Journal of Colloid and Interface Science 527 (2018) 172–179

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Journal of Colloid and Interface Science

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

Regular Article

Compositional engineering of acceptors for highly efficient bulk

heterojunction hybrid organic solar cells
S. Amber Yousaf, M. Ikram ⇑, S. Ali
Solar Cell Applications Research Lab, Department of Physics, Government College University Lahore, 54000 Punjab, Pakistan

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

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

Article history: The wet chemical synthesis of chromium oxide (Cr2O3) nanoparticles (NPs) and its application in active
Received 2 February 2018 layer of inverted bulk heterojunction organic solar cells is documented in this research. Chromium oxide
Revised 5 May 2018 NPs of 10–30 nm size range having a band gap of 2.9 eV were successfully synthesized. These NPs were
Accepted 11 May 2018
used in inverted organic solar cells in amalgamation with P3HT:PCBM and PTB7:PCBM polymers. The
Available online 25 May 2018
fabricated hybrid devices improves PCE significantly for P3HT:PCBM and PTB7:PCBM systems. The pho-
tophysical energy levels, optoelectrical properties and microscopic images have been systematically
Keywords:
studied for the fabricated devices. The introduction of Cr2O3 nanoparticles (NPs) enhances light
Chromium oxide
Polymers
harvesting and tunes energy levels into improved electrical parameters. A clear red shift and improved
Fullerene absorption have been observed for ternary blended devices compared to that observed with controlled
Efficiency organic solar cells. Apparently, when the amount of NPs in the binary polymer blend exceeds the required
Absorption optimum level, there is a breakdown of the bulk heterojunction leading to lowering of the optical and
Binary blend electrical performance of the devices.
Ó 2018 Elsevier Inc. All rights reserved.

1. Introduction junction solar cells (OBHJSC) have attracted extensive research

attention owing to benefits of reduced fabrication cost, and
In renewable energy resources, electricity through solar energy promising features like eco-friendliness, use of earth-abundant
offers an attractive alternative but it accounts for only 1% of total materials, large area, lightweight, mechanical flexibility and tun-
world’s power consumption [1]. Tremendous research in the field able energy level alignment [2–5]. Hence, rapid and significant
has resulted in the development of various types of photovoltaic investigations have been carried out to improve the power conver-
cells (PVCs). Among these, solution-processed organic bulk hetero- sion efficiency (PCE). The several approaches that can increase PCE
include interface engineering, surface modification of charge trans-
⇑ Corresponding author. port layers, insertion of buffer layers/optical spacer, combination of
E-mail address: [email protected] (M. Ikram). new donor (D) and acceptor (A) materials, use of additives, various

https://doi.org/10.1016/j.jcis.2018.05.027
0021-9797/Ó 2018 Elsevier Inc. All rights reserved.
 S. Amber Yousaf et al. / Journal of Colloid and Interface Science 527 (2018) 172–179 173

