Materials Chemistry and Physics 188 (2017) 86e94

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Materials Chemistry and Physics

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

Improving the performance of solution-processed organic solar cells

by incorporating small molecule acceptors into a ternary bulk
heterojunction based on DH6T:Mq3:PCBM (M ¼ Ga, Al)
Fahmi F. Muhammad a, b, c, Mohd Yazid Yahya a, *, Khaulah Sulaiman d
a
Center for Composites, Institute for Vehicle Systems & Engineering, Faculty of Mechanical Engineering, Universiti Teknologi Malaysia, 81310 Johor Bahru,
Johor, Malaysia
b
Soft Materials & Devices Lab, Department of Physics, Faculty of Science & Health, Koya University, Koya, Kurdistan Region, Iraq
c
Development Center for Research and Training, University of Human Development, Sulaimani, Kurdistan Region, Iraq
d
Low Dimensional Materials Research Centre, Department of Physics, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Ternary solution-processed OSCs

including Gaq3 and Alq3 acceptors
were realized.
 The power and efficiency of the de-
vices were increased by an order of
5.8.
 Broadened absorption and improved
crystallinity were achieved for the
active layers.

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

Article history: Improvement in the overall performance of solution-processed organic solar cells based on a ternary
Received 7 April 2016 heterostructure was realized by means of incorporating small molecules of tris(8-hydroxyquinoline)
Received in revised form gallium (Gaq3) or Alq3 electron acceptors. The donor host polymer was a,u-dihexyl-sexithiophene
21 November 2016
(DH6T), while the ultimate acceptor was fullerene (PC61BM). The results showed that short circuit cur-
Accepted 23 November 2016
rent (ISc), open circuit voltage (Voc), and fill factor (FF) of the devices were pronouncedly enhanced by the
Available online 24 November 2016
inclusion of Gaq3 or Alq3. The maximum output power and conversion efficiency of the ternary devices
were increased by an order of 5.8 times compared to that of the control devices. These improvements
Keywords:
Composite materials
were ascribed to the broadened light absorption, energy levels alignment between the donor-acceptor
Organometallic compounds components, a balanced charge transfer, and increased crystallinity of the devices active layer. The re-
Coatings sults were ascertained and analyzed by means of UVeVis, PL, XRD, IV and TEM investigations.
TEM © 2016 Published by Elsevier B.V.

1. Introduction

In recent years, the development of low cost, environmental

* Corresponding author.
E-mail address: yazidyahya@utm.my (M.Y. Yahya).
friendly, easily processed and efficient photovoltaic devices for

