Research article

Received: 19 January 2014, Revised: 1 March 2014, Accepted: 5 March 2014, Published online in Wiley Online Library: 30 June 2014

(wileyonlinelibrary.com) DOI: 10.1002/pat.3304

Design and synthesis of pyromellitic diimide-

based donor–acceptor conjugated polymers
for photovoltaic application
Chunhua Luoa*, Zhitao Shenb, Xiangjian Menga*, Li Hana, Shuo Suna,
Tie Lina, Jinglan Suna, Hui Pengb and Junhao Chua

Three of conjugated polymers based on pyromellitic diimide (PMDI) as the acceptor unit and thienothiophene (TT)
as the donor unit were successfully synthesized by Stille coupling. The effect of the side chain length and thiophene
π-bridge on the polymers’ optical and electrochemical properties was investigated. Electrochemical characterization
indicated that these polymers have deep highest occupied molecular orbital energy levels between 5.7 and
5.8 eV. Polymer solar cells were fabricated by using these PMDI-based polymers as the donor and [6,6]-phenyl-C61-
butyric acid methyl ester as the acceptor. The polymer P1 whose PMDI unit was functionalized with 2-ethylhexyl side
chain shows the higher short-circuit current (Jsc) and fill factor (FF) compared with that of P2 with a 2-octyldodecyl
side chain on the PMDI unit. The results also illustrate that the insertion of a thiophene π-bridge between PMDI and
TT (the polymer P3) leads to the broader absorption and better photovoltaic performance. The best performance was
obtained from the cell based on the polymer P3 with a power conversion efficiency of 0.43% under the illumination
of AM 1.5 G, 100 mW/cm2. Copyright © 2014 John Wiley & Sons, Ltd.

Keywords: pyromellitic diimide; thienothiophene; D–A conjugated polymer; synthesis; polymer solar cell

INTRODUCTION
Harvesting energy from sunlight using photovoltaic effect is a
promising approach to solve the global energy crisis with
a clean, renewable resource. Polymer solar cells (PSCs) have
been attracting more and more interest because they can be
fabricated on flexible, large area substrates using solution
processable techniques and are cost effective compared with
traditional inorganic solar cells.[1,2] So far, the most efficient
architecture for PSCs is the bulk heterojunction structure based
on a blend of an electron donor (conjugated polymer) and an
electron acceptor (usually fullerene derivative) as an active layer.
As the key part of the PSCs, the semiconductors’ properties of
active layers play an important role in the photovoltaic efficiency
and stability of the devices. Owing to the limit absorption in the
visible-to-near-infrared ranges of n-type fullerene derivatives,
the development of p-type conjugated polymers with a low
band gap is crucial to achieve highly efficient PSCs. Several strat-
egies have been used for the design of conjugated polymers
with a low band gap. Among these, the donor–acceptor (D–A)
approach where alternating electron-donating and electron-
withdrawing units are incorporated into the backbone of one
polymer enables the precise tuning of band gap and energy
level and is the most promising technique.[3,4] For example, Yu
et al. synthesized a new low band gap polymer PTB7 and the
solar cell based on the blend film of PTB7 with PC71BM exhibited
an efficiency up to 7.4%.[5] You et al. synthesized the polymer
PDTP-DFBT (band gap: 1.38 eV) and the tandem cell PSC based
on this polymer reaching 10.6%.[6]
Aromatic tetracarboxylic diimides are considered as promising
n-type semiconductors due to their good stabilities, relatively
high electron affinity and high electron mobility.[7,8] There have
been a lot of studies on n-type small molecule semiconductors
based on aromatic tetracarboxylic diimides,[8–12] particularly on
perylene diimide (PDI)[13] and naphthalene diimide (NDI) .[14,15]
Furthermore, they can also be used as electron-deficient units
to construct D–A conjugated polymers. The conjugation with
an electron-donating unit enables the tuning of the band gap
while maintaining the lowest unoccupied molecular orbital
(LUMO) energy level. At the same time, the attachment of side
chain to the imide nitrogen atom allows the adjustment of the
solubility and the solid state morphology of the corresponding
polymers.[16,17] For example, Guo et al. synthesized a series
of pyromellitic diimide (PMDI)-based D–A polymers and found
that the solubility of the resulting polymers depends on the
side chain volume fraction, the relative placement and symmetry
of side chains along the polymer backbone.[17] The use of
PDI-based and NDI-based polymers as n-type materials in organic
electronics has been extensively studied.[7,18] For example, Zhou
et al. reported the synthesis of six PDI-based conjugated polymers,
* Correspondence to: Chunhua Luo and Xiangjian Meng, National Laboratory
for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy
of Science, Shanghai, 200083, China.
E-mail: chunhua_luo@hotmail.com; xjmeng@mail.sitp.ac.cn
a C. Luo, X. Meng, L. Han, S. Sun, T. Lin, J. Sun, J. Chu
National Laboratory for Infrared Physics, Shanghai Institute of Technical Phys-
ics, Chinese Academy of Science, Shanghai, 200083, China
b Z. Shen, H. Peng
Key Laboratory of Polarized Materials and Devices, Ministry of Education, East
China Normal University, Shanghai, 200241, China
809

