An acrylated fullerene derivative for efficient and thermally stable polymer solar cells

Article abstract of DOI:10.1016/j.tetlet.2017.05.049

The continuous microstructure evolution occurring in active layers of polymer-fullerene solar cells is one of the main causes for their device instability. With aim to tackle it, this work developed a new polymerizable fullerene acceptor, [6,6]-phenyl-C

Full text of DOI:10.1016/j.tetlet.2017.05.049

Accepted Manuscript
An Acrylated Fullerene Derivative for Efficient and Thermally Stable Polymer
Solar Cells
Jin-Long Wang, Xue-Qiang Chen, Xiang Yao, Si-Cheng Wu, Li-Na Liu, Wen-
Jing Xiao, Hongyu Wang, Jingjing Li, Zhengquan Lu, Wei-Shi Li
PII:
S0040-4039(17)30634-2
DOI:
http://dx.doi.org/10.1016/j.tetlet.2017.05.049
TETL 48942
Reference:
To appear in:
Tetrahedron Letters
Received Date:
Accepted Date:
22 April 2017
15 May 2017
Please cite this article as: Wang, J-L., Chen, X-Q., Yao, X., Wu, S-C., Liu, L-N., Xiao, W-J., Wang, H., Li, J., Lu,
Z., Li, W-S., An Acrylated Fullerene Derivative for Efficient and Thermally Stable Polymer Solar Cells, Tetrahedron
Letters (2017), doi: http://dx.doi.org/10.1016/j.tetlet.2017.05.049
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Tetrahedron Letters
An Acrylated Fullerene Derivative for Efficient and Thermally Stable Polymer Solar
Cells
a,b
b
b
b
b
b
Jin-Long Wang, Xue-Qiang Chen, Xiang Yao, Si-Cheng Wu, Li-Na Liu, Wen-Jing Xiao, Hongyu
a,*
c
c
b,c,*
Wang, Jingjing Li, Zhengquan Lu, and Wei-Shi Li
a
Department of Chemistry, College of Science, Shanghai University,99 Shangda Road, Shanghai 200444, P. R. China
Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai Institute of Organic Chemistry, Chinese Academy of
b
Sciences, 345 Lingling Road, Shanghai 200032, P. R. China
c
Engineering Research Center of Zhengzhou for High Performance Organic Functional Materials, Zhengzhou Institute of Technology, 6 Yingcai Street, Huiji
District, Zhengzhou 450044, P. R. China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
The continuous microstructure evolution occurring in active layers of polymer-
fullerene solar cells is one of the main causes for their device instability. With aim
to tackle it, this work developed a new polymerizable fullerene acceptor, [6,6]-
phenyl-C -pentyl acrylate (PC PA). It was found that PC PA has similar light-
6
1
61
61
Available online
absorption properties and HOMO and LUMO energy levels as [6,6]-phenyl-C -
61
butyric acid methyl ester (PC BM), and can be converted into insoluble oligomers
6
1
upon heating at 150 C. Polymer-fullerene solar cells using poly(3-hexylthiophene)
(
P3HT) as donor and PC PA as acceptor exhibited an optimized efficiency of
6
1
Keywords:
3.54%, the performance comparable to P3HT/PC BM cells (optimized efficiency:
61
Polymer solar cells
Organic photovoltaic materials
Fullerene
Stability
Polymerizable
3.70%). But, the former possess much better thermal stability than the latter owing
to aggregation suppression by the polymerized PC PA. These results indicate that
6
1
PC PA, unlike most previous reported, is a unique polymerizable fullerene
6
1
derivative that can be used alone as acceptor to achieve both efficient and thermally
stable polymer solar cells.
2
009 Elsevier Ltd. All rights reserved.
1
. Introduction
Bulk heterojunction (BHJ) polymer solar cells (PSCs) have
magnitude of exciton effective diffusion length (10~20 nm) for a
high exciton migration efficiency. Although it is still known
little about what governing microstructure formation for a
physical blend of two materials and how to precisely control their
formation, a number of PSC systems have achieved nearly ideal
configuration after careful optimization on device fabrication
parameters and procedures, including donor/acceptor ratio,
processing solvent and temperature, additives, concentration,
spin-coating rate, thermal annealing, solvent vapor annealing,
standing alone, and so on, and thus endowed them with high
attracted considerable attention owing to their advantages of light
weight, flexibility, adaptability to low cost solution processing
and large area device fabrication. With great success in material
innovation and device engineering in the past decades, PSCs
have achieved a significant progress with power conversion
efficiency (PCE) record raised from 3~5% in 2000s to
nowadays over 10%. Although such efficiency level is needed
to be further improved for their real use, it is appropriate to pay
1
1, 2
1
, 3
1-3
performance. Since no specific factors and interactions are
4
attention on device stability issue at the same time.
engaged to hold blend components still, the so-formed nanoscale
phase-separated microstructures are not thermally stable, and
absolutely continue to evolve into large phase separation. And
even in many reported cases, large aggregates were clearly naked
identified when their active layers were subjected to thermal
According to light-to-electric conversion mechanism, a BHJ
active layer is generally composed of a physical blend of electron
donor (D) and acceptor (A) materials. In order to provide a
large D/A interface for efficient exciton dissociation (or charge
separation) and meanwhile the transportation pathways for both
hole and electron charge carriers, a bi-continuous interpenetrating
D/A biphasic microstructure should be formed in the active layer.
Moreover, their domain widths are better to keep in the same
1
5
treatment. Therefore, such microstructure evolution occurring in
PSC active layers mostly leads to reduction on the size of D/A
interface, destruction on the hole and electron transportation
networks, and thus degradation on device performance. In fact,
this is a major immanent reason accounting for the instability
issue of PSCs, which is different from chemical degradation
factors caused by material instability and the invasion of oxygen
and moisture.