processing methods, and device architectures [6,7]. The efficiencies respectively. The prepared solutions were stirred overnight at 70
of OBHJSCs is apparently approaching to its limit i.e. 10–12%. [8]. °C to ensure complete dissolution of the polymers in solvents.
PCBM based devices have attained the maximum efficiency of Chromium oxide NPs were separately dispersed in DCB and CB
11.6% and 13% is obtained with non-fullerene acceptors. [9,10]. and then added into the polymer solutions at different weight
However, further progress in the performance of the binary struc- ratios (1–4%) of polymer to nanoparticles.
ture is rather challenging due to low charge mobility, short exciton To fabricate the devices, first a thin layer of electron transport
diffusion length and recombination losses. The weak absorption of layer of ZnO was spin coated on cleaned and patterned ITOs at
the devices in the visible region also restricts further advancement. 5000 rpm for 45sec and heated on a hot plate at 150 °C for 20
A facile strategy could involve blending organic and inorganic min [31]. The binary and ternary hybrid solutions (composed of
semiconductors in the active layer of BHJ as organic-inorganic polymers and nanoparticles) were spun cast onto ZnO coated
hybrid bulk heterojunction solar cells-HBHJSCs exhibit rising pro- substrates at 1500 rpm for1min and P3HT-based devices were
spects to integrate the potential advantages of both materials. subsequently heated at 110 °C for 20 min. Finally, a thin layer of
Semiconducting nanoparticles (NPs) have high physical-chemical 10 nm-MoO3 and 100 nm-Ag were thermally evaporated at high
stability and strong electronic-photoconducting properties [11]. vacuum (10 7 mbar) on the devices.
The combined absorption band of polymer and nanocrystals can Hereafter, ITO/ZnO/P3HT:Cr2O3:PC60BM/MoO3/Ag structured-
effectively enhance the absorption range and build efficient path- based inverted devices are referred to as D1 (0%), D2 (1%), D3
ways for exciton dissociation at D/A interfaces [12]. (2%), D4 (3%), D5 (4%) and ITO/ZnO/PTB7:Cr2O3:PC70BM/MoO3/Ag
In past, hybrid devices with polymer/nanomaterials binary architecture inverted devices as D6 (0%), D7 (1%), D8 (2%), D9
blends have been reported by many researchers [13–17]. There (3%), D10 (4%).
are also reports on the use of ternary and quaternary blends-
based hybrid organic solar cells with promising results, generating 2.4. Characterization
a lot of interest in PV research [18–20]. The reported increase in
efficiencies for TiO2, ZnO, CuO, NiO, CdSe, PbS, CuInS2 are 7%, X-ray diffractometer (model: PAN Analytical X’pert PRO)
23%, 18%, 40%, 28%, 23%, 47%, 97%, respectively [21–27]. equipped with Cu-Ka radiation (1.54 Å) and 2h values 20–80°,
In this work, we attempted to fabricate ternary HBHJSC devices was used to obtain structural and phase information on the sam-
and to study the influence of incorporation of Cr2O3 nanoparticles ples. Absorption profile of NPs in solution form, polymer:PCBM
in the active layer consisting of P3HT, PC60BM and PTB7, PC70BM. and polymer:PCBM:Cr2O3 blend in the thin film were recorded
Chromium oxide is one of the extensively studied p-type semicon- using UV–Vis spectrophotometer (model: Genesys 10S). To charac-
ductor metal oxide and has a large band gap of 3.0–3.3 eV [28,29]. terize electrical parameters at 1 sun-1000 Wm 2 (Xenon bulb
The incorporation is expected to upsurge the device performance coupled with AM 1.5 filter) the solar simulator CT 100AAA with
as Cr2O3 is highly stable with high electrical conductivity [28] Keithley 2420 source meter unit was used. AFM images were taken
and its large band-gap can effectively block holes and excitons on a JEOL JSPM-5200 in tapping mode. External quantum efficiency
which can redistribute light in the active layer [30]. (EQE) measurements were recorded via model QEX 10PV.

