Benzo[1,2-b:4,5- b ′]diselenophene-fused nonfullerene acceptors with alternative aromatic ring-based and monochlorinated end groups: A new synergistic strategy to simultaneously achieve highly efficient organic solar cells with the energy loss of 0.49 eV

Article abstract of DOI:10.1039/c9ta03177d

Herein, a new synergistic strategy using electron-rich core units and alternative aromatic structure-based 1,1-dicyanomethylene-3-indanone (IC) end-groups for nonfullerene PSCs was reported and investigated in an attempt to simultaneously obtain excellent PCE with extremely low E_loss. Specifically, two benzo[1,2-b:4,5-b′]diselenophene-based, A-D-A-type chlorinated NF-SMAs (BDSeThCl and BDSePhCl) were synthesized, which were linked with a new 2-chlorothienyl-based IC and a conventional monochlorinated phenyl-based IC as end-groups, respectively. BDSePhCl exhibited a wider and red-shifted absorption and downshifted energy levels than BDSeThCl. The blend films of BDSePhCl:PM7 exhibited better charge generation properties, more suitable phase separation, and more balanced charge mobilities as compared to those of BDSeThCl:PM7. Therefore, compared to the BDSeThCl:PM7 blends with the best PCE of 11.91% and the E_loss of 0.58 eV, the optimal BDSePhCl:PM7 blends showed the enhanced PCE of 13.68% with the reduced E_loss of 0.49 eV. Notably, the excellent PCE of 13.68% is the highest value recorded to date for A-D-A-type NF-SMAs with a monochlorinated IC group in binary PSCs. The E_loss of 0.49 eV is the lowest value reported to date for A-D-A-type NF-SMAs in binary PSCs with the PCE > 13%. These results demonstrate that tailoring of the monochlorinated aromatic ring-based IC is an effective strategy to simultaneously improve the PCE and reduce the E_loss in binary PSCs.

Full text of DOI:10.1039/c9ta03177d

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ISSN 2050-7488
PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS2 nanocages as a lithium ion battery anode material
rsc.li/materials-a

Page 1 of 11
JPolueransael odfoMnaotetraiadljsuCshtemmairsgtriynsA
Journal Name
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DOI: 10.1039/C9TA03177D
ARTICLE
Benzo[1,2-b:4,5-b']diselenophene-fused nonfullerene acceptors
with alternative aromatic ring-based and monochlorinated end
group: new synergistic strategy to simultaneously achieve highly
efficient organic solar cells with energy loss of 0.49 eV
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Shi-Sheng Wan,a,# Xiaopeng Xu,b,# Jin-Liang Wang,a, #,* Gui-Zhou Yuan,a Zhao Jiang,a Gao-Yang Ge,a Hai-Rui Bai,a Zheng Li,a
Qiang Peng b,*
A new synergistic strategy using electron-rich core units and altering the aromatic structure-based 1,1-dicyanomethylene-3-
indanone (IC) as end-groups for nonfullerene PSCs is reported and investigated how to obtain excellent PCE with extreme
low Eloss simultaneously. Specifically, two Benzo[1,2-b:4,5-b']diselenophene-based, A-D-A-type chlorinated NF-SMAs
(BDSeThCl and BDSePhCl) are synthesized, which are linked with a new 2-chlorothienyl-based IC and a conventional
monochlorinated phenyl-based IC as end-group, respectively. BDSePhCl exhibited a wider and red-shifted absorption and
downshifted energy levels than that of BDSeThCl. The blend films of BDSePhCl:PM7 perform better charge generation
properties, more suitable phase separation, and more balanced charge mobilities in comparison with that of BDSeThCl:PM7.
Therefore, compared to the best PCE of 11.91% with Eloss of 0.58 eV for BDSeThCl:PM7 blends, the optimal BDSePhCl:PM7
blends show an enhanced PCE of 13.68% with reducing Eloss of 0.49 eV. Notably, the excellent PCE of 13.68% is the highest
record for A-D-A-type NF-SMAs with monochlorinated IC group in binary PSCs. The Eloss of 0.49 eV is the lowest value reported
for A-D-A typed NF-SMAs in binary PSCs with PCE >13%. These results demonstrate that tailoring the monochlorinated
aromatic ring-based IC is an effective strategy to improve the PCE and reduce the Eloss simultaneously in binary PSCs.