Corresponding authors. E-mail: wanghy@shu.edu.cn (H. Wang),
liws@mail.sioc.ac.cn (W.-S. Li).

2
Tetrahedron
In order to address it, a strategy has been proposed in the
past to utilize crosslinkable photovoltaic materials for BHJ active
6
layers. After desired microstructure is achieved by means of all
applicable techniques and methods, crosslinking reaction is
initiated and performed to “lock” or “freeze” active layer
components, and thus avoid or retard further phase separation
and stabilize the obtained microstructure. This strategy has been
widely applied in polymer donor materials, firstly on poly(3-
5
-7
hexylthiophene) (P3HT) and later on donor-acceptor (D-A)
6
, 8
conjugated polymers. Therefore, a great number of
crosslinkable polymer donors having vinyl, bromo, oxetane, or
azide functionality on part of their side chains were synthesized
and found they can more or less improve device thermal stability.
More recently, we also demonstrated the combination of this
strategy with the present known high performance D-A polymers
can produce crosslinkable donor materials for PSCs with both
9
high efficiency and long-term stability. However, in these
Scheme 1. Synthesis of PC PA.
61
works, acceptor molecules (PC BM in the most cases) still kept
6
1
movable since no crosslinking took place on them. In order to
fix acceptor component, it is necessary to develop
1
05
crosslinkable/polymerizable fullerene acceptor materials at the
meantime. However, compared with a large number of
crosslinkable donor materials, only a few works were focused on
acceptor materials. For example, an epoxide-functionalized
100
95
1
0
fullerene acceptor, PCBG, was reported in 2005. Solar cells
based on P3HT/PCBG displayed an initial efficiency of >2%, but
strong degraded upon heating at 140 C for several minutes. In
9
8
0
5
2
010, Hsu, Chen, and their coworkers developed a [6,6]-phenyl-
C -butyric styryl dendron ester (PCBSD) having a dendron
6
1
1
1
shape with two styryl crosslinkers. It was firstly used as for
fabrication of crosslinked interlayer,
P3HT/PC BM active layer, both achieving improved device
1
1, 12
and later as additive to
100 200 300 400 500
Temperature (ºC)
1
3
6
1
efficiency and stability. But, it was never used as acceptor
material alone to combine with donor material for PSCs. In 2013,
Chen et al. reported a vinyl-terminated fullerene derivative,
PCBD, and used it in combination with vinyl-modified D-A
donor material, PBDTTT-V, for inter-crosslinked solar cells.
Device based on PBDTTT-V/PCBD exhibited a much better
1
.0
.5
0
8
c
0.0
-0.5
-1.0
-1.5
stability than PBDTTT-V/PC BM. The former cell had smaller
6
1
initial device efficiency than the latter (2.5% vs. 3.3%). Later in
014, two azido-functionalized fullerene derivatives were
reported and also used as a second acceptor material to
2
1
4
P3HT/PC BM blend. More recently, Bucknall et al. reported a
6
1
1
5
benzocyclobutene-attached fullerene material. Although the
device based on it and P3HT displayed a good stability, its initial
efficiency was only ~1.2%. Therefore, the polymerizable or
crosslinkable fullerene derivative, which can not only greatly
improve device stability but also compete with PC BM in device
0
50 100 150 200 250 300
Temperature (ºC)
Figure 1. (a) TGA profile and (b) DSC traces of PC PA with a
temperature ramping rate of 10 ºC /min under N atmosphere.
6
1
6
1
2
efficiency as acceptor component alone, has not yet been
developed so far.
2
. Results and discussion
The Synthesis of PC PA followed the similar method for
Analyzing the chemical structures of the above reported
crosslinkable or polymerizable fullerene materials, one can find
that all of them were prepared from PC BM, which was
61
1
6
PC BM, which is outlined in Scheme 1. Starting from lactone,
61
6
1
a -hydroxyl phenyl ketone 1 was obtained in a yield of 80%.
After refluxing with p-toluenesulfonyl hydrazide in MeOH, it
converted into 2, an important tosylhydrazone intermediate for
,3-dipolar addition of fullerene. Afterwards, compound 2 was
first treated with MeONa in pyridine to produce the active diazo
intermediate and then added with C60 o-dichlorobenzene (ODCB)
solution, affording PC P-OH, a hydroxyl-functionalized
fullerene derivative, in a yield of 45%. After esterification with
acryloyl chloride in the presence of Et N, the final product,
PC PA, was obtained in a yield of 65%. Both PC P-OH and
PC PA are readily soluble in chlorinated solvents, such as
chloroform, chlorobenzene, ODCB etc. Their structures were
unambiguously identified by H and C NMR spectroscopy,
hydrolyzed into carboxylic acid firstly and then reacted with
corresponding crosslinker unit-containing reagents. This may be
the reason that the obtained new fullerene materials showed
inferior device efficiency than PC BM. Therefore, in this study,
1
6
1
we propose a new synthetic strategy for polymerizable fullerene
materials and obtained an acrylated fullerene derivative, PC PA
6
1
(Scheme 1). Since it has similar molecular size and shape as
61
PC BM, it is expected to display comparable device efficiency
6
1
as PC BM. Meanwhile, the acrylate functionality could enable
3
6
1
its in-situ polymerization by means of thermal activation and thus
achieve high device stability.
61
61
61
1
13