2. Experimental details
3. Results and discussion
2.1. Materials
X-ray diffraction pattern obtained on the chromium oxide pow-
Glass substrates coated with ITO of sheet resistance 8-12O were der is shown in Fig. 1. The observed prominent peaks were indexed
obtained from Delta Technologies, USA. Poly[[4,8-bis[(2-ethylhexyl) to the rhombohedral phase (Cr2O3) based on JCPDS No. 38-1479,
oxy]benzo[1,2-b:4,5-b’]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethyl except the peak at 2h = 31.63° (2 0 0) plane was indexed to
hexyl)carbonyl]thieno[3,4-b] thiophenediyl]][6,6]) (PTB7) was orthorhombic phase (CrO3) based on JCPDS No. 03-065-1388. The
received from 1-Material (Canada) and poly(3-hexylthiophene- characteristic peak intensity and positions at 2h = 24.7°, 33.7°,
2,5-diyl) (P3HT) from Ossila, UK. 99.99% pure PCBM was purchased 36.29°, 41.59°, 45.38°, 50.3°, 54.70°, 63.37°, 65.18°, 73.09°, and
from Solenne. Chromium chloride (CrCl3) was procured from 76.9° correspond to the crystal plane of (0 1 2), (1 0 4), (1 1 0),
Sigma-Aldrich, and sodium hydroxide (NaOH) from Panreac. (1 1 3), (2 0 2), (0 2 4), (1 1 6), (2 1 4), (3 0 0), (1 1 9), and (2 2 0) of
crystalline Cr2O3 and CrO3 phases without any traces of impurities
2.2. Synthesis of Cr2O3 nanoparticles [29,32]. The average crystallite size of the particles was estimated
using the Debye-Scherrer equation shown below and applied to
The Cr2O3 nanoparticles with rhombohedral structure were syn- all diffraction peaks.
thesized by a wet chemical method. Typically, 0.1 M solutions of
CrCl3 and NaOH were prepared separately in distilled water. The
d ¼ kk=bh cosh ð1Þ
solutions were then mixed and stirred for 2 h at room temperature. where k is a shape factor which normally ranges between 0.9 and
CrCl3 +3NaOH!Cr(OH)3 +3NaCl 1.0 (in this study K = 0.9), k is the X-ray wavelength, and b and h
are the half width of the peak and half of the Bragg angle, respec-
Cr(OH)3 precipitate was collected and washed several times tively. Using the equation, the crystallite sizes of Cr2O3 nanoparti-
with distilled water to remove impurities. The washed precipitates cles were found to be in the range of 10–40 nm. FESEM
were aged at 60 °C for 48 h and the dried Cr(OH)3 was heated in a photograph image collected at 20,000 magnification and shown
muffle furnace at 450 °C for 30 min to obtain Cr2O3. in Fig. 1(b) reveals the presence of an uniform and homogenous dis-
2Cr(OH)3 !2Cr2 O3 +3H2 O tribution of NPs in the form of cluster agglomerations. The inset
demonstrates the transparent magnified image of nanostructure
at 370,000 magnification. The particle size of nanoparticles in
2.3. Device fabrication the range 10–13 nm from higher resolution FESEM image is in con-
firmation with the average crystallite size obtained from XRD. The
P3HT:PC60BM (1:0.8) and PTB7:PC70BM (1:1.5) solutions were UV–Vis absorption spectrum of Cr2O3 NPs is shown in Fig. 1(c). As
prepared in 1, 2 dichlorobenzene (DCB) and chlorobenzene (CB), displayed, Cr2O3 NPs have intense absorption in the ultraviolet
174 S. Amber Yousaf et al. / Journal of Colloid and Interface Science 527 (2018) 172–179

Fig. 1. (a) XRD pattern of synthesized Cr2O3 nanoparticles (b) FESEM image (c) UV–Vis spectrograph of Cr2O3.

region i.e. 270 nm and 370 nm as reported in the literature [32]. Fig. 3(a) and (b) indicate current density (J) Vs voltage (V)
The synthesized NPs have a bandgap 2.9 eV as calculated by Tauc’s curves of P3HT/PTB7:Cr2O3:PCBM-based devices and the various
plot shown in inset (1c). performance electric output parameters obtained from these
Fig. 2 represents energy diagram of the fabricated inverted curves are summarized in Table 1. The extracted values of control
devices in flat-band conditions and shows proposed charge trans- and doped devices are gained through several experiments and
port mechanism. The highest occupied molecular orbital (EHOMO) averaged over 10 devices. It can be seen that devices with NPs out-
and lowest unoccupied molecular orbital (ELUMO) of P3HT, PTB7 perform the pure polymers blended (P3HT/PTB7:PCBM) solar cells.
and PCBM are 3.2–5.2 eV, 3.5–5.1 eV and 4.3–6.0 eV respectively The significant increase between the binary and ternary blend-
[33]. Cr2O3 (conduction level (Ec) = 4.0 eV) [30] in active layer based devices parameters was found in Jsc, Voc and fill factor (FF).
may lower HOMO of polymer. The reorganization of energy levels The doped free devices (D1, D6) exhibit Jsc (8.77, 14.77 mAcm 2),
could result in change in Voc [34] and can facilitate charge trans- Voc of (0.57, 0.701 V) and FF of (50.2, 54.2%) leading to PCE of
port along with PCBM. Upon light irradiation, polymer absorbs (2.51, 5.61%) for P3HTand PTB7-based devices respectively. As
photons to generate excitons and the charge separation might take expected, incorporation of NPs enhanced electrical properties pro-
place at D/NP and D/PCBM interfaces [11]. The generated electrons viding a maximum Jsc of (9.94, 15.73 mA cm 2), Voc (0.59, 0.716 V)
can transfer from polymer to Cr2O3, polymer to PCBM and Cr2O3 to and FF of (62.6, 59.6%) with PCE to (3.67, 6.72%) for P3HT- and
PCBM and finally reach ITO. The hole transportation is realized PTB7-based ternary devices (D4, D8) respectively. The decrease
inversely to their respective electrode. The large band gap of in series resistance Rs for D1 to D4, and D6 to D8 (Table 1) suggest
Cr2O3 can efficiently block holes resulting in reduced recombina- that initial incorporation of NPs shortens the electron transport
tion losses. path by introducing percolation network and facilitates the
 S. Amber Yousaf et al. / Journal of Colloid and Interface Science 527 (2018) 172–179 175