respectively, aiming to further enhance the performance of the
PSCs.[29-59]
Introduction
Among various chemical modification of the NF-SMAs, we noted
that the halogenated 1,1-dicyanomethylene-3-indanone (IC)-based
NF-SMAs have a great chance to achieve impressive PCEs,[60-65] owing
to the enhanced intramolecular charge transfer (ICT) effect[66], the
rich non-covalent interactions,[67-68] and the better film
morphology.[69] Moreover, introducing halogen atoms into NF-SMAs
is a feasible strategy to downshift the lowest unoccupied molecular
orbital (LUMO) and highest occupied molecular orbital (HOMO)
energy levels simultaneously, especially for LUMO energy levels,
leading to the reduction in optical bandgap (Egopt). On the other hand,
halogenated IC-based NF-SMAs are facile to synthesize, especially
chlorinated IC-based NF-SMAs, which made them more suitable for
PSCs application.[70] Actually, the effects of different halogen atoms
or the number of halogenated substituents in IC terminated group
based A-D-A type NF-SMAs on device performance have been
systematically investigated.[71,72] It is noted that all of halogenated IC-
based NF-SMAs with A-D-A structure were originated to phenyl-
based IC, which attached one or two halogen atoms to phenyl
backbone. In fact, the non-halogenated thienyl or naphthyl-fused IC
based NF-SMAs can enhance intermolecular π-π interactions and
facilitate charge transport owing to sulfur-sulfur interaction or
extended π-conjugation length, thus higher device performance was
achieved in comparison with corresponding non-halogenated
phenyl-fused IC based NF-SMAs.[73-75] However, because of the
critical challenge of the synthesis and a dearth of appropriate starting
materials, NF-SMAs incorporating halogenated atoms in non-phenyl
typed aromatic ring fused IC have never been reported for high
With the multiple unique advantages such as low cost, light weight,
abundant raw materials, good flexibility, and easy large-area
fabrication, bulk-heterojunction (BHJ) polymer solar cells (PSCs) have
achieved impressive progress.[1-8] The most common system of BHJ
PSCs is fullerene system and nonfullerene system, and the two
systems have a great evolution on PCEs, the best PCEs are up to 11%
and 15%, respectively.[9-11] Recently, various nonfullerene acceptors
(NFAs) are the hot spot of concern, owing to the advantages of the
broader and stronger absorption, more facile energy level and
structure modulation in comparison with that of fullerene system.[12-
21]
Among various types of NFAs, the structures of planar and linear
acceptor-donor-acceptor (A-D-A) type nonfullerene small molecule
acceptors (NF-SMAs) such as ITIC,[22] ITCC,[23]ITCPTC[24] have become
the most typical and successful NF-SMAs. The advanced single-
junction and tandem PSCs based on polymer/A-D-A type NF-SMAs-
based devices can provide over 14% and 17% PCEs, respectively,[7,25-
28]
indicating that these type devices have potential commercial
application value. Thus, a variety of chemical modification methods
have been applied on the non-conjugated side chain, the donor
central core unit (D) and the electron-deficient end-groups (A),
a.Key Laboratory of Cluster Science of Ministry of Education, Beijing Key Laboratory
of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and
Chemical Engineering, Beijing Institute of Technology, 5 South Zhongguancun
Street, Beijing, 100081, China. E-mail: jinlwang@bit.edu.cn
b.College of Chemistry, Sichuan University, Chengdu 610064, P. R. China. E-mail:
qiangpengjohnny@yahoo.com
# These authors contributed equally to this work.
Electronic Supplementary Information (ESI) available: See DOI: 10.1039/x0xx00000x
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performance polymer solar cells. Therefore, it would be important to study the effect of end-capped aromatic ring on theVpiehwoAtrotipclheyOsnilcinael
DOI: 10.1039/C9TA03177D
systematically vary the end-capped aromatic ring on a family of properties, morphology of films, and performance of PSCs fabricated
halogenated IC-based A-D-A type NF-SMAs and comprehensively by the halogenated IC-based NF-SMAs with A-D-A structure.
Figure 1. (a) Molecular structure of these NF-SMAs and PM7 donor. (b) Absorption spectra of BDSeThCl and BDSePhCl in thin films. (c) Cyclic voltammograms of BDSeThCl and
BDSePhCl films on Pt electrode in 0.1 M Bu4NPF6 in CH3CN solution versus Ag/AgNO3 (0.01 M in anhydrous acetonitrile) reference electrode with a scan rate of 100 mV/s.