http://dx.doi.org/10.1016/j.matchemphys.2016.11.048
0254-0584/© 2016 Published by Elsevier B.V.
 F.F. Muhammad et al. / Materials Chemistry and Physics 188 (2017) 86e94
solar energy harvesting has been receiving a great deal of attention
by the researchers of the field [1e3]. Conventional solar cells
(photovoltaics) whose are basically made from inorganic materials
are suffering the barrier of high cost and high energy requirement
during the production process. As such, searching for potential
materials to replace the inorganic ones has opened new routes for
realizing flexible, solution-processed and light weight organic solar
cells (OSCs) [4,5]. Besides, the application of semiconductor
organic/polymeric materials has been further extended in various
electronic devices such as transistor, memories, sensor and diodes
[6e9]. The main advantages of organic materials for photovoltaic
application, which make them prevailed over inorganic ones, are
their high absorption coefficient and optoelectronic tunability
[10,11]. The major pre-requisites for OSC active materials (materials
contributing to the absorption of light) are their energy bands
alignment and miscibility [12,13]. In order to facilitate efficient
charge transfer between the electron donor (D) and electron
acceptor (A) active components, the lower unoccupied molecular
orbital (LUMO) of the acceptor should be located below that of the
donor and the higher occupied molecular orbital (HOMO) of the
donor should lie above that of the acceptor [14]. The transport of
charge carriers is originated from the dissociation of excitons
(bounded electron-hole). This dissociation can only be occurred at
the boundary of D-A moieties [15], from where free electrons and
holes start to migrate towards their corresponding electrodes.
Consequently, bulk heterojunction (BHJ) structures [16] were
developed aiming at increasing the D-A interfaces, thereby
improving the charge transport response and hence enhancing the
devices performance in comparison to those of the bilayer D-A
based ones [17]. However, one prominent obstacle in front of BHJ
structures is the presence of inexact interplay between the D/
positive electrode and A/negative electrode. This is because of the
inherent contact of the acceptor component with the positive
electrode and vice versa. Interestingly, ternary bulk heterojunction
(TBHJ) architectures [18] have been proposed to improve the
percolation pathways in between the D-A boundaries and to ach-
ieve a complementary absorption of light by the active layers [19].
Comprehensive reviews about OSCs based on ternary bulk heter-
ojunction [20e23] reveal that it is possible for these devices to
show a promising future [24]. In these contexts, researchers have
added third component into the BHJ to obtain a charge transport
balance [25], the prevention of phase separation and increasing the
active layer crystallinity [26]. Despite the presence of numerous
works on ternary organic solar cells, a complete understanding of
some electrical parameters [27,28] governing the performance of
these devices has not yet been achieved. Extensive literature re-
views showed that little attention has been paid on the incorpo-
ration of secondary acceptor component into the hetero-structured
ternary organic solar cells, while the inclusion of secondary donor
component has been widely investigated aiming at improving the
performance of ternary OSC devices [29e31]. In this work we
report on the improvement of ternary based OSCs through the
introduction of small molecule acceptors of tris(8-
hydroxyquinoline) gallium (Gaq3) and its Alq3 counterpart into
the devices active layer. Organometallic materials of Gaq3 and Alq3
[32] have been well known for their applications in organic light
emitting diodes [33] and spintronics [34]. Besides, it has been
recently found that the performance of binary organic solar cells
was improved when Alq3 was added into their active layers [35].
The impact of Alq3 inclusion on the performance of bulk hetero-
junction organic solar cells based on MEH-PPV:PCBM was also re-
ported by Liu et al. [36], in which the Alq3 component was served
as the active layer dopant and as thermally coated buffer layer
between the aluminum electrode and active layer. The interest in
the application of small molecular organics for ternary systems has
87
been receiving considerable attention owing to the important
features offered by these materials such as high charge carrier
mobility, better crystallinity and reasonable batch-to-batch pro-
duction [37]. Several research works were previously devoted to
the utilization of small donor molecules in the ternary based
organic solar cells [38e40]. In the current work, however, the small
molecules of Gaq3 and Alq3 are acceptor components and are
responsible for the transport of electrons.
2. Materials and methods
The small acceptor molecules, Gaq3 and Alq3 were purchased
from Sigma Aldrich in powder form and were used to be incorpo-
rated into the bulk heterojunction of DH6T:PCBM without further
purification. As such, the active layer of the ternary organic solar
cells was made from a donor, two acceptor semiconductors and a
hole transporting layer (PEDOT:PSS). Fig. 1 shows the devices ar-
chitecture and molecular structures of the applied materials. The
donor semiconductor was a,u-dihexyl-sexithiophene (DH6T),
while the acceptor semiconductors were methanofullerene; [6,6]-
phenyl C61 butyric acid methyl ester (PCBM), tris(8-
hydroxyquinoline) gallium (Gaq3) or Alq3, respectively. In the
experimental procedures, a specified molar amount of Gaq3 or Alq3
(25%) was incorporated into the binary DH6T:PCBM (1:2) bulk
heterojunction, that was to realize organic solar cells based on
active layers of ternary bulk heterojunction (TBHJ).
The indium tin oxide (ITO) coated glass substrates (H. W. Sands
Co., Ltd.) with sheet resistance of ~10 U/sq were patterned through
a wet etching process starting by immersing the substrates in a
bath of hydrochloric acid and distilled water (0.4:1), then they were
agitated at temperature of 60  C for 15 min. The PEDOT:PSS (H. C.
Starck, Baytron P VPAI 4033) layer was spin-coated onto the ITO at
3000 rpm for 20 s, then baked at 130  C for 5 min to achieve a
thickness of ~35 nm. Later on, blends of DH6T:PCBM (1:2 M ratio),
prepared in chlorobenzene (30 mg/ml), was spin-coated onto the
PEDOT:PSS layer to achieve a thickness of ~200 nm. Finally,
aluminum electrode (~50 nm thick) was thermally evaporated onto
the DH6T:PCBM layer through a metal mask under a vacuum at
105 mbar. Consequently, devices with active area of 14 mm2
(2 mm  7 mm) have been fabricated, which made them ready for
the performance analysis. In order to investigate the impact of
incorporating 25% molar of Gaq3 or Alq3 into the binary
DH6T:PCBM (1:2) active layer, a second batch of devices based on
ternary bulk heterojunction (~200 nm thick) of DH6T:Mq3:PCBM
([0.75þ0.25]:2) was fabricated following the same procedures
described before. In order to analysis the photovoltaic performance
of the devices, Keithley 236 instrument was used under standard
illumination (100 mW/cm2) to record the current densityevoltage
(JeV) response for four identical solar cells fabricated on the same
substrate. The average data of the measurements was then taken to
produce the JeV figures. The absorption spectra of the films were
recorded using Jasco V-570 UVeViseNIR spectrophotometer in the
wavelength range from 300 to 800 nm, while the photo-
luminescence activity was measured by LS50B Perkin Elmer lumi-
nescence spectrometer in the wavelength range from 350 to
800 nm. The X-ray diffractometer (Bruker AXS), using Cu Ka radi-
ation of wavelength l ¼ 1.5406 Å as a source, was utilized to
perform the structural investigations in the glancing angle range
from 5 to 80 . Moreover, in order to visual the nanoscale distri-
bution of the components, a transmission electron microscopy
(TEM LEO LIBRA-120) was utilized. All the measurements were
made in ambient condition and at the lab temperature of 24  C.
88 F.F. Muhammad et al. / Materials Chemistry and Physics 188 (2017) 86e94

S S S
C6H13
C6H13
S S S

DH6T

OMe N .
O O O .
O
O M
N S .
+
. S
N
O H
O O O S O
M = Ga, Al O .
q = 8-hydroxyquinolinate

PC61BM Mq3 PEDOT:PSS

(c)
Fig. 1. Device structures of organic solar cells based on (a) DH6T:Mq3:PCBM ternary bulk heterojunction, and (b) DH6T:PCBM binary bulk heterojunction.

3. Results and discussion 3.0

The estimated molar amount of Gaq3 and Alq3 that has been
2.8 DH6T:Alq3 composite
added into the DH6T:PCBM active layer was speculated from the DH6T:Gaq3 composite
plot of energy gap variation of DH6T:Mq3 system versus the molar
2.6
Energy gap (eV)