Fig. 2. Energy band diagram and device structure of inverted devices.

Fig. 3. J-V graphs of inverted devices (a) P3HT:Cr2O3:PCBM (b) PTB7:Cr2O3:PCBM.

Table 1
J-V data of P3HT:Cr2O3:PCBM and PTB7:Cr2O3:PCBM-based inverted device extracted from Fig. 3(a) and (b).
2
Devices Cr2O3 doping Jsc (mA cm ) Voc (V) FF (%) PCE (%) Rsh [O cm2] Rs [O cm2]
D1 0% 8.77 0.57 50.2 2.51 4129 6.139
D2 1% 9.12 0.58 54.9 2.90 6225 3.409
D3 2% 9.45 0.58 57.9 3.17 8908 3.081
D4 3% 9.94 0.59 62.6 3.67 9007 2.267
D5 4% 7.79 0.58 56.8 2.61 5519 2.616
D6 0% 14.77 0.701 54.2 5.61 3942 3.876
D7 1% 15.27 0.71 55.9 6.09 3970 3.210
D8 2% 15.73 0.72 59.6 6.72 5455 2.831
D9 3% 15.43 0.72 57.13 6.31 5248 3.245
D10 4% 14.93 0.70 52.16 5.46 2940 3.574

transfer of generated electrons from polymer to PCBM that subse- increment in FF with increasing concentration of NPs in the active
quently increases FF and Jsc of hybrid active layers [35]. layer indicates higher mobility of charges [37]. The enhanced effi-
The percolation network suppresses leakage current as indi- ciency of PTB7-based devices can mainly be attributed to improv-
cated by increased values of Rsh. The higher electron mobility of ing FF as there is no significant increase in Jsc.
NPs also aids to the electron transportation and collection to the It is also evident that increasing quantity of NPs over the opti-
respective electrodes [12]. The Voc of P3HT-based ternary devices mum amount in P3HT/PTB7:PCBM matrix produced a negative
increased from 0.57 to 0.59 V (D1 to D4) and for PTB7 from effect on PCE as a large-scale agglomeration of NPs removes charge
0.70 to 0.72 V (D6 to D8). This increase in Voc can be attributed collection pathways [38].
to the efficient charge separation between P3HT/PTB7:PCBM, Surface SEM images of the doped free and doped samples were
P3HT/PTB7:Cr2O3 and Cr2O3:PCBM interfaces [36] as the difference captured to observe the solubility of NPs in the solvent and to
between Ec of NPs and EHOMO of P3HT/PTB7 is greater than the dif- gauge their morphology. The surface morphology of P3HT/PTB7:
ference between ELUMO of PCBM and EHOMO of P3HT/PTB7 [26]. The PCBM:Cr2O3 active layer shown in Fig. 4 indicates that the Cr2O3
176 S. Amber Yousaf et al. / Journal of Colloid and Interface Science 527 (2018) 172–179

