnO (10.1 k cm2). The Voc
data in ZnO/FBA are much dierent from the device with
untreated ZnO as change of the eective work function of FBA
treated ZnO, whereas the Voc data of PSCs with BBA and MBA
treated ZnO are not much dierent from the device with
untreated ZnO regardless of a sharp change in the eective
work function of ZnO compared to those of ZnO/BBA and
ZnO/MBA. The high drop of Voc data in ZnO/FBA compared

is directly proportional to the eective work function dierence.

The change in the semiconductor surface potential varies
linearly with the electron anity of the substituent of the
benzoic acid derivatives. The dipole moment of benzoic acid
derivatives reects the electron-withdrawing and -donating
power of the substituent. The strong electron-donating power
substituent on benzoic acid reduces the surface potential and
work function of the semiconductor. Very similar correlations
are observed in SAM modied ZnO with benzoic acid
derivatives. From the KPM results, we conrm that direction
of the formation of the interface dipole and variation of the
work function of ZnO illustrated in Figure 1 are reasonable. As
shown in Figure 3, the surface energy reects the substituent on
the benzoic acid derivative. The hydrophobic uorine and tertbutyl substituent decrease the surface energy of the ZnO
surface.
Photovoltaic Properties. Figure 4 shows current density
voltage curves of inverted type PSCs under AM 1.5G simulated

Figure 4. Current densityvoltage curves of inverted type PSCs (a)

under AM 1.5G simulated illumination with an intensity of 100 mW/
cm2 and (b) under the dark condition (square, FBA SAM modied;
circle, without SAM; triangle, BBA SAM modied; inverted triangle,
MBA SAM modied).

illumination with an intensity of 100 mW/cm2 and under the

dark condition. The photovoltaic parameters and eciency of
the best PSCs with various SAM treated ZnO are summarized
in Table 1 and Figure 5. As shown in Table 1 and Figure 5(a),
the Voc data of the device based on ZnO/MBA are 0.63 V,
which is higher than those of PSC with ZnO/BBA (0.62 V),
untreated ZnO (0.61 V), and ZnO/FBA (0.53 V). This is
because the eective work function of ZnO treated with MBA
shows the smallest value than the others. As for ZnO/FBA, Voc
is smaller than that of the device based on untreated ZnO. This
2649

dx.doi.org/10.1021/jp311148d | J. Phys. Chem. C 2013, 117, 26462652

The Journal of Physical Chemistry C

Article

Table 1. Best Photovoltaic Parameters and Eciencies of PSCs with Various SAM Treated ZnOa
Voc (V)
FBA
no SAM
BBA
MBA

0.53
0.60
0.62
0.63

(0.55
(0.61
(0.62
(0.62

0.01)
0.01)
0.004)
0.004)

Jsc (mA/cm2)
7.55
7.83
7.88
8.77

(7.23
(7.80
(8.11
(8.51

0.15)
0.07)
0.17)
0.13)

FF (%)
45.1
53.0
60.4
60.5

(45.0
(51.6
(57.6
(59.8

PCE (%)
0.43)
1.14)
1.40)
0.82)

1.81
2.49
2.94
3.34

(1.78
(2.44
(2.88
(3.16

0.03)
0.07)
0.05)
0.06)

Rs
(cm2)b

Rp
(kcm2)c

nd

J0
(A/cm2)e

13.7
5.17
3.15
2.82

1.03
2.45
6.22
10.1

2.37
2.22
1.77
1.66

0.93
0.091
0.033
0.059

The averages for photovoltaic parameters of each device are given in parentheses with mean variation. bSeries resistance (estimated from the device
with best PCE value). cParallel resistance (estimated from the device with best PCE value). dIdeality factor (estimated from the device with best PCE
value). eSaturation current density (estimated from the device with best PCE value).