Typically, in the process of pursuing various chemical rarely reported. To better address the limitation, it is necessary to
modification of the NF-SMAs, the essential purpose is desire to find other more effective strategies to achieve better balance
achieve the best suitable trade-off between the open circuit voltage between the Voc and Jsc, then further improving the PCE of PSCs and
(Voc) and short circuit current density (Jsc) for efficient PCE. From the reducing Eloss, simultaneously.
aspect of Jsc, the more number of extracted charges is a key
To address above challenges, as shown in Figure 1a, a pair of
parameter for high Jsc, which was achieved at the expense of large
monochlorinated IC-based A-D-A type NF-SMAs with benzo[1,2-
energy loss (Eloss).[76,77] However, for the materials with a given
b:4,5-b']diselenophene-functionalized core, namely BDSeThCl and
bandgap, the large Eloss (by the general equation energy loss (Eloss) =
BDSePhCl, end-capping with different aromatic ring fused electron-
opt
opt
Eg – eEVoc, where Eg is the smaller optical bandgap of two
materials) will cause the unnecessary waste of driving force and is
harmful to Voc. Thus, it is necessary to minimize Eloss and to overcome
negative trade-off between Jsc and Voc, thereby boosting PCEs of PSCs
further. Actually, minimize the energy offset between the polymer
donor and NF-SMAs is a rational strategy for reducing Eloss. For
example, from the chemical structural view, the common methods
for reducing the HOMO-HOMO energy offset are based on either
introducing electron-donating non-conjugated side-chain on central
deficient monochlorinated IC (2-chlorothienyl-based IC or
monochlorinated phenyl-based IC have been synthesized and
systematically investigated, respectively. Our design rationales are as
follows: 1) The molecular structures containing benzo[1,2-b:4,5-
b']diselenophene-functionalized electron-rich donor core and two
monochlorinated IC end-capped group are positive to enhance the
absorption in NIR region and excellent device performance; 2)
Providing a platform to investigate the effect of two electron-
deficient monochlorinated (2-chlorothienyl unit or monochlorinated
phenyl unit) on absorption bandgaps/energy levels, the
morphologies of blend films, and photovoltaic properties of A-D-A
core units or extending conjugate length by aromatic heterocycle
[37,78]
ring, thus obtaining a low Eloss
.
However, the balance point of
improving PCE and reducing Eloss in these methods tend to be limited
by absence of suitable polymeric donor and the complexity of
synthetic route of core units. Therefore, for high performance (PCE >
13%) of the PSCs based on A-D-A type NF-SMAs, Eloss < 0.5 eV is still
type NF-SMAs; 3) Evaluating how to reduce Eloss based on the
opt
equation Eloss = Eg
– eEVoc through monochlorinated group
variations while keeping high PCE of A-D-A-structural NF-SMAs. The
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first strategy aim to improve the value of eEVoc by a new 2- blend films, the optimal BDSePhCl:PM7 based device achieved a
View Article Online
DOI: 10.1039/C9TA03177D
chlorothienyl-based IC, while the second aspect aim to decrease the maximum PCE of 13.68%, which was much higher than that of
opt
value Eg by introducing a conventional monochlorinated phenyl- optimal BDSeThCl:PM7. It is noted that 13.68% is the highest value
based IC. Indeed, BDSePhCl exhibited stronger and broader for binary PSCs with monochlorinated end group based A-D-A type
absorption relative to BDSeThCl in thin films owing to the enhanced structural NF-SMAs. In addition, both of devices showed relative
intramolecular ICT effect of BDSePhCl. Moreover, BDSePhCl showed lower Eloss (<0.6 eV) and Eloss was easily modulated by our two
lower energy levels and smaller Egopt (1.41 eV) than that of BDSeThCl monochlorinated IC strategies. More exciting, owing to the
(1.55 eV). Besides, the photovoltaic performance of the PSCs using conventional monochlorinated phenyl-based IC as end-group, when
BDSeThCl or BDSePhCl as acceptors blended with polymer donor the optimal BDSePhCl:PM7-based devices achieve PCE of 13.68%,
PM7 and the morphology of the blend films are also well investigated Eloss is only 0.49 eV, which is one of the lowest values for efficient
and comprehensively compared. The optimal BDSeThCl-based binary devices based on A-D-A type NF-SMAs. Our study
devices exhibits a PCE of 11.91% with a high Voc of 0.97 eV, which is demonstrates the strategy that introducing different aromatic group
one of the highest PCE and Voc for A-D-A structural NF-SMAs based in monochlorinated IC units to delicately tune the properties of A-D-
on the 2-thienyl-fused IC as end-groups. Owing to the more balanced A-type NF-SMAs is an effective method to boost the PCE and reduce
charge mobility and more favorable morphology of BDSePhCl:PM7 the Eloss of PSCs simultaneously.