0
0
0
0
.6
.4
.2
.0
5
0
5
PC61BM
PC61PA
P3HT/PC61BM cell
P3HT/PC61PA cell
400 500 600 700
Wavelength (nm)
-
-
10
3
00 400 500 600 700 800
Wavelength (nm)
-
0.2 0.0 0.2 0.4 0.6 0.8
Voltage (V)
Figure 3. Current density-voltage curves of the optimized solar
cells based on P3HT/PC PA and P3HT/PC BM under an
6
1
61
2
illumination of AM1.5G with a light density of 100 mW/cm .
PC61BM
PC61PA
Table 1. Device parameters of the optimized PSCs as shown in
Figure 3.
2
Device
VOC (V) JSC (mA/cm ) FF (%) PCE (%)
P3HT/PC PA
0.59
0.59
8.71
9.07
69.1
69.0
3.54
3.70
6
1
P3HT/PC BM
6
1
chloroform displayed an almost identical absorption spectrum as
PC BM with a set of absorption peaks at 329, 431, ~490 (weak
-
2.0
-1.0
0.0
1.0
2.0
61
+
and broad) and 690 nm. Moreover, both compounds displayed
an onset absorption point around 710 nm, suggesting they
possess a same optical energy bandgap of 1.74 eV. In its CV
profile (Figure 2b), the onset reduction and oxidation potentials
Voltage (V vs. Ag/Ag )
Figure 2. (a) UV-vis absorption spectra in chloroform and (b) CV
profiles measured in ODCB/acetonitrile (4/1, v/v) solution of PC PA
and PC BM. Inset in (a) shows an enlarged spectra in the region
6
1
6
1
+
were measured to be -0.84 and 1.28 V vs. Ag/Ag respectively,
of 400~750 nm.
which are almost the same as to those of PC BM (-0.86 and 1.26
6
1
+
+
V vs. Ag/Ag ). Since ferrocene/ferrocenium (Fc/Fc ) couple
mass spectroscopy and elemental analysis, as shown in
Supplementary Material.
having an absolute vacuum energy level of 4.8 eV was detected
+
17
to be 0.18 V vs. Ag/Ag under the same conditions, the energy
level of the lowest unoccupied molecular orbital (LUMO) was
calculated to be -3.78 eV for PC61PA and -3.76 eV for PC61BM,
while those for the highest occupied molecular orbitals (HOMO)
were -5.90 and -5.88 eV, respectively. These data clearly
illustrate that PC61PA possesses similar optical, electrochemical
properties and material energy levels as PC61BM. This is not
surprising when considering their molecular structures are almost
the same except a small difference in the direction of ester
moieties.
Thermogravimetric analysis (TGA) found that PC PA
6
1
possesses a good thermal stability in N atmosphere with a 5%-
2
weight-loss temperatures (T ) of 452.1 ºC (Figure 1a). In
d
differential scanning calorimetry (DSC) as shown in Figure 1b, it
was found that a broad exothermic peak starting around 170 ºC
st
and reaching its apex at 182 ºC appeared in the 1 heating
process. Since acrylated monomers are well known to be easily
self-polymerized by means of heat activation, we suspected this
exothermic peak is associated with self-polymerization of
PC PA. In order to confirm it, PC PA was heated at 150 C
6
1
61
The photovoltaic performance of PC PA used as acceptor
6
1
and found its 63.5% part became insoluble in chloroform. This
proves our suspicion and indicates that PC PA can undergo self-
material alone was evaluated by PSC devices using P3HT as a
donor material and a device configuration of
ITO/PEDOT:PSS/P3HT:PCPA/Ca/Al. Meanwhile, for the
purpose of comparison, the similar PSCs with a device
6
1
polymerization upon heating. Besides this exothermic peak, a
sharp endothermic peak at 233.6 C, a small endothermic at
2
47.2 C, and a very broad exothermic peak in the temperature
st
configuration but using PC61BM as acceptor component were
fabricated and characterized. Both kinds of PSCs were carefully
optimized on donor/acceptor ratio, concentration, spin-coating
rate, thermal annealing and solvent annealing etc. It was found
that both kinds of PSC devices presented their best performance
at a donor/acceptor weight ratio of 1/1 and a concentration of 30
mg/mL in ODCB. But, P3HT/PC PA cells should be stand still
region of 240~300 C were also viewed in the 1 heating trace of
DCS. Although their assignment are not understood at present,
the former endothermic peak may originate from the melting
phase transition of the survived PC PA that had no time to
6
1
undergo polymerization during the rapid heating process, while
the broad exothermic peak may come from the polymerization of
those remained PC PA and further convert into higher molecular
6
1
6
1
for 8 h and then annealed at 150 C for 1 h, while those of
P3HT/PC61BM should stand still for a while and then subjected
to anneal at 120 C for 10 min. Of interest, both P3HT/PC PA
weight polymers. After first heating process, no obvious peaks
st
nd
were found in the 1 cooling process and the 2 heating-cooling
cycle of DSC except glass transition peaks around 238 C in the
cooling process while around 248 C at heating process.
6
1
and P3HT/PC BM devices after optimization displayed almost
6
1
the same photovoltaic performance, as shown in Figure 3 and
The optical and electrochemical properties of PC PA were
Table 1. The former optimized cell exhibited a VOC of 0.59 V, a
6
1
2
investigated by means of UV-vis absorption spectroscopy and
cyclic voltammetry (CV). As shown in Figure 2a, PC PA in
J
SC of 8.71 mA/cm , a FF value of 69.1%, and a PCE of 3.54%,
2
while the latter showed a VOC of 0.59 V, a JSC of 9.07 mA/cm , a
6
1