Polym. Adv. Technol. 2014, 25 809–815 Copyright © 2014 John Wiley & Sons, Ltd.

the power conversion efficiency of all-polymer solar cell based on
PT1/PC-PDI reached 2.23%.[18] Kim et al. synthesized an NDI-based
conjugated polymer PNDI-TVT, organic field effect transistor based
on PNDI-TVT showed electron mobility up to 1.8 cm2 V 1 s 1.[19]
Pyromellitic diimide, which has only a benzene ring as the
centre core, is the most compact aromatic tetracarboxylic
diimide that has been used as building block for insulating
aromatic polyimides.[20] PMDI has relatively high electron affinity
that can interact with electron rich π-systems through charge
transfer in both solution and solid state and has been used in
the construction of supramolecular architectures.[21,22] The
organic field effect transistor based on a modified PMDI exhibited
high electron mobility up to 0.079 cm2 V 1 s 1.[12] PMDI has a
modest LUMO energy level (ELUMO = ~3.6 eV).[17] It is possible to
use it to construct D–A conjugated polymers, which could be used
as the acceptor materials in all-polymer solar cells, or the donor
materials in polymer-fullerene composite solar cells.[23] However,
compared with PDI and NDI, the application of PMDI-based D–A
conjugated polymers in PSCs is rarely investigated.
In this work, we report the synthesis of three of D–A
conjugated polymers based on PMDI as the acceptor unit and
thienothiophene (TT) as the donor unit through Stille coupling.
For comparison, two different alkyl side chains, 2-ethylhexyl
and 2-octyldodecyl, were functionalized to the nitrogen atom
in the PMDI unit and a thiophene π-bridge was introduced
between PMDI and TT. The optoelectronic properties of resulting
polymers were characterized by UV-vis spectroscopy and electro-
chemical measurements. The solar cells were fabricated by using
these PMDI-based polymer as the donor and [6,6]-phenyl-C61-
butyric acid methyl ester (PCBM) as the acceptor. The device
performances related to active layer compositions and annealing
temperatures were studied.
EXPERIMENTAL
Materials
All reagents were purchased from Aldrich, Alfa Aesar, TCI and
other commercial resource and used as received unless other-
wise stated. Tetrahydrofuran (THF) and toluene were dried over
sodium/benzophenone and distilled prior to use. Acetic acid
was refluxed with 2.5% (w/w) KMnO4 and 5% (w/w) acetic
810
Scheme 1. Synthesis of pyromellitic diimide monomers M1, M2, and M3.
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C. LUO ET AL.
anhydride under nitrogen for 4 hr and distilled before use. 2-
Octyl-1-dodecylamine was prepared from 2-octyl-dodecanol
by using the Gabriel synthesis route.[16,24]
Synthesis
The synthesis routes are shown in Schemes 1 and 2.
3,6-Dibromopyromellitic dianhydride (4)
3,6-Dibromopyromellitic dianhydride was synthesized through
three-step reactions from tetramethylbenzene by bromination,
oxidation, and then amidation to afford the dianhydride product
(shown in Scheme 1) , according to the published procedure.[17,25]
1
H NMR (400 MHz, DMSO-d6, δ): no signals. 13C NMR (300 MHz,
DMSO-d6, δ): 158.54, 137.33, 115.32.
3,6-Dibromo-N,N′-(2-ethylhexyl)- pyromellitic diimide (M1)
To a three-neck flask equipped with a nitrogen inlet and
a dropping funnel were added 3,6-dibromopyromellitic
dianhydride (2.4 g, 6.38 mmol), glacial acetic acid (30 ml), and
2-ethylhexylamine (2.61 ml, 15.96 mmol). The reaction solution
was refluxed overnight. After the reaction, the mixture was con-
centrated under reduced pressure. Then 50 ml of methanol
was added, and the precipitate was collected by filtration. The
crude product was purified by column chromatography (silica
gel, dichloromethane: hexane 3:1) to give a colorless solid (3.15 g,
82%). 1H NMR (400 MHz, CDCl3, δ): 3.55 (d, 4H), 1.77(m, 2H), 1.24
(m, 16H), 0.83 (m, 12H). 13C NMR (300 MHz, CDCl3, δ): 163.28,
135.65, 113.63, 42.42, 37.75, 30.07, 28.02, 23.43, 22.45, 13.56, 9.89.
3,6-Dibromo-N,N′-(2-octyldodecyl)- pyromellitic diimide (M2)
The synthesis of 3,6-dibromo-N,N′-(2-octyldodecyl)-pyromellitic
diimide was similar to that of M1 by using 3,6-dibromopyromellitic
dianhydride and 2-octyl-1-dodecylamine. After purification of the
crude product by column chromatography, a light yellow solid
was obtained (Yield = 79%). 1H NMR (400 MHz, CDCl3, δ): 3.60
(d, 4H), 1.86 (m, 2H), 1.24 (m, 64H), 0.87 (m, 12H). 13C NMR
(300 MHz, CDCl3, δ): 163.67, 136.07, 114.05, 43.28, 36.88, 31.89,
31.85, 31.44, 29.87, 29.59, 29.55, 29.50, 29.32, 29.25, 26.22, 22.66,
22.64, 14.09.
Polym. Adv. Technol. 2014, 25 809–815