fraction of Mq3. The value of energy gap for the pure Alq3, Gaq3,
DH6T and DH6T:Mq3 system was determined from their absorp-
tion spectra following a detailed procedure described elsewhere 2.4
[41e43]. Fig. 2 shows that the optimum molar fraction of Alq3 or
Gaq3 to produce a minimum energy gap in the DH6T:Mq3 system is 2.2
about 25%. Therefore, the incorporation of Gaq3 and Alq3 in the
current work was fixed to be in ratio of 0.25 M compared to that of 2.0
the DH6T host.
Fig. 3 shows the normalized absorbance for the BHJ active layers 1.8
as well as for the Alq3, Gaq3 and DH6T films. Two peaks were
observed for the Alq3 and Gaq3 films that were ascribed to the 1.6
presence of p  p* and p  p* electronic transitions in the low and 0.0 0.2 0.4 0.6 0.8 1.0
high wavelength absorption regions, respectively [32]. The DH6T
and PCBM films showed absorption bands at 370 and 340 nm, Molar fraction of Mq3 (M= Al, Ga)
respectively, which are close enough to those reported previously
Fig. 2. Energy gap variation versus molar% of Mq3 (M ¼ Al, Ga) in the DH6T:Mq3
[44,45]. These bands were assigned to the p  p* electronic tran- composite system.
sitions that are taken place between the molecular orbitals. The
 F.F. Muhammad et al. / Materials Chemistry and Physics 188 (2017) 86e94
1.2
DH6T:Gaq3:PCBM
Normalized Absorbance (a.u.)
([0.75+0.25]:2)
1.0
0.8
0.6
0.4
0.2
0.0
320 400 480 560
Wavelength (nm)
Fig. 3. Normalized absorbance of Alq3, Gaq3, DH6T, PCBM, DH6T:PCBM and
DH6T:Mq3:PCBM films.
presence of a red shift in the absorption spectra of DH6T:PCBM
blends with respect to that of DH6T was noticed, indicating an
enhanced photo-induced charge transfer between the donor-
acceptor moieties [46]. The shape consistency of the PCBM ab-
sorption spectra in the wavelength range from 250 to 350 nm is
attributed to the strong intermolecular interaction between DH6T
and PCBM molecules, as PCBM triplet photoexcited state absorbs
light energy more efficiently than its ground state [47]. It is worth
noting that the inclusion of Gaq3 or Alq3 has made the absorption
spectra to be red shifted to up to 750 nm, suggesting a significant
contribution of these small molecule acceptors to broaden the ab-
sorption response of ternary DH6T/Mq3/PCBM bulk hetero-
junction. This broadened spectrum is ascribed to the increased
strength of p  p* overlap [48]. Noticeably, the addition of Gaq3
resulted in a broader absorption spectrum of the TBHJ film
compared to that of the Alq3 added one. This could be due to a
better alignment of molecular energy levels between the
DH6T:Gaq3:PCBM components in comparison to that of the
DH6T:Gaq3:PCBM blend, as shown in Fig. 4.
Fig. 5 shows the photoluminescence (PL) activities of DH6T,
DH6T:PCBM, ternary DH6T:Alq3:PCBM and DH6T:Gaq3:PCBM
films excited at a wavelength source of 360 nm. Luminescence in
Fig. 4. The alignment of HOMO and LUMO energy levels between DH6T:Gaq3:PCBM
(a) and DH6T:Alq3:PCBM (b) ternary bulk heterojunctions.
89
Alq3
Gaq3
PCBM
DH6T
DH6T:Alq3:PCBM
([0.75+0.25]:2)
DH6T:PCBM
(1:2)
640 720 800
Fig. 5. PL spectra of DH6T, DH6T:PCBM, DH6T:Gaq3:PCBM and DH6T:Alq3:PCBM films
with 25% molar fraction of Gaq3 and Alq3.
these films is a direct measure to the probability of radiative charge
recombination due to weak intermolecular interaction [49]. The PL
spectrum of DH6T showed dual characteristic peaks, one peak is
relatively sharp at about 530 nm and it is close enough to that
observed for DH6T in chloroform [9,45], while the other peak is
located at 395 nm. This dual PL characteristic is originated from the
conjugation length of the thiophene oligomer and its hexyl chains
[50]. The PL spectrum of DH6T demonstrated equally spaced small
peaks, each separated by about 15 nm (0.9 eV). This feature is
interpreted as a vibronic coupling of the electronic transitions
[51,52]. One can see that the addition of Gaq3 or Alq3 has made the
PL intensity of DH6T:PCBM to decrease considerably, implying that
a weakened radiative recombination have been achieved. Further-
more, the PL peak in the visible region has slightly shifted towards
lower energy (higher wavelength) compared to that of the DH6T,
supporting the agreement of improved p  p stacking density, as it
was observed earlier from the absorption spectra. The quenched PL
activity is therefore a strong indication of facilitating efficient
charge transfer between the DH6T:Mq3:PCBM moieties when light
radiation is exposed to the ternary system. A stronger PL quenching
was observed for the Gaq3 introduced film compared to that of the
Alq3 added one. This might be because of two reasons; first, the
existence of a well matched HOMO and LUMO energy levels be-
tween DH6T:Gaq3:PCBM components compared to that of the
DH6T:Alq3:PCBM and second the contribution of higher refractive
index for Gaq3 compared to that of Alq3 [32], by which more ex-
citons can be dissociated at the donor-acceptor boundaries as a
consequence of stronger internal electric field and space charge
accumulation [53]. Another interesting phenomenon observed was
for Stokes shift, which is the difference in wavelength between
positions of the band maxima of the absorption and photo-
luminescence of the same electronic transition. This was noticed for
all the films, indicating that the films act upon dissipating part of
the absorbed radiation [54].
To investigate the structural and orientation distribution of the
blend molecules, we carried out X-ray diffraction analysis. Fig. 6
shows the XRD patterns recorded for the films of Alq3, Gaq3, bi-
nary DH6T:PCBM and ternary DH6T:Mq3:PCBM heterojunctions.
The crystallite peaks at 6.5 and 21.5 were assigned to DH6T [55],
while those at 25 , 30 and 64 were associated to PCBM [56]. The
DH6T peaks correspond to the a-axis orientation, which means that
90 F.F. Muhammad et al. / Materials Chemistry and Physics 188 (2017) 86e94

400 0.5
350 Alq3 PCBM

Current density (mA.cm-2)

300
DH6T:Alq3:PCBM 0.0
Gaq3
250
Intensity (a.u.)

DH6T:Gaq3:PCBM -0.5
200 DH6T
DH6T:PCBM
150 -1.0
PCBM
100 Gaq3 DH6T:PCBM (1:2)
-1.5 DH6T:Alq3:PCBM ([0.75+0.25]:2)
50 DH6T:Gaq3:PCBM ([0.75+0.25]:2)
Alq3
0
-0.2 0.0 0.2 0.4 0.6 0.8 1.0
0 10 20 30 40 50 60 70 80
Voltage (V)
2 theta
Fig. 7. The JeV characteristics of binary DH6T:PCBM and ternary DH6T:Mq3:PCBM
Fig. 6. XRD patterns of Alq3, Gaq3, DH6T:PCBM, DH6T:Alq3:PCBM and bulk heterojunctions.
DH6T:Gaq3:PCBM films with 25% molar fraction of Gaq3 and Alq3.