FBA.54 This is due to the formation of an unfavorable interface

dipole between ZnO and the active layer in FBA treated ZnO.
FBA SAM with ZnO forms an unfavorable dipole across the
ZnO, and the active layer results in Schottky contact and shows
poor device performance. On the contrary, BBA and MBA
treated ZnO have a favorable dipole across the ZnO and active
layer and generate better contact so that the devices show
better performances.
Morphology of the Active Layer. We conrm that the
Voc data vary by the direction of interface dipole, which is easily
tuned by the SAM molecules with dierent dipole moment.
However, the variation of Jsc and FF data is not explained by the
change of interface dipole. Among the photovoltaic parameters,
the PCE of PSC with ZnO/MBA is signicantly higher than
that of the device with untreated ZnO regardless of the small
change in Voc data of PSCs with ZnO/MBA compared to that
of PSCs with untreated ZnO. This is due to the big change of
Jsc and FF value, which are strongly related with morphological
property of the active layer.55 For ecient charge separation
and transporting in PSCs, it should have phases of P3HT and
PCBM in the order of 1020 nm.1,56 To obtain morphology of
the active layer, transmission microscopy (TEM) and atomic
force microscopy (AFM) were taken to investigate the
morphology of the active layer on SAM treated ZnO. Figure
7 shows TEM images of active layers. The active layer was

Figure 5. (a) Voc (square) and PCE (triangle), (b) Jsc (square) and FF
(triangle), and (c) Rs (square) and Rp (triangle) vs with and without
SAM treated ZnO and (d) Voc vs eective work function of SAM
treated ZnO.

Figure 7. TEM images of the active layer deposited on (a) ZnO/FBA,

(b) ZnO, (c) ZnO/BBA, and (d) ZnO/MBA.

delaminated from the ITO substrate by dissolving a ZnO layer

in HCl solution. The bright region in TEM images (Figure 7)
indicates a P3HT-rich local phase. Figure 7(a) shows a very
good interpenetrating network and P3HT:PCBM phase
separated morphology. However, the size of PCBM aggregates
is 80130 nm, and the TEM image shows very big size of
P3HT domains. The maximum size of the PCBM aggregate is

Figure 6. IPCE spectra of PSCs with SAM modied ZnO.

to that of the device with untreated ZnO seems to be attributed

to the highest Rs and lowest Rp value of the device with ZnO/
2650

dx.doi.org/10.1021/jp311148d | J. Phys. Chem. C 2013, 117, 26462652

The Journal of Physical Chemistry C

Article

modication with a series of benzoic acid derivative SAM

treatments. The work function of ZnO depends on the
orientation of the dipole moment of SAM molecules. Also, we
have observed that the substituent on the 4-position of benzoic
acid aects the morphology of the active layer. The
performances of inverted type polymer solar cells can be
improved by the appropriate choice of SAM molecule. Our
results in this paper provide an alternative strategy to improve
the performances of PSCs by the control of interface property
between inorganic and organic materials in polymer solar cells.

very close to the thickness of the active layer (200 nm). The
r.m.s. roughness of the active layer on ZnO/FBA (13.39 nm)
(Figure 8(a)) also supports that a FF of the device with ZnO/

AUTHOR INFORMATION

Corresponding Author

*E-mail: jkim@pknu.ac.kr.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This research was supported by Converging Research Center
Program through the Ministry of Education, Science and
Technology (2012K001279) and Basic Science Research
Program through the National Research Foundation of Korea
(NRF) funded by the Ministry of Education, Science and
Technology (2012-0001356).

Figure 8. AFM topography images of thermally annealed P3HT/

PCBM lm on (a) ZnO/FBA, (b) ZnO, (c) ZnO/BBA, and (d) ZnO/
MBA (x, y = 1 m/div., z = 100 nm/div.).