PYROMELLITIC DIIMIDE-BASED POLYMERS FOR PHOTOVOLTAIC APPLICATION
Scheme 2. Synthesis of pyromellitic diimide-based polymers P1, P2, and P3.
3,6-Bis(thiophen-2-yl)-N,N′-(2-octyldodecyl)-pyromellitic diimide (5)
To a three-neck Schlenk flask were added M2 (935 mg,
1.0 mmol), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3)
(45.6 mg), and tri(o-tolyl)phosphine (P(o-tol)3) (60 mg). The flask
was subjected to three cycles of evacuation and addition of
nitrogen. Then toluene (30 ml) and 2-(tributylstannyl)thiophene
(934 mg, 2.5 mmol) were injected into the flask under vigorous
stirring. The reaction mixture was stirred overnight at 80°C.
After the reaction, the solvent was removed under reduced
pressure, and the solid was purified by silica chromatography
with dichloromethane: hexane = 1: 1 as the eluent to afford
the compound 5 as bright yellow solid (929 mg, yield = 98.7%).
1
H NMR (400 MHz, acetone-d6, δ): 7.72 (q, 2H), 7.27 (q, 2H), 7.18
(q, 2H), 3.45 (d, 4H), 1.80(m, 2H), 1.25 (m, 64H), 0.86 (m, 12H).
3,6-Bis(5-bromothiophen-2-yl)-N,N′-(2-octyldoecyl)-pyromellitic
diimide (M3)
To a three-neck flask equipped with a dropping funnel were
added the compound 5 (470.7 mg, 0.5 mmol), 5 ml chloroform
and 1 ml 40% aqueous hydrobromic acid. A mixture of bromine
and 40% aqueous hydrobromic acid (1:1, v/v) was added
dropwise under vigorous stirring at 50°C, and the reaction was
monitored by TLC. After the disappearance of the starting mate-
rial, the reaction solution was cooled to room temperature then
poured into water. The mixture was extracted with chloroform
for three times. The organic phase was combined, then washed
with 10% sodium thiosulfate solution and water, and dried
(Mg2SO4). The organic solvent was removed under reduced
pressure to give yellow crude product. The crude product was
purified by column chromatography on silica gel (hexane/
dichloromethane, 1:1) to give M3 as yellow solid (yield = 82.4%).
1
H NMR (400 MHz, acetone-d6, δ): 7.25 (d, 2H), 7.12 (d, 2H), 3.50
(d, 4H), 1.82 (m, 2H), 1.26 (m, 64H), 0.86 (m, 12H). 13C NMR
(300 MHz, CDCl3, δ): 164.76, 135.18, 130.94, 130.65, 129.77,
129.61, 115.51, 43.98, 36.76, 31.86, 31.82, 31.42, 29.91, 29.57,
29.49, 29.43, 29.29, 29.23, 26.12, 22.63, 14.07.
Synthesis of polymer P1
To a Schlenk flask were added 180 mg of M1 (0.3 mmol, 1 equiv.),
140 mg of 2,5-bis(trimethylstannyl)-thieno[3,2-b]thiophene
(0.3 mmol, 1 equiv), Pd2(dba)3 (9.0 mg, 5 mol %.), and P(o-tol)3
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(18 mg, 16 mol %). The flask was subjected to three cycles of
the evacuation and admission of nitrogen. Then 25 ml of toluene
was injected into the flask, and the reaction mixture was stirred
at 100 °C for 48 hr. After the reaction, the solution was concen-
trated and precipitated into methanol (100 ml). The collected
precipitate was extracted using Soxhlet apparatus with methanol
for 24 hr and with hexane for 24 hr, and then extracted with
chloroform until the extraction solution appeared colorless. The
chloroform fraction was filtered by using a 4–5 cm celite 545
column and then concentrated. The concentrated chloroform
solution was precipitated into methanol (200 ml) to afford a
bright red solid (78 mg, yield = 45%). 1H NMR (400 MHz, CDCl3,
δ): 7.49 (broad, 2H), 3.49 (broad, 4H), 1.75 (broad, 2H), 1.23
(broad, 16H), 0.82 (broad, 12H).
Synthesis of polymer P2
The synthesis procedure of the polymer P2 was the same as that
of P1 by using the monomer M2 (281 mg). After purification, a
bright red solid was obtained (255 mg, yield = 93%). 1H NMR
(400 MHz, CDCl3, δ): 7.49 (broad, 2H), 3.49 (broad, 4H), 1.79
(broad, 2H), 1.18 (broad, 64H), 0.80 (broad, 12H).
Synthesis of polymer P3
The synthesis procedure of the polymer P3 was the same as that
of P1 by using the monomer M3 (220 mg). After purification, a
dark red solid was obtained (183 mg, yield = 85%). 1H NMR
(400 MHz, CDCl3, δ): 7.34 (broad, 2H), 7.27 (broad, 2H), 3.46
(broad, 4H), 1.78 (broad, 2H), 1.18 (broad, 64H), 0.79 (broad, 12H).
Characterization
The molecular weight measurement was performed on a Waters
515 gel permeation chromatography system by using THF as the
eluent and polystyrene as standard at 35 °C. UV-vis absorptions
were recorded on a Persee TU-1901 UV-Visible spectrometer.
Cyclic voltammetry (CV) was performed on a Metrohm Autolab
Aut 85013 Electrochemical Workstation in 0.2 mol / L LiClO4
acetonitrile solution. A glassy carbon electrode (diameter 3.0 mm)
coated with a thin layer of the polymer, a Pt wire, and a Ag/AgCl
electrode were used as the working, counter, and reference
electrodes, respectively. The CV curves were calibrated using the
811
ferrocene/ferrocenium (Fc/Fc+) redox couple as an external
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C. LUO ET AL.