system. According to the accepted theory on the origin of Voc [58],

the thiophene backbone was deposited parallel to the substrate which is directly related to the (HOMO)De (LUMO)A, the Voc of the
surface [55]. Upon close inspection into the results, one can observe investigated devices can be still enlarged via optimizing the donor-
that the incorporation of Gaq3 or Alq3 into the DH6T:PCBM blends acceptor components. Referring to Fig. 4, one can see that the
has made the DH6T peaks to disappear and the PCBM peaks shifted HOMO and LUMO levels of the DH6T:Gaq3:PCBM system are more
towards higher diffraction angle. This might be referred to the preferably aligned than those of the DH6T:Alq3:PCBM. This proper
occurrence of strong intermolecular interaction between the moi- alignment reduces the probability of electron-hole recombination,
eties of DH6T and Mq3, by which the rotation of DH6T molecules is which in turn results in an effective PL quenching (see Fig. 5). The
more favoured and hence the crystallinity of Mq3 molecules is inexact energy levels alignment between DH6T:Alq3:PCBM com-
prevailed over that of the PCBM ones [57]. It is worth noting that ponents assists some of the generated holes to take their path from
ternary BHJ based on DH6T:Gaq3:PCBM showed larger crystalline Alq3 towards PCBM, leading to a larger electron-hole recombina-
portions in comparison to those of DH6T:Alq3:PCBM and tion and higher PL activity compared to those of the
DH6T:PCBM heterojunctions. The increment of crystalline portion DH6T:Gaq3:PCBM. Moreover, based on the (HOMO)D-(LUMO)A
was found to be directly correlated with the photoluminescence estimation for Voc, the 0.3 eV difference in between the HOMOs of
quenching [54]. Therefore, the decreased PL activity for Mq3 Alq3:PCBM might have played a role in weakening the electric field
incorporated BHJ films shown in Fig. 5 is in good agreement with responsible to dissociate excitons, thereby lowering the Voc of the
their increased crystallinity, as depicted in Fig. 6. Since PL device. Therefore, devices based on DH6T:Alq3:PCBM presented a
quenching is the result of decreased charge carrier recombination, smaller Voc (0.58 eV) compared to that of the DH6T:Gaq3:PCBM
the crystalline region acts upon promoting the movement of charge based ones (Voc ¼ 0.74 eV). Nevertheless, the origin of Voc in the
carriers to longer distances before they relapse or recombine ternary BHJ has remained a matter of debate and it is controversial
together. Consequently, the higher PL quenching and larger crys-
talline grains in DH6T:Gaq3:PCBM films indicated improved
exciton dissociation compared to that of DH6T:Alq3:PCBM films.
Noteworthy, the achievement of crystalline active layers in organic
solar cells is always desirable for facilitating efficient charge
transfer and increased exciton dissociation at the grain boundaries
[56].
Fig. 7 shows the current density-voltage characteristics of the
organic solar cells based on binary and ternary bulk hetero-
junctions with incorporating Gaq3 or Alq3 into the devices active
layers. The results showed a pronounced enhancement in the
photocurrent and output voltage of the devices when Gaq3 or Alq3
is incorporated. By adding Alq3, the short current density (Jsc) was
increased from 0.63 mA to 1.06 mA and the open circuit voltage
(Voc) shifted from 0.30 V to 0.58 V, while the addition of Gaq3
facilitated an increment in Jsc from 0.63 mA to 1.26 mA and Voc from
0.30 V to 0.74 V. Consequently, the Jsc and Voc were increased by an
order of about 2 and 2.5, respectively through incorporating Gaq3.
These increments are thought to be originated from a comple-
mentary enhancement of the photo-absorption ranging from
300 nm to about 750 nm, which was brought about by the inclusion
of Gaq3 (see Fig. 3). Interestingly, the highest attainable Voc ¼ 0.74 V
was recorded for the devices based on DH6T:Gaq3:PCBM ternary Fig. 8. The PeV characteristics of binary DH6T:PCBM and ternary DH6T:Mq3:PCBM
bulk heterojunctions.
 F.F. Muhammad et al. / Materials Chemistry and Physics 188 (2017) 86e94
yet.
Fig. 8 shows the power density-voltage (PeV) characteristics of
the TBHJ devices with and without incorporating Gaq3 or Alq3. The
results showed an increment in the generated maximum power
from 0.05 to 0.17 mW and from 0.05 to 0.28 mW for the Alq3 and
Gaq3 incorporated devices, respectively. It was found that the ef-
ficiency of Gaq3 included devices was improved by an order of
approximately six times compared to that of the controlled devices
(DH6T:PCBM). Nevertheless, the overall efficiency of the ternary
BHJ solar cells is still low, which we think is because of two main
reasons; first, the devices were fabricated in ambient condition, in
which neither glove box nor nitrogen atmosphere were utilized
and second the active layer solutions were not filtered, that is due
to the unavailability of these facilities during the work imple-
mentation. It was noticed that the shape of the PeV curves is
semicircle and deviated from that of bilayer devices [17], support-
ing the existence of blended ternary bulk heterojunction. It has
been reported that fill factor (FF) is limited due to the unbalanced
electrons and holes mobility in the devices active layer [59]. In the
current study, FF was increased from 26% to 27% and to 29% once
Alq3 and Gaq3 incorporated, respectively, suggesting that upon the
addition of Mq3 into the DH6T:PCBM blends, the charge carriers
transport is getting more balanced.
The parallel connection of a constant current source (Isc) with an
ideal diode that produces a voltage drop (Voc) at open circuit con-
dition can be utilized to model an ideal organic solar cell. However,
an additional series (Rs) and parallel (Rsh) resistance are required to
be connected to approach a real device behavior. In the OSCs
modeling, the Rs and Rsh are basically correlated with the charge
transport and recombination properties, respectively.
In order to elaborate the electrical response of the devices, their
series resistance (Rs) and shunt resistance (Rsh) were determined
from the inverse gradient of the JeV curve around the points where
Jsc ¼ 0 and Voc ¼ 0, respectively (see Fig. 9). Table 1 tabulates the
obtained photovoltaic and electrical parameters of the TBHJ de-
vices. One can notice that the value of Rs has increased from 887 to
985 U and to 936 U by incorporating Alq3 and Gaq3, respectively.
This increment was attributed to the disruption of electron mobility
upon the addition of Mq3, as Mq3 materials retain smaller electron
mobility compared to that of PCBM [46,60]. Nevertheless, because
of the higher electron mobility of Gaq3 [60] compared to that of
Fig. 9. Illustrates the regions where Rs and Rsh can be extracted from the JeV char-
acteristics of the devices.
91
Alq3, the devices with Gaq3 incorporation showed a lower Rs.
Noteworthy, the value of Rsh was pronouncedly increased from 5.5
to 6.2 kU and to 7.7 kU when Alq3 and Gaq3 were introduced,
respectively. This can be due to the formation of extra percolating
pathways; helping the charge carriers to diffuse for longer dis-
tances and hence reducing the PL activity (see Fig. 5).
Fig. 10 shows the JeV characteristics of the devices in dark and
light conditions from 1 to 2 V. It can be seen that by illuminating
the devices, a notable shape consistency of the curves in the for-
ward region is achievable, indicating stable device operation and
satisfactory reproducibility. Meanwhile, a considerable shape
change (downwards shifting) was observed for the curves in the
reverse biased region. This gradient shift in the JeV curve is referred
to as the occurrence of photovoltaic effect (photo-current produc-
tion), which in turn making these devices to act as efficient light
detectors. More computational and practical works on the TBHJs
are in progress in terms of optimizing the devices parameters and
their architectural design.
Fig. 11 shows the double log JeV characteristics of ternary
organic solar cells with and without incorporating Gaq3 or Alq3 in
the dark condition. Noteworthy, the current variation in the low
voltage range is almost linear (JfV 1:2 ) for all the devices, as
observed in region A (Ohmic regime). In region B, the current be-
comes space charge limited (SCLC) due to the presence of traps, and
therefore it is proportional to the square of the applied voltage
(JfV 2 ) [61]. The region where the slope of the curve is higher than
two can be described as a trap-filling space charge limited current
(TFSCLC) region and charges are injected into the bulk of active
layer [62,63]. In this region charge injection into the device occurs
by tunneling and the bulk is able to use up all the injected charges
in the conduction of current, until such a point where the bulk
becomes saturated, and injected charges start to accumulate near
the injected electrode. In region C, the rate of increasing current
with voltage decreases (as the current approaches to JfV 5 ). This is
due to the fact that all possible traps are filled and current ap-
proaches the trap-free SCLC. It should be pointed out that the SCLC
region was predominantly observed for the devices based on
DH6T:Gaq3:PCBM since the traps were filled rapidly and the cur-
rent raised up by several orders of magnitude (JfV 10:8 ). Mean-
while, the DH6T:PCBM based devices exhibited the expected
dependence of current density on V 2 . The results concluded that
Gaq3 incorporated devices show a larger exciton dissociation and
lower trap densities compared to those of the Alq3 incorporated
ones.
Fig. 12 shows the TEM images taken for solution blends of the
ternary heterojunction based on DH6T:Gaq3:PCBM with 0.25 M of
Gaq3. The composite system showed a planar distribution (see
Fig. 12-a), indicating a crystalline nature. This result is in a good
agreement to that observed by the XRD. Noticeably, the small
molecular acceptor (Gaq3) have been contributed in a nanoscale
phase separation, thereby producing a ball shaped aggregation in
the vicinity of the host polymer matrix (DH6T), as can be seen in
Fig. 12-b.
4. Conclusions
The improvement of ternary bulk heterojunction (TBHJ) based
on DH6T:Mq3:PCBM was realized by means of incorporating small
molecule acceptors of Gaq3 or Alq3 into the devices active layers.
The addition of Gaq3 resulted in a broader absorption spectrum and
stronger photoluminescence quenching of the TBHJ films compared
to those of the Alq3 added ones. These are because of two reasons;
first, the existence of a well matched HOMO and LUMO energy
levels between DH6T:Gaq3:PCBM components compared to that of
the DH6T:Alq3:PCBM and second, the contribution of higher
92 F.F. Muhammad et al. / Materials Chemistry and Physics 188 (2017) 86e94