FBA is much lower than that of the device with untreated ZnO.
Figure 7(c) and (d) shows TEM images of the active layer on
ZnO/BBA and ZnO/MBA, respectively. The size of the PCBM
aggregates of ZnO/BBA and ZnO/MBA are 3040 nm and
1020 nm, respectively, which are smaller than those of the
active layer on untreated ZnO (4060 nm) and FBA treated
ZnO. Moreover, the boundaries between PCBM aggregates and
P3HT domains of active layers on ZnO/BBA and ZnO/MBA
are sharper than those of the active layer on untreated ZnO.
This indicates that the FF data of ZnO/BBA and ZnO/MBA
are much higher than those of the other devices. The
distribution of PCBM aggregates on ZnO/MBA is more
uniform than the case of ZnO/BBA. Moreover, the size of
PCBM aggregates on ZnO/MBA is very close to the optimum
condition, indicating that the Jsc and FF of the device with
ZnO/MBA are signicantly improved compared to the other
devices. Even though TEM images do not provide exact
information about vertically phase separated structures across
both electrodes, we conrm that ZnO/MBA exhibit optimized
phase separated morphology among the devices by TEM
images. As shown in Figure 8, the r.m.s. roughness of the active
layer on ZnO/MBA is 4.24 nm, which is not much dierent
from the r.m.s. roughness data of the active layer on ZnO (2.89
nm) and ZnO/BBA (1.62 nm). The performances of the device
seem to be unaected by the surface energy of SAM modied
ZnO. However, the morphology of the active layer seems to be
aected by the substituent on the 4-position of benzoic acid.
The eective work function data and morphological changes of
the active layer strongly support that the device based on ZnO/
MBA exhibits the best performances.

REFERENCES

(1) Gunes, S.; Neugebauer, H.; Sariciftci, N. S. Chem. Rev. 2007, 107,
13241338.
(2) Brabec, C. J.; Sariciftci, N. S.; Hummelen, J. C. Adv. Funct. Mater.
2001, 11, 1526.
(3) Kim, J. Y.; Lee, K.; Coates, N. E.; Moses, D.; Nguyen, T. Q.;
Dante, M.; Heeger, A. J. Science 2007, 317, 222225.
(4) Friend, R. H.; Gymer, R. W.; Holmes, A. B.; Burroughes, J. H.;
Marks, R. N.; Taliani, C.; Bradley, D. D. C.; Dos Santos, D. A.; Bredas,
J. L.; Logdlund, M.; et al. Nature 2001, 397, 121128.
(5) Shaheen, S. E.; Barbec, C. J.; Scriciftci, N. S.; Padinger, F.;
Fromherz, T.; Hummelen, J. C. Appl. Phys. Lett. 2001, 78, 841843.
(6) Li, G.; Shrotriya, V.; Huang, J.; Yao, Y.; Moriarty, T.; Emery, K.;
Yang, Y. Nat. Mater. 2005, 4, 864868.
(7) Ma, W.; Yang, C.; Gong, X.; Lee, K.; Heeger, A. J. Adv. Funct.
Mater. 2005, 15, 16171622.
(8) Peet, J.; Kim, J. Y.; Coates, N. E.; Ma, W. L.; Moses, D.; Heeger,
A. J.; Bazan, G. C. Nat. Mater. 2007, 6, 497500.
(9) Wong, W. Y.; Wang, X. Z.; He, Z.; Djurisic, A. B.; Yip, C. T.;
Cheung, K. Y.; Wang, H.; Mak, C. S. K.; Chan, W. K. Nat. Mater.
2007, 6, 521527.
(10) Krebs, F. C. Sol. Energy Mater. Sol. Cells 2009, 93, 465475.
(11) Vak, D.; Kim, S. -S.; Jo, J.; Oh, S. -H.; Na, S. -I.; Kim, J.; Kim, D.
Y. Appl. Phys. Lett. 2007, 91, 0811021- 0811023.
(12) Yip, H.-L.; Hau, S. K.; Baek, N. S.; Ma, H.; Jen, A. K. -Y. Adv.
Mater. 2008, 20, 23762382.
(13) Li, G.; Shrotriya, V.; Huang, J. S.; Yao, Y.; Moriarty, T.; Emery,
K.; Yang, Y. Nat. Mater. 2005, 4, 864868.
(14) Ma, W. L.; Yang, C. Y.; Gong, X.; Lee, K.; Heeger, A. J. Adv.
Funct. Mater. 2005, 15, 16171622.
(15) Kim, K.; Liu, J.; Namboothiry, M. A. G.; Carroll, D. L. Appl.
Phys. Lett. 2007, 90, 1635111 - 1625113.
(16) Thompson, B. C.; Frechet, J. M. J. Angew. Chem., Int. Ed. 2008,
47, 5877.
(17) Zhang, F. L.; Johansson, M.; Andersson, M. R.; Hummelen, J.
C.; Inganas, O. Adv. Mater. 2002, 14, 662665.
(18) Bacher, E.; Bayerl, M.; Rudati, P.; Reckefuss, N.; Muller, C. D.;
Meerholz, K.; Nuyken, O. Macromolecules 2005, 38, 16401643.
(19) Jungermann, S.; Riegel, N.; Muller, D.; Meerholz, K.; Nuyken,
O. Macromolecules 2006, 39, 89118911.