standard, which was measured under the same conditions.
Thermogravimetric measurements were carried out by using an
STA449F3 thermogravimetric analyzer from Netzsch instruments.
Sample was heated from ambient to 600°C at a heating rate of
10 °C min 1 under an inert atmosphere of nitrogen. Differential
scanning calorimetry (DSC) experiments were carried out using a
Perkin-Elmer DSC-7 instrument, and samples were purged with
dry nitrogen at a ramping rate of 10 °C min 1. The morphologies
of active layers of PSCs were characterized by using atomic force
microscopy (AFM) with a Dimension 3100 system (Digital Instru-
ments/Veeco) operating in tapping mode.
Solar cell fabrication and characterization
Polymer solar cells were fabricated with the structure of indium
tin oxide (ITO)/PEDOT: PSS/Polymer: PCBM/LiF/Al on ITO-coated
glass substrates. The ITO-coated glass substrates (the surface
resistance of ~20 Ω sq 1) were cleaned in an ultrasonic bath in
detergent, D.I. water, acetone, and isopropyl alcohol each for
15 min. After drying, a thin layer (40 nm) of PEDOT:PSS (poly
(3,4-ethylenedioxythiophene)-poly(styrene sulfonate)) was spin-
coated (3500 rpm, 30 s) on the ITO substrate and dried at 90 °C
for 30 min in a vacuum oven. Subsequently, the photosensitive
active layer (80 nm) was deposited on the top of the PEDOT:PSS
layer by spin coating (1000 rpm, 15 s) from the composite solution
(the polymer/PCBM with a total concentration of 15 mg ml 1 in
chloroform). The resulting films were annealed at 110 or 150 °C
for 15 min in a vacuum oven. The devices were completed by
thermal evaporating a thin layer of LiF (1 nm) and the aluminum
cathode (~150 nm) on the active layers under a shadow mask.
The active area of the devices was 4 × 4 mm2 defined by the mask.
The current–voltage (J–V) characteristics were measured under
simulated AM 1.5G irradiation (100 mW cm 2) by using an Abet
technologies sun 2000 solar simulator. All cells were prepared
and measured under ambient conditions.
Stille copolymerization. The product yields and the molecular
weights are summarized in Table 1. It can be seen that the product
yields for P2 and P3 are over 85%, but P1 has a relatively low prod-
uct yield of 45%. P1 also has a smaller number average molecular
weight (Mn, 4.7 KDa) compared with the other two polymers. This
is because P1 was functionalized with a 2-ethylhexyl side chain,
which has a relatively low side chain volume fraction, resulting in
the poor solubility and the precipitation of P1 from the reaction
solution during the Stille coupling. P1 is soluble in chloroform,
while P2 and P3, which were functionalized with a 2-octyldodecyl
side chain, are readily soluble in common organic solvents, such
as chloroform, dichloromethane, THF, toluene, and chlorobenzene.
This result illustrates that the longer alkyl side chain along the
polymer backbone improve the solubility of the polymers, which
will benefit the fabrication of PSCs by the solution process. P3
has the highest molecular weight because the insertion of a
thiophene bridge between PMDI and TT units decreases the steric
hindrance caused by the side chain and benefits the formation
of the polymers with a high molecular weight. The chemical
structures of polymers were characterized by proton NMR. In the
1
H NMR spectra of polymers P1–P3, signals between 0.8–4 ppm
are assigned to alkyl side chain protons in the PMDI units and
signals observed between 7 and 8 ppm are corresponding to
aromatic protons of the donor units.
The thermal stabilities of the prepared polymers were
studied by the thermogravimetric analysis, and the results are
shown in Figure 1. The 5% weight loss temperature was chosen