Table 1
Photovoltaic parameters of organic solar cells based on ternary bulk heterojunction incorporating Gaq3 or Alq3.

Active layer Jsc. (mA) Voc. (V) Rs (U) Rsh (kU) FF % h%

DH6T:PCBM (1:2) 0.63 0.30 887 5.5 26 0.06
DH6T:Gaq3:PCBM ([0.75þ0.25]:2) 1.29 0.75 936 7.7 29 0.35
DH6T:Alq3:PCBM ([0.75þ0.25]:2) 1.06 0.60 985 6.2 27 0.21

3
dark (DH6T:PCBM)
dark (DH6T:Alq3:PCBM)
dark (DH6T:Gaq3:PCBM)
2 light (DH6T:PCBM)
light (DH6T:Alq3:PCBM)
Current density (mA.cm )
-2

light (DH6T:Gaq3:PCBM)

1
reverse bias

forward bias
-1

-2
-1 0 1 2
Voltage (V)
Fig. 10. The dark and light JeV characteristics of ternary organic solar cells incorporating 25 M% of Gaq3 and Alq3.

(a) DH6T:Mq3:PCBM (b)

1000 DH6T:PCBM
DH6T:Alq3:PCBM J αV5.2
100 DH6T:Gaq3:PCBM
10 J αV2
Mq3
DH6T:Mq3:PCBM

J αV5.8
1 J αV 1.1

0.1
J αV1.2
Log J

0.01 planar
1E-3 J αV 10.8 region C
1E-4
J αV1.3
1E-5
DH6T:PCBM

1E-6 region B
1E-7 region A

0.1 1 (c) (d)