4. CONCLUSION
We have fabricated inverted polymer solar cells with a series of
benzoic acid derivative SAM treated ZnO as the electron
injection/transporting layer. The work function and surface
property of ZnO can be successfully tuned by the interfacial
2651

dx.doi.org/10.1021/jp311148d | J. Phys. Chem. C 2013, 117, 26462652

The Journal of Physical Chemistry C

Article

(52) Waldauf, C.; Schilinsky, P.; Hauch, J.; Brabec, C. J. Thin Solid
Films 2004, 451452, 503507.
(53) Xue, J.; Uchida, S.; Rand, B. P.; Forrest, S. R. Appl. Phys. Lett.
2004, 84, 30133015.
(54) Schafer, S.; Petersen, A.; Wagner, T. A.; Kniprath, R.;
Lingenfelser, D. Phys. Rev. B 2011, 83, 165311.
(55) van Durun, J. K. J.; Yang, X.; Loos, J.; Bulle-Lieuwma, C. W. T.;
Sieval, A. B.; Hummenlen, J. C.; Janssen, R. A. J. Adv. Funct. Mater.
2004, 14, 425434.
(56) Yu, G.; Gao, J.; Hummelen, J. C.; Wudl, F.; Heeger, A. J. Science
1995, 270, 17891791.