4
Tetrahedron
3.5
3.0
2.5
2.0
1.5
1.0
P3HT/PC61PA
Figure 5. Optical images of P3HT/PC BM and P3HT/PC PA
blend films in weight ratio of 1/1 upon thermal treatment at 150 C
for various times.
6
1
61
P3HT/PC61BM
0
5
10 15 20 25 30 35
Time (h)
P3HT/PC PA blend film, no any changes were observed even
after 35 h thermal treatment. From the aforementioned DSC
6
1
Figure 4. PCE changes of the active layers of P3HT/PC PA and
P3HT/PC BM subjected to thermal treatment at 150 C for
6
1
profile and related experiment, PC PA upon 150 C heating is
6
1
6
1
known to undergo polymerization. Thus during above 150 C
various times.
thermal treatment experiments, PC PA converted into fullerene
6
1
polymers or oligomers, which have much less potential to diffuse.
Therefore, the morphology of the active layer can be reserved
during thermal treatment, and thus rendering the P3HT/PC PA
FF value of 69.0%, and a PCE of 3.70%. The same VOC should
be closely associated with the almost same LUMO energy levels
6
1
of PC PA and PC BM, while the almost same values of J and
6
1
61
SC
cell has a good thermal stability.
FF suggest both cells would have similar microstructure and
possess similar hole and electron charge mobilities in their active
layers. It is valuable to point out PC PA is the first fullerene
3. Conclusion
6
1
In this work, an innovative polymerizable fullerene derivative,
PC PA, has been successfully developed. Compared with
derivative reported so far that carries certain polymerizable
functionality but also displays comparable photovoltaic
performance as PC BM for using as acceptor material alone.
6
1
PC BM, it exhibits almost identical optical and electrochemical
6
1
6
1
properties as well as bandgap and HOMO and LUMO energy
levels. Moreover, it can be used as acceptor component alone for
polymer-fullerene solar cells and displays comparable
In order to know the usage of acrylate functionality in PC PA
6
1
for device stability improvement, both P3HT/PC PA and
6
1
P3HT/PC BM active layers were subjected to thermal treatment
photovoltaic performance to PC BM. It is evidenced by the
6
1
61
at 150 C for various times in a N -filled glove box. After that,
optimized solar cell based on P3HT/PC PA displayed a PCE of
2
61
the top Ca/Al electrodes were deposited to finish device
3.54%, while that of P3HT/PC BM reported a PCE of 3.70%.
6
1
fabrication and produced a series of cells. As shown in Figure 4,
in the case of P3HT/PC PA cell series, the cell without thermal
Owing to its carrying acrylate functionality, PC PA can be
61
6
1
polymerized upon thermal activation at 150 C and turns into
insoluble polymers. This capability enables P3HT/PC61PA
active layer reserving its morphology even after long time
thermal treatment and thus endows its solar cells a much better
thermal stability than those based on P3HT/PC BM. Therefore,
treatment reported an initial efficiency of 2.45%. When the
device was fabricated after 30 min thermal treatment, the
efficiency quickly enhanced to be 3.14%. And this efficiency
level almost kept intact for the devices fabricated for 15 h
thermal treatment. After that, further prolonging thermal
treatment resulted in gradually decrease in device efficiency. But