Log V
Fig. 12. The TEM images for binary blends of DH6T:PCBM (d) and ternary blends of
Fig. 11. Double logarithmic plot of JeV characteristics for ternary organic solar cells DH6T:Mq3:PCBM with 0.25 M of Mq3 (aec).
incorporating 25 M% of Gaq3 and Alq3.
 F.F. Muhammad et al. / Materials Chemistry and Physics 188 (2017) 86e94
refractive index of Gaq3 compared to that of Alq3. It was noted that
TBHJ based on DH6T:Gaq3:PCBM showed larger crystalline por-
tions in comparison to those of DH6T:Alq3:PCBM and DH6T:PCBM
heterojunctions. The DH6T peaks corresponded to the a-axis
orientation, which means that the thiophene backbone was
deposited parallel to the substrate surface.
The results concluded a photovoltaic enhancement through
increasing the short circuit current and open circuit voltage (Voc) of
the devices by an order of about 2 and 2.5, respectively when Gaq3
was incorporated. These increments were thought to be originated
from a complementary enhancement of the photo-absorption
ranging from 300 nm to about 750 nm.
Consequently, the efficiency of Gaq3 included devices was
improved by an order of approximately six times compared to that
of the controlled devices (DH6T:PCBM). Meanwhile, the fill factor
(FF) was increased from 26% to 27% and to 29% once Alq3 and Gaq3
incorporated, respectively, suggesting that upon the addition of
Mq3 into the DH6T:PCBM blends, the charge carriers transport is
getting more balanced. Noteworthy, the value of shunt resistance
(Rsh) was pronouncedly increased from 5.5 to 6.2 kU and to 7.7 kU
when Alq3 and Gaq3 were introduced, respectively. This was
ascribed to the formation of additional percolating pathways;
helping the charge carriers to diffuse for longer distances and hence
reducing the PL activity. The results concluded that Gaq3 incorpo-
rated devices show a larger exciton dissociation and lower trap
densities compared to those of the Alq3 incorporated ones. These
improvements were attributed to the broadened absorption
spectra of the active layer blends, enhanced photo-induced charge
transfer and increased crystallinity of the devices by the incorpo-
ration of Gaq3 or Alq3.
Acknowledgments
The authors thank Universiti Teknologi Malaysia for the finan-
cial scheme (RADIS2016) to support this work. The author Fahmi F.
Muhammad would also like to thank Koya University and Ministry
of Higher Education of Kurdistan Region for the permission given to
carry out part of his research activities abroad.
References
[1] A. Cominetti, A. Pellegrino, L. Longo, R. Po, A. Tacca, C. Carbonera,
M. Salvalaggio, M. Baldrighi, S.V. Meille, Polymer solar cells based on poly(3-
hexylthiophene) and fullerene: pyrene acceptor systems, Mater. Chem. Phys.
159 (2015) 46e55.
[2] A. Hadipour, B. de Boer, P.W.M. Blom, Organic tandem and multi-junction
solar cells, Adv. Funct. Mater. 18 (2008) 169e181.
[3] S. Sankaran, K. Glaser, S. Ga €rtner, T. Ro
€ dlmeier, K. Sudau, G. Hernandez-Sosa,
A. Colsmann, Fabrication of polymer solar cells from organic nanoparticle
dispersions by doctor blading or ink-jet printing, Org. Electron. 28 (2016)
118e122.
[4] G. Dennler, N.S. Sariciftci, Flexible conjugated polymer-based plastic solar
cells: from basics to applications, Proc. IEEE 93 (2005) 1429e1439.
[5] B. Yin, L. Yang, Y. Liu, Y. Chen, Q. Qi, F. Zhang, S. Yin, Solution-processed Bulk
Heterojunction Organic Solar Cells Based on an Oligothiophene Derivative,
AIP, 2010.
[6] R.R. Nejm, A.I. Ayesh, D.A. Zeze, A. Sleiman, M.F. Mabrook, A. Al-Ghaferi,
M. Hussein, Electrical characteristics of hybrid-organic memory devices based
on Au nanoparticles, J. Electron. Mater. 44 (2015) 2835e2841.
[7] S. Grigalevicius, R. Zostautiene, D. Sipaviciute, B. Stulpinaite, D. Volyniuk,
J.V. Grazulevicius, L. Liu, Z. Xie, B. Zhang, Polymers containing diphenylvinyl-
substituted indole rings as charge-transporting materials for OLEDs,
J. Electron. Mater. 45 (2015) 1210e1215.
[8] M. Evyapan, A.D.F. Dunbar, Controlling surface adsorption to enhance the
selectivity of porphyrin based gas sensors, Appl. Surf. Sci. 362 (2016)
191e201.
[9] J.-H. Kwon, M.-H. Chung, T.-Y. Oh, H.-S. Bae, B.-K. Ju, Organic thin film tran-
sistors based oligothiophine derivatives using a,u-Dihexyl(quarter- & sexi-)
Thiophene, World Acad. Sci. Eng. Technol. 55 (2009) 490e493.
[10] S. Tavazzi, G. Barbarella, A. Borghesi, F. Meinardi, A. Sassella, R. Tubino, Ab-
sorption coefficient of sexithiophene thin films grown by organic molecular
beam deposition, Synth. Met. 121 (2001) 1419e1420.
93
[11] S.B. Aziz, Modifying poly(vinyl alcohol) (PVA) from insulator to small-bandgap
polymer: a novel approach for organic solar cells and optoelectronic devices,
J. Electron. Mater. 45 (2015) 736e745.
[12] P. Sehati, S. Braun, L. Lindell, L. Xianjie, L.M. Andersson, M. Fahlman, Energy-
level alignment at metal-organic and organic-organic interfaces in bulk-
heterojunction solar cells, IEEE J. Sel. Top. Quantum Electron. 16 (2010)
1718e1724.
[13] N.D. Treat, M.A. Brady, G. Smith, M.F. Toney, E.J. Kramer, C.J. Hawker,
M.L. Chabinyc, Interdiffusion of PCBM and P3HT reveals miscibility in a