RESULTS AND DISCUSSION

Synthesis and characterization of polymers
The monomers M1 and M2 based on PMDI, as shown in Scheme 1,
were synthesized according to the published procedure,[17,25]
and the monomer M3 was synthesized from the monomer M2.
The PMDI-based polymers P1–P3 (Scheme 2) were synthesized Figure 1. Thermogravimetric analysis thermograms of pyromellitic
from dibromopyromellitic diimide monomers with bis diimide-based polymers P1, P2, and P3. This figure is available in colour
(trimethylstannyl) thienothiophene comonomer via Pd-catalyzed online at wileyonlinelibrary.com/journal/pat

Table 1. Product yields, molecular weight distributions, thermal properties, optical properties, and electrochemical data for poly-
mers P1–P3

λmax λmax λonset

Polymer Yield (%) Mna (KDa) Mw/Mn Td (°C) Tg (°C) (soln,nm) (film,nm) (film,nm) Eopt
g (eV)
b
EHOMO (eV) c
ELUMO (eV)
P1 45 4.7 1.07 451 — 409 403 505 2.46 5.77 3.31
P2 93 30.8 4.22 345 — 413 422 515 2.41 5.77 3.36
P3 85 80.4 2.30 436 — 453 466 566 2.19 5.74 3.55
a
Molecular weight distribution were determined by gel permeation chromatography using tetrahydrofuran as the eluent and
polystyrene as standard;
b
calculated from the onset oxidation peaks based on the equation: EHOMO = (Eonset
ox + 4.4) eV;
c
calculated based on equation: ELUMO = EHOMO + Eopt
812

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PYROMELLITIC DIIMIDE-BASED POLYMERS FOR PHOTOVOLTAIC APPLICATION

as the onset decomposition temperature. Two weight loss Electrochemical properties

stages were observed for polymers P1 and P3. On heating up
Cyclic voltammetry experiments were performed on the thin films
to 500°C, there was an initial weight loss, which should be
of the polymers P1–P3 to examine their electrochemical redox
due to the loss of alkyl side chain as judged by the percentage
properties and estimate their frontier orbital energy levels. The
of weight loss. The second stage weight loss above 500°C
obtained voltammograms are shown in Figure 3. For comparison,
corresponds to pyrolytic degradation. The onset decomposi-
the voltammogram of bare glassy carbon electrode in the electro-
tion temperatures of P1 and P3 were 451°C and 436°C, respec-
lyte solution is also given in Figure 3. It can be seen that the
tively. Compared with P1 and P3, P2 showed decreased thermal
voltammograms of P1 and P2 are very similar. The oxidation peaks
stability with onset decomposition temperature observed at
appear in the range of 1.0 to 1.7 V during the positive potential
345°C. Furthermore, the weight loss related to the loss of alkyl
scan. This is reasonable because the polymer backbones of P1
side chain was divided to two steps. The reason for the
and P2 are exactly the same. This result also indicates that the alkyl
decreased thermal stability and different thermal behavior of
side chains used in this work have negligible effect on the electro-
P2 is probably related to the broad molecular weight distribu-