even after 35 h treatment, the produced cell still displayed an
efficiency of 2.51%. However, in the case of P3HT/PC BM
6
1
to the best of our knowledge, this acrylated fullerene derivative
can be served as the first fullerene acceptor material that have
both comparable photovoltaic performance to PC BM and
6
1
6
1
crosslinkable function for enhancing device thermal stability.
The exploitation of its combination with the present known high
performance donor polymers for efficient and stable polymer
solar cell construction and the development of its C70 analogue
are the subjects worthy further investigation.
series, the situation was completely different. Its cell without
thermal treatment gave an efficiency of 2.91%. The short-time
thermal treatment (< 2 h) slightly enhanced cell efficiency to the
largest value of 3.03%. After that, thermal treatment led to
quickly decrease in device efficiency. The cell treated for 35 h
showed a PCE of as small as 1.21%. This huge discrepancy in
PCE change upon thermal treatment at 150 C unambiguously
Acknowledgments
illustrates that P3HT/PC PA has a much higher thermal stability
6
1
This work was financially supported by National Natural
Science Foundation of China (Nos. 21474129 and 21674125),
International Science and Technology Cooperation Program of
China (No. 2015DFG62680), Strategic Priority Research
Program of Chinese Academy of Sciences (No. XDB20020000),
Science and Technology Open Cooperation Project of Henan
Province (No. 162106000018) and Zhengzhou Institute of
Technology.
than P3HT/PC BM cell.
6
1
For understanding the origin of different PCE changes that
P3HT/PC PA and P3HT/PC BM cells presented, optical
6
1
61
microscopy (OM) was applied to monitor the morphology change
of their active layers during thermal treatment procedure. As
shown in Figure 5, the P3HT/PC BM blend film quickly
6
1
presented a number of black dots after 0.5 h thermal treatment.
These dots grew bigger and bigger and finally assembled into
large dendritic aggregates when prolonging thermal treatment.
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5
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Graphical Abstract
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An Acrylated Fullerene Derivative for
Efficient and Thermally Stable Polymer
Solar Cells
Leave this area blank for abstract info.
*
Jin-Long Wang, Xue-Qiang Chen, Xiang Yao, Si-Cheng Wu, Li-Na Liu, Wen-Jing Xiao, Hongyu Wang,
*
Jingjing Li, Zhengquan Lu, and Wei-Shi Li

Highlights
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A polymerizable fullerene derivative, PC61PA, was designed and synthesized.
PC61PA has a similar molecular shape and size as PC61BM, but carries a polymerizable acrylate
functionality.
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PC61PA displays similar basic optoelectronic properties, including light absorption,
electrochemistry, band gap, HOMO and LUMO energy levels, as PC61BM.
Polymer solar cells based on P3HT/PC PA exhibited similar efficiency to those based on
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P3HT/PC61BM, but the former cells possessed much better thermal stability than the latter.