photovoltaically active blend, Adv. Energy Mater. 1 (2011) 82e89.
[14] F.F. Muhammad, Design approaches to improve organic solar cells, J. Technol.
Innov. Renew. Energy 3 (2014) 1e8.
[15] J.-H. Huang, C.-M. Teng, Y.-S. Hsiao, F.-W. Yen, P. Chen, F.-C. Chang, C.-W. Chu,
Nanoscale correlation between exciton dissociation and carrier transport in
silole-containing cyclopentadithiophene-based bulk heterojunction films,
J. Phys. Chem. C 115 (2011) 2398e2405.
[16] D. Gebeyehu, B. Maennig, J. Drechsel, K. Leo, M. Pfeiffer, Bulk-heterojunction
photovoltaic devices based on donor-acceptor organic small molecule blends,
Sol. Energy Mater. Sol. Cells 79 (2003) 81e92.
[17] F.F. Muhammad, K. Sulaiman, Photovoltaic performance of organic solar cells
based on DH6T/PCBM thin film active layers, Thin Solid Films 519 (2011)
5230e5233.
[18] L. Lu, T. Xu, W. Chen, E.S. Landry, L. Yu, Ternary blend polymer solar cells with
enhanced power conversion efficiency, Nat. Phot. 8 (2014) 716e722.
[19] H. Cha, D.S. Chung, S.Y. Bae, M.-J. Lee, T.K. An, J. Hwang, K.H. Kim, Y.-H. Kim,
D.H. Choi, C.E. Park, Complementary absorbing star-shaped small molecules
for the preparation of ternary cascade energy structures in organic photo-
voltaic cells, Adv. Funct. Mater. 23 (2013) 1556e1565.
[20] B.M. Savoie, S. Dunaisky, T.J. Marks, M.A. Ratner, The scope and limitations of
ternary blend organic photovoltaics, Adv. Energy Mater. 5 (2015) n/a-n/a.
[21] F. Goubard, G. Wantz, Ternary blends for polymer bulk heterojunction solar
cells, Polym. Int. 63 (2014) 1362e1367.
[22] T. Ameri, P. Khoram, J. Min, C.J. Brabec, Organic ternary solar cells: a review,
Adv. Mater. 25 (2013) 4245e4266.
[23] L. Lu, M.A. Kelly, W. You, L. Yu, Status and prospects for ternary organic
photovoltaics, Nat. Phot. 9 (2015) 491e500.
[24] N. Li, P. Kubis, K. Forberich, T. Ameri, F.C. Krebs, C.J. Brabec, Towards large-
scale production of solution-processed organic tandem modules based on
ternary composites: design of the intermediate layer, device optimization and
laser based module processing, Sol. Energy Mater. Sol. Cells 120 (Part B)
(2014) 701e708.
[25] E.D. Peterson, G.M. Smith, M. Fu, R.D. Adams, R.C. Coffin, D.L. Carroll, Charge
balance and photon collection in polymer based ternary bulk heterojunction
photovoltaic devices containing cadmium selenide nanoparticles, Appl. Phys.
Lett. 99 (2011) 073304.
[26] R.C. Mulherin, S. Jung, S. Huettner, K. Johnson, P. Kohn, M. Sommer, S. Allard,
U. Scherf, N.C. Greenham, Ternary photovoltaic blends incorporating an all-
conjugated donoreacceptor diblock copolymer, Nano Lett. 11 (2011)
4846e4851.
[27] R.A. Street, D. Davies, P.P. Khlyabich, B. Burkhart, B.C. Thompson, Origin of the
tunable open-circuit voltage in ternary blend bulk heterojunction organic
solar cells, J. Am. Chem. Soc. 135 (2013) 986e989.
[28] R.A. Street, P.P. Khlyabich, A.E. Rudenko, B.C. Thompson, Electronic states in
dilute ternary blend organic bulk heterojunction solar cells, J. Phys. Chem. C
118 (2014) 26569e26576.
[29] A. Kumar, A. Bansal, B. Behera, S.L. Jain, S.S. Ray, Ternary hybrid polymeric
nanocomposites through grafting of polystyrene on graphene oxide-TiO2 by
surface initiated atom transfer radical polymerization (SI-ATRP), Mater. Chem.
Phys. 172 (2016) 189e196.
[30] B.H. Lessard, J.D. Dang, T.M. Grant, D. Gao, D.S. Seferos, T.P. Bender, Bis(tri-n-
hexylsilyl oxide) silicon phthalocyanine: a unique additive in ternary bulk
heterojunction organic photovoltaic devices, ACS Appl. Mater. Interfaces 6
(2014) 15040e15051.
[31] R. Lin, M. Wright, B. Puthen Veettil, A. Uddin, Enhancement of ternary blend
organic solar cell efficiency using PTB7 as a sensitizer, Synth. Met. 192 (2014)
113e118.
[32] F.F. Muhammad, K. Sulaiman, Utilizing a simple and reliable method to
investigate the optical functions of small molecular organic films - Alq3 and
Gaq3 as examples, Measurement 44 (2011) 1468e1474.
[33] J.-r. Lian, Y.-b. Yuan, L.-f. Cao, J. Zhang, H.-q. Pang, Y.-f. Zhou, X. Zhou,
Improved efficiency in OLEDs with a thin Alq3 interlayer, J. Lumin. 122e123
(2007) 660e662.
[34] T.-N. Lam, Y.-L. Lai, C.-H. Chen, P.-H. Chen, D.-H. Wei, H.-J. Lin, C.T. Chen, J.-
T. Sheu, Y.-J. Hsu, Interfacial symmetry of CoeAlq3eCo hybrid structures for
effective spin filtering, Appl. Surf. Sci. 354 (Part A) (2015) 90e94.
[35] P.-C. Kao, S.-Y. Chu, H.-H. Huang, Z.-L. Tseng, Y.-C. Chen, Improved efficiency
of organic photovoltaic cells using tris (8-hydroxy-quinoline) aluminum as a
doping material, Thin Solid Films 517 (2009) 5301e5304.
[36] X.-D. Liu, Z. Xu, F.-J. Zhang, S.-L. Zhao, T.-H. Zhang, W. Gong, J.-L. Song, C. Kong,
G. Yan, X.-R. Xu, Influence of small-molecule material on performance of
polymer solar cells based on MEH-PPV: PCBM blend, Chin. Phys. B 19 (2010)
118601.
[37] Y. Zhang, D. Deng, K. Lu, J. Zhang, B. Xia, Y. Zhao, J. Fang, Z. Wei, Synergistic
effect of polymer and small molecules for high-performance ternary organic
solar cells, Adv. Mater. 27 (2015) 1071e1076.
94 F.F. Muhammad et al. / Materials Chemistry and Physics 188 (2017) 86e94