NPs are randomly dispersed in the film. These grains may already blend films (P3HT/PTB7:PCBM), are relatively smooth (a, f) with root
be present in solution and remaining are forced to the topmost mean square (RMS) values of 0.639 nm and 2.39 nm respectively.
polymer layer where they further coalesce [12,39]. The NPs show The addition of NPs increased the roughness gradually of the films.
small and large clusters (D4, D8) because of weak binding energy The RMS values of optimized films are 6.08 nm (D4) and 12.3 nm
between pyridine and NPs [36,40]. These aggregates have the (D8) for P3HT-and PTB7-based ternary blend films. The increase in
larger size between (400 and 600) nm than the active layer thick- roughness is attributed to the presence of large size clusters of
ness and participates to increase the surface roughness to form NPs. This increased roughness might have originated due to the dif-
percolation pathways in the active layer which facilitate charge fused reflection between the active layer and the top electrode that
transportation. At higher NP concentrations, larger agglomeration consequently results in the substantial harvesting of incident light
(D5, D10) of nanoparticles breaks the percolation network, and enhancement in absorption [22,41,42]. The SEM and AFM
suggesting destruction of favorable thin film morphology. results conclude that there is no distinctive difference between bin-
To further investigate the effect of Cr2O3 NPs incorporation on the ary and ternary blend films at micrometer scale [12,43].
devices performance, atomic force microscopy (AFM) was Fig. 6(a) and (b) illustrate UV–Vis absorption spectra of binary
performed Fig. 5(a)–(i) to determine micro morphology and film and ternary blended films. It is observed that the two peaks
roughness. The AFM images revealed that the surfaces of binary around 330 nm and 500 nm correspond to PCBM and P3HT

Fig. 4. SEM images of P3HT:Cr2O3:PC60BM (D1, D4, D5) and PTB7:Cr2O3:PC70BM (D6, D8, D10).
 S. Amber Yousaf et al. / Journal of Colloid and Interface Science 527 (2018) 172–179 177

Fig. 5. AFM images of P3HT:Cr2O3:PCBM (a–e) and PTB7:Cr2O3:PCBM (f–h).

respectively. With the incorporation of Cr2O3, the absorption agrees well with the device parameters of different D/A-based
intensity increased in the visible region with red shift and shoul- binary and ternary systems. The maximum EQE for P3HT- and
ders at 550 nm and 600 nm, respectively. The observed red shift PTB7-based ternary devices (D4 and D8) is nearly 80% and 74%,
and more pronounced shoulder were credited to the higher respectively. The improvement in EQE can be credited to the
crystallinity of P3HT with the addition of NPs [18]. With a small increased photon absorption and charge mobility. Heterojunction
amount of doping, no significant change was found in the electric field formed between NPs and organic materials also con-
absorption spectra of PTB7:PCBM films as wide range strong tribute to the enhanced photoelectric conversion property [22]. As
absorption of PTB7:PCBM system dominated Cr2O3. The discussed earlier, incorporation of NPs provides multiple pathways
increased area under the absorption profile at different wave- for electron transfer that subsequently improved the device
lengths of ternary blends indicates that more photons are performance and EQE.
harvested [36]. The enhanced absorption could be related to
the increased roughness of films, as discussed earlier; high
roughness might increase the light scattering in the active layer, 4. Conclusions
resulting in increased absorption in ternary blend films [38].
The EQE measurements shown in Fig. 7(a) and (b) highlights the Chromium oxide (Cr2O3) nanoparticles were utilized for the
same behavior as Jsc of the devices and photocurrent response first time in the active layer of bulk heterojunction organic solar

Fig. 6. UV–Vis absorption spectra of inverted films (a) P3HT:Cr2O3:PCBM (b) PTB7:Cr2O3:PCBM.
178 S. Amber Yousaf et al. / Journal of Colloid and Interface Science 527 (2018) 172–179

Fig. 7. EQE profile of (a) P3HT:Cr2O3:PCBM (b) PTB7:Cr2O3:PCBM.

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