chemical properties of the polymers. The voltammogram of P3 is
tion (Table 1). The thermogravimetric analysis results confirm
significantly different from those of P1 and P2. There are two obvi-
that the thermal stability of these PMDI-based polymers is
ous oxidation peaks located at 1.54 and 1.79 V during the positive
good enough for their applications in OPV and other opto-
scan. This difference indicates that the introduction of a thiophene
electronic devices.[26] DSC was carried out to investigate the
π-bridge between the PMDI and TT units, greatly improve the
thermal transition behaviors of P1–P3. There is no thermal tran-
electroactivity of the polymer. During the negative potential scan,
sition observed for these polymers up to 300°C.
there are no obvious reduction peaks observed for any of the three
PMDI-based polymers. These results indicate that the prepared
Optical properties polymers are more likely to be p-type materials.
The highest occupied molecular orbital (HOMO) energy levels
The UV-vis absorption spectra of P1, P2, and P3 in a chloroform were estimated from the onset oxidation potentials (Eonset ox ). The
solution and as solid thin film on a quartz substrate are repre- half-wave potential of Fc/Fc+ was found to locate at 0.40 V
sented in Figure 2. The photophysical data are summarized in related to the Ag/AgCl electrode. The HOMO energy levels of the
Table 1. In the solution, the absorption profiles of P1 and P2 polymers were then calculated from the onset oxidation
are very similar and contain one major absorption band in the
range of 325 to 550 nm, which should be associated to the intra-
molecular D–A charge–transfer interaction.[27,28] Compared with
P1 and P2, the absorption band of P3 is broader and also red-
shifted, because the insertion of a thiophene π-bridge between
PMDI and the electron-donating unit can decrease the intramo-
lecular steric hindrance and improve the molecular coplanarity
and conjugation of the polymer.
In the thin film state, the absorption peaks of P2 and P3, which
were functionalized with the 2-octyldodecyl side chain, are slightly
red-shifted by 9 and 13 nm, respectively, compared with those in
the solution. These results indicate the existence of strong
intermolecular interaction and ordering in these thin polymer
films. On the contrary, a small blue shift (6 nm) from the solution
to solid was observed for P1, which suggests that the aggregation
could exist in the solution for the polymer bearing 2-ethylhexyl
side chain. The optical band gaps estimated from the low-energy
Figure 3. Cyclic voltammograms of films for polymers P1–P3 on glassy
absorption onset wavelengths (Eopt g = 1240 λonset) of the polymer
1
carbon plate in an acetonitrile solution of 0.2 M LiClO4 with a potential
films are 2.46 eV for P1, 2.41 eV for P2, and 2.19 eV for P3. These 1
scan rate of 50 mV s . This figure is available in colour online at
PMDI-based polymers show relatively large Eoptg . wileyonlinelibrary.com/journal/pat