[38] L. Xiao, K. Gao, Y. Zhang, X. Chen, L. Hou, Y. Cao, X. Peng, A complementary
absorption small molecule for efficient ternary organic solar cells, J. Mater.
Chem. A 4 (2016) 5288e5293.
[39] L. Ye, H.-H. Xu, H. Yu, W.-Y. Xu, H. Li, H. Wang, N. Zhao, J.-B. Xu, Ternary bulk
heterojunction photovoltaic cells composed of small molecule donor additive
as cascade material, J. Phys. Chem. C 118 (2014) 20094e20099.
[40] W. Chen, Z. Du, M. Xiao, J. Zhang, C. Yang, L. Han, X. Bao, R. Yang, High-per-
formance small molecule/polymer ternary organic solar cells based on a layer-
by-layer process, ACS Appl. Mater. Interfaces 7 (2015) 23190e23196.
[41] F.F. Muhammad, K. Sulaiman, Effects of thermal annealing on the optical,
spectroscopic, and structural properties of tris (8-hydroxyquinolinate) gal-
lium films grown on quartz substrates, Mater. Chem. Phys. 129 (2011)
1152e1158.
[42] F.F. Muhammad, M.Y. Yahya, K.A. Ketuly, A.J. Muhammad, K. Sulaiman,
A study on the spectroscopic, energy band, and optoelectronic properties of
a,u-dihexylsexithiophene/tris(8-hydroxyquinolinate) gallium blends; DH6T/
Gaq3 composite system, Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 169
(2016) 144e151.
[43] F.F. Muhammad, A.I. Abdul Hapip, K. Sulaiman, Study of optoelectronic energy
bands and molecular energy levels of tris (8-hydroxyquinolinate) gallium and
aluminum organometallic materials from their spectroscopic and electro-
chemical analysis, J. Organomet. Chem. 695 (2010) 2526e2531.
[44] S. Cook, H. Ohkita, Y. Kim, J.J. Benson-Smith, D.D.C. Bradley, J.R. Durrant,
A photophysical study of PCBM thin films, Chem. Phys. Lett. 445 (2007)
276e280.
[45] J.-H. Kwon, J.-H. Seo, p-type semiconducting a,u-dihexylsexithiophene for an
organic thin film transistor, J. Appl. Phys. 101 (2007) 064502.
[46] R. Koeppe, N.S. Sariciftci, Photoinduced charge and energy transfer involving
fullerene derivatives, Photochem. Photobiol. Sci. 5 (2006) 1122e1131.
[47] F. Wudl, Fullerene materials, J. Mater. Chem. 12 (2002) 1959e1963.
[48] I. Hernandez, W.P. Gillin, Influence of high hydrostatic pressure on Alq3, Gaq3,
and Inq3 (q ¼ 8-Hydroxyquinoline), J. Phys. Chem. B 113 (2009)
14079e14086.
[49] A. Sassella, R. Tubino, A. Borghesi, C. Botta, S. Destri, W. Porzio, G. Barbarella,
Optical properties of oriented thin films of oligothiophenes, Synth. Met. 101
(1999) 538e541.
[50] T. Sato, M. Fujitsuka, H. Segawa, T. Shimidzu, K. Tanaka, Dual photo-
luminescence of polythiophene thin films, Synth. Met. 95 (1998) 107e112.
[51] G. Horowitz, S. Romdhane, H. Bouchriha, P. Delannoy, J.-L. Monge, F. Kouki,
P. Valat, Optoelectronic properties of sexithiophene single crystals, Synth.
Met. 90 (1997) 187e192.
[52] M.A. Loi, G. Bongiovanni, A. Mura, Q. Cai, C. Martin, H.R. Chandrasekhar,
M. Chandrasekhar, W. Graupner, F. Garnier, High pressure effects on the
photoluminescence intensity of sexithiophene single crystals, Synth. Met. 116
(2001) 311e315.
[53] H.S.O. Chan, S.C. Ng, Synthesis, characterization and applications of
thiophene-based functional polymers, Prog. Polym. Sci. 23 (1998) 1167e1231.
[54] F.F. Muhammad, K. Sulaiman, Optical and morphological modifications in
post-thermally treated tris(8-hydroxyquinoline) gallium films deposited on
quartz substrates, Mater. Chem. Phys. 148 (2014) 473e477.
[55] N. Kiriy, A. Kiriy, V. Bocharova, M. Stamm, S. Richter, M. Plo € tner, W.-J. Fischer,
F.C. Krebs, I. Senkovska, H.-J. Adler, Conformation, molecular packing, and
field effect mobility of regioregular b, b’-dihexylsexithiophene, Chem. Mater.
16 (2004) 4757e4764.
[56] P.G. Karagiannidis, S. Kassavetis, C. Pitsalidis, S. Logothetidis, Thermal
annealing effect on the nanomechanical properties and structure of P3HT:
PCBM thin films, Thin Solid Films 519 (2011) 4105e4109.
[57] J. Sakai, T. Taima, T. Yamanari, K. Saito, Annealing effect in the sexithiophene:
C70 small molecule bulk heterojunction organic photovoltaic cells, Sol. Energy
Mater. Sol. Cells 93 (2009) 1149e1153.
[58] T. Yamanari, T. Taima, J. Sakai, K. Saito, Origin of the open-circuit voltage of
organic thin-film solar cells based on conjugated polymers, Sol. Energy Mater.
Sol. Cells 93 (2009) 759e761.
[59] D. Gupta, S. Mukhopadhyay, K.S. Narayan, Fill factor in organic solar cells, Sol.
Energy Mater. Sol. Cells 94 (2010) 1309e1313.
[60] B.J. Chena, X.W. Sun, Influences of central metal ions on the electrolumines-
cence and transport properties of tris-„8-hydroxyquinoline metal chelates,
Appl. Phys. Lett. 82 (2003) 3017e3019.
[61] J.H. Scho€n, C. Kloc, S. Berg, T. Siegrist, B. Batlogg, Two-dimensional band-like
charge transport in [alpha]-sexithiophene, Org. Electron. 2 (2001) 135e142.
[62] G.D. Sharma, P. Suresh, S.K. Sharma, M.S. Roy, Optical and electrical properties
of hybrid photovoltaic devices from poly (3-phenyl hydrazone thiophene)
(PPHT) and TiO2 blend films, Sol. Energy Mater. Sol. Cells 92 (2008) 61e70.
[63] K. Sulaiman, M.S. Fakir, Electrical conduction and photovoltaic effects of TPA-
derivative solar cells, Thin Solid Films 519 (2011) 5219e5222.