(20) Liu, S.; Jiang, X.; Ma, H.; Liu, M. -S.; Jen, A. K. -Y.
Macromolecules 2000, 33, 35143517.
(21) Liu, M. -S.; Niu, Y. -H.; Ka, J. -W.; Yip, H. -L.; Huang, F.; Luo,
J.; Kim, T. -D.; Jen, A. K. -Y. Macromolecules 2008, 41, 95709580.
(22) Lim, Y.; Park, Y.-S.; Kang, Y.; Jang, D. Y.; Kim, J. H.; Kim, J. -J.;
Sellinger, A.; Yoon, D. -Y. J. Am. Chem. Soc. 2011, 133, 13751382.
(23) Khodabakhsh, S.; Sanderson, B. M.; Nelson, J.; Jones, T. S. Adv.
Funct. Mater. 2006, 16, 95100.
(24) Goh, C.; Scully, S. R.; McGehee, M. D. J. Appl. Phys. 2007, 101,
114503111450312.
(25) Monson, T. C.; Lloyd, M. T.; Olson, D. C.; Lee, Y.-J.; Hsu, J. W.
P. Adv. Mater. 2008, 20, 47554759.
(26) Hau, S.; Yip, H.; Acton, O.; Baek, N. S.; Ma, H.; Jen, A. K. Y. J.
Mater. Chem. 2008, 18, 51135119.
(27) Brabec, C. J.; Shaheen, S. E.; Winder, C.; Sariciftci, N. S.; Denk,
P. Appl. Phys. Lett. 2002, 80, 12881290.
(28) Veenstra, S. C.; Heeres, A.; Hadziioannou, G.; Sawatzky, G. A.;
Jonkman, H. Y. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 661666.
(29) De Renzi, V.; Rousseau, R. D.; Marchetto, D.; Biagi, R.;
Scandolo, S.; del Pennino, U. Phys. Rev. Lett. 2005, 95, 046804.
(30) Zhang, F.; Ceder, M.; Inganas, O. Adv. Mater. 2007, 19, 1835
1838.
(31) Choi, H.; Park, J. S.; Jeong, E.; Kim, G. -W.; Lee, B. R.; Kim, S.
O.; Song, M. H.; Woo, H. Y.; Kim, J. Adv. Mater. 2011, 23, 2759
2763.
(32) Oh, S. -W.; Na, S. -I.; Jo, J.; Lim, B.; Vak, D.; Kim, D. -Y. Adv.
Funct. Mater. 2010, 20, 19771983.
(33) Jo, M. Y.; Ha, Y. E.; Kim, J. H. Sol. Energy Mater. Sol. Cells 2012,
107, 18.
(34) Hayakawa, A.; Yoshikawa, O.; Fujieda, T.; Uehara, K.;
Yoshikawa, S. Appl. Phys. Lett. 2007, 90, 16351711635173.
(35) Kim, J. Y.; Kim, S. H.; Lee, H. H.; Lee, K.; Ma, W.; Gong, X.;
Heeger, A. J. Adv. Mater. 2006, 18, 572576.
(36) Lee, K.; Kim, J. Y.; Park, S. H.; Kim, S. H.; Cho, S.; Heeger, A. J.
Adv. Mater. 2007, 19, 24452449.
(37) Scharber, M. C.; Muhlbacher, D.; Koppe, M.; Denk, P.;
Waldauf, C.; Heeger, A. J.; Brabec, C. J. Adv. Mater. 2006, 18, 789
794.
(38) Roest, A. L.; Kelly, J. J.; Vanmaekelbergh, D.; Meulenkamp, E.
A. Phys. Rev. Lett. 2002, 89, 036801.
(39) Gilot, J.; Wienk, M. M.; Janssen, R. A. J. Appl. Phys. Lett. 2007,
90, 143512.
(40) Lao, C.; Wong, C. P.; Wang, Z. L. Nano Lett. 2007, 7, 1323
1328.
(41) Hau, S. K.; Yip, H.-L.; Baek, N. S.; Zou, J.; Kevin OMalley, K.;
Jen, A. -K. Y. Appl. Phys. Lett. 2007, 92, 25330112533013.
(42) Sun, Y.; Seo, J. W.; Takacs, C. J.; Seifter, J.; Heeger, A. J. Adv.
Mater. 2011, 23, 16791683.
(43) Bekci, D. R.; Karsli, A.; Cakir, A. C.; Sarica, H.; Guloglu, A.;
Gunes, S.; Erten-Ela, S. Appl. Energy 2012, 96, 417421.
(44) Bulliard, X.; Ihn, S. -G.; Yun, S.; Kim, Y.; Choi, D.; Choi, J. -Y.;
Kim, M.; Sim, M.; Park, J. -H.; Choi, W.; et al. Adv. Funct. Mater. 2010,
20, 43814387.
(45) Hau, S. K.; Yip, H.-L.; Ma, H.; Jen, A. K.-Y. Appl. Phys. Lett.
2008, 93, 23330412333043.
(46) Monson, T. C.; Lloyd, M. T.; Olson, D. C.; Lee, Y.-J.; Hsu, J. W.
P. Adv. Mater. 2008, 20, 47554759.
(47) Seo, H. O.; Park, S. -Y.; Shim, W. H.; Kim, K. -D.; Lee, K. H.; Jo,
M. Y.; Kim, J. H.; Lee, E.; Kim, D. -W.; Kim, Y. D.; et al. J. Phys. Chem.
C 2011, 115, 2151721520.
(48) Bruening, M.; Moons, E.; Yaron-Marcovich, D.; Cahen, D.;
Libman, J.; Shanzer, A. J. Am. Chem. Soc. 1994, 116, 29722977.
(49) Bruening, M.; Moons, E.; Cahen, D.; Shanzer, A. J. Phys. Chem.
1995, 99, 83688373.
(50) Bastide, S.; Butruille, R.; Cahen, D.; Dutta, A.; Libman, J.;
Shanzer, A.; Sun, L.; Vilan, A. J. Phys. Chem. B 1997, 101, 26782684.
(51) Xu, C.; Xu, G.; Liu, Y.; Wang, G. Solid State Commun. 2002,
122, 175179.
2652

dx.doi.org/10.1021/jp311148d | J. Phys. Chem. C 2013, 117, 26462652