Figure 2. Normalized UV-vis absorption spectra of polymers P1–P3 (A) in CHCl3 solution and (B) as thin film on quartz substrates. This figure is avail-
813

able in colour online at wileyonlinelibrary.com/journal/pat

Polym. Adv. Technol. 2014, 25 809–815 Copyright © 2014 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/pat

potentials based on the equation: EHOMO = (Eonset ox + 4.4) eV,[29]
where Eonset
ox is the measured potential relative to the Ag/AgCl
reference electrode. The LUMO energy levels were calculated from
the optical band gap and the HOMO energy level based on the
following equation: ELUMO = EHOMO + Eopt opt
g , where Eg is the optical
band gap obtained from the UV-vis spectra. The corresponding
HOMO and LUMO energy levels are listed in Table 1. The HOMO
energy level of P1, P2, and P3 are found to be 5.77, 5.77, and
5.74 eV, respectively, which are lower than the air oxidation
threshold (approx. 5.2 eV) and insure their good resistance to
the oxidation under ambient conditions.[30] In addition, the rela-
tively low-lying HOMO energy will benefit the enhancement of
open-circuit voltage (Voc) of devices, because the HOMOs of the
polymers are considered to be propitious to the Voc of the polymer
solar cell.[31] Polymers P1 and P2 showed similar HOMO and LUMO
energy levels, which indicates that the side chains had little influ-
ence on the energy levels. With the introduction of a thiophene
π-bridge between the PMDI and TT units, P3 displayed a relatively
low-lying LUMO energy level in contrast to P2.
Solar cell performance
The PSCs with a conventional cell structure of glass/ITO/PEDOT:
PSS/Polymer:PCBM/LiF/Al were fabricated by employing the pre-
pared polymer as the electron donors and PCBM as the electron
acceptor. To determine the optimum composition of the active
layer, the weight ratios of the polymer to PCBM were varied from
2:1, 1:1 to 1:2, and the best device performance was achieved
with a 1:2 D–A weight ratio for the polymers P1, P2, and P3.
Then, the effect of pre-thermal annealing on solar cell perfor-
mance was examined by thermal treatment of the active layer
compositions at 110 °C or 150 °C in a vacuum oven before the
deposition of LiF and Al layers. It was found that the pre-thermal
Figure 4. (A): J–V curve of pyromellitic diimide-based polymer solar cells with active layer composition of Polymer: PCBM (1:2, w/w) under illumination of AM
2
1.5 G, 100 mW cm and (B) energy band diagrams for the photovoltaic devices. This figure is available in colour online at wileyonlinelibrary.com/journal/pat
Table 2. Photovoltaic properties of the polymer solar cells under AM 1.5 G illumination at 100 mW cm
Polymer :PCBM (w/w) Solvent Pre-annealing (°C)
P1 :PCBM (1:2) ODCB no
P2 :PCBM (1:2) ODCB no
P3 :PCBM (1:2) ODCB 110
814
wileyonlinelibrary.com/journal/pat Copyright © 2014 John Wiley & Sons, Ltd.
10991581, 2014, 8, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pat.3304 by University Of Nebraska Lincoln, Wiley Online Library on [16/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
C. LUO ET AL.
annealing did not improve the power conversion efficiencies
(PCEs) of the cells based on P1 and P2, and the PCEs decreased
with the increase of the thermal annealing temperature. The
PCEs of the cell based on P3 were improved after the active
layers annealed at 110 °C, but drastically decreased after the cell
annealed at 150 °C. The different behavior of device based on P3
is possibly due to the different backbone structure of P3. The
enhancement in the performance of solar cell based on P3 could
be due to the improved active layer morphology after thermal
annealing. Figure 4 shows the representative current density–
voltage (J–V) curves of the prepared PSCs under an illumination
of AM 1.5 G, 100 mW cm 2 and the energy band diagrams for the
photovoltaic devices. The photovoltaic performance data of the
PSCs, including the Voc, Jsc, FF, and PCE values, are summarized
in Table 2 for comparison. Although P1 and P2 possess nearly
identical band gaps and their absorption profiles are very similar,
the polymer solar cells based on P1 displayed much higher Jsc
and FF than those of P2. The PSCs based on P3 showed the
better performance than those based on P1 and P2 due to the
better match of the adsorption spectrum of P3 with the solar
spectrum. The cell based on P3/PCBM after pre-thermal
annealing at 110 °C had a Voc of 0.59 V, a Jsc of 2.05 mA cm 2, a
calculated FF of 35%, and a PCE of 0.43%.
Compared with P2, the higher photovoltaic performance of
2-ethylhexyl functionalized polymer (P1) probably results from
the better active layer morphology when it is blended with PCBM.
To verify this, the tapping model AFM was employed to study the
morphologies of the active layers, and the corresponding AFM
topographies of the blend films on PEDOT:PSS for P1, P2, and P3
are shown in Figure 5. The blended film prepared from P1 and
PCBM clearly shows a phase-separated morphology with nanoscale
domains. In contrast, large domains of aggregated PCBM can be
seen for the film prepared from P2. It is well-known that the relative
2
Voc (V) Jsc (mA cm 2) FF (%) PCE (%)
0.44 0.676 40 0.12
0.67 0.121 27 0.022
0.59 2.05 35 0.43
Polym. Adv. Technol. 2014, 25 809–815

PYROMELLITIC DIIMIDE-BASED POLYMERS FOR PHOTOVOLTAIC APPLICATION
Figure 5. Atomic force microscopy topographies of P:PCBM (1:2, w/w) blend films on PEDOT:PSS for: (A) P1, (B) P2, and (C) P3. This figure is available in
colour online at wileyonlinelibrary.com/journal/pat
solubility of the polymer to the fullerene in the processing solvent
could significantly change the final film morphology.[32,33] The
polymer P2 bearing the large branched 2-octyldodecyl side chain
has higher solubility in the processing solvent than PCBM. As a
result, PCBM molecules precipitated out first in the film formation
process to form large domains. However, the solubility of P1 is
poor, and it precipitated out in a short time during the film forming
process, leaving less space and time for PCBM to form large
domain. The introduction of a thiophene π-bridge between PMDI
and TT units led to the better phase-separated morphology of
P3/PCBM compared with P2/PCBM. These results suggest that both
the polymer backbone and the alkyl side chain of conjugated
polymers have to be carefully optimized for use in bulk
heterojunction PSCs.
CONCLUSIONS
Three of D–A conjugated polymers based on pyromellitic diimide
as the electron acceptor unit were synthesized by Stille coupling.
These polymers have good thermal stability, modest LUMO energy
levels between -3.3 and -3.6 eV, and deep HOMO energy levels
between -5.70 and -5.80 eV. The functionalization with a long alkyl
side chain improves the solubility of the resulting polymers. Photo-
voltaic devices using these PMDI-based polymer as the donor and
PCBM as the acceptor were fabricated. Although the longer side
chain improves the solubility of the resulting polymers, the PSCs
based on the polymer P1 bearing the shorter 2-ethylhexyl side
chain have the higher Jsc and FF. The insertion of a thiophene
π-bridge between PMDI and the electron donor unit decreases
the intramolecular steric hindrance and results in the broader
absorption, which improves the photovoltaic performance of the
cell. The cell based on P3/PCBM (1/2, w/w) after pre-thermal
annealing at 110 °C had a Voc of 0.59 V, a Jsc of 2.05 mA cm 2, a
calculated FF of 35%, and a PCE of 0.43%.
Acknowledgements
This work was financially supported by National Program on Key
Basic Research project (no. 2013CB922302), China Postdoctoral
Science Foundation (no. 2012M510897), National Natural Science
Foundation of China (no. 61306020), and NCET.
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