Results and discussion
Scheme 1. Synthetic routes of the new end-group ThCl and two chlorinated NF-SMAs.
The synthetic routes of the new end group ThCl and these two end group ThCl was received by the reaction between compound 3
NF-SMAs (BDSeThCl and BDSePhCl) were showed in Scheme 1. The and malononitrile using ethanol as a solvent at room temperature in
end group ThCl was prepared from 5-Chloro-2-thiophenecarboxylic 77% isolated yield. In principle, because compound 3 is asymmetric
acid (compound 1) through
a
three-step process. First, structure and the reactivity of the two carbonyl group is similar, thus
acylchlorination of compound 1 using the thionyl chloride as a the end group ThCl has two isomers. The mole ratio of the two
1
chlorinating reagent to afford the compound 2. The resulting isomers is about 2:1 according to the H NMR spectra. Finally, The
acylchlorinated reagent 2 was used directly to the next step without NF-SMA BDSeThCl was prepared by the Knoevenagel condensation
further purification. Second, compound 3 was prepared through between ThCl and BDSeT-CHO[72] in 84% yield. PhCl was prepared by
Friedel-Crafts reaction between malonyl dichloride and compound 2 relevant reference method,[64] which is also composed of the two
with aluminium trichloride as catalyst in 41% isolated yield. Third, the isomers. Another NF-SMA BDSePhCl was obtained between BDSeT-
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CHO and PhCl in a high yield of 93%. Therefore, the BDSeThCl and thermogravimetric analysis (TGA) has been carried out to investigate
View Article Online
DOI: 10.1039/C9TA03177D
BDSePhCl are also a mixture comprised of three isomers with steady the thermal stability of BDSeThCl and BDSePhCl under N2, Figure S1
ratio, respectively. All these intermediates, BDSeThCl and BDSePhCl displayed the TGA plots of BDSeThCl and BDSePhCl and indicated
were completely characterized by 1H NMR, 13C NMR, and MALDI- their good thermal stability with the decomposition temperature of
TOF-MS/ESI-MS
(see
Supporting
Information).
The 363 and 353 oC at 5% weight-loss, which is enough for PSCs.
Table 1. Optical properties and electronic energy levels of BDSeThCl and BDSePhCl.
sol. a)
film
film b)
λmax
λmax
λonset
[nm].
HOMOcv
[eV]
-5.58
LUMOcv
[eV]
-3.82
-3.96
NF-SMA
Egopt. c) [eV]
[nm].
685
725
[nm].
706
790
BDSeThCl
BDSePhCl
794
875
1.55
1.41
-5.61
a)In chloroform solution; b) In neat film; c) Egopt = 1240/λonset
.
Molecular geometry and LUMO/HOMO energy levels for the
The UV-vis absorption spectra of BDSeThCl and BDSePhCl were
BDSeThCl or BDSePhCl with three isomers are calculated, measured in chloroform solutions and thin films to study the effect
respectively, by density functional theory (DFT) at the B3LYP/6-31G on the optical properties. All of the absorption properties were
levels, and the methyl groups replace alkyl substituents to simplify displayed in Table 1. As shown in Figure S3, BDSeThCl and BDSePhCl
the calculations aiming to display the effect of chlorinated aromatic exhibit broad absorption in the region of 500-800 nm, in chloroform
structure-based IC on basic properties of BDSeThCl and BDSePhCl. As solutions. Absorption spectra of BDSePhCl shows an obvious slight
shown in Figure S2, BDSeThCl and BDSePhCl are highly planar owe red-shift in comparison with that of BDSeThCl. In details, BDSeThCl
to the fused ring core unit has an excellent planarity. The LUMO shows a maximum absorption peak at 685 nm with an extinction
orbital of BDSeThCl and BDSePhCl distributed mainly on the whole coefficient of 1.88 × 105 M−1 cm−1, while BDSePhCl shows a redshifted
backbone, so when altering chlorinated the aromatic structure-based maximum absorption peak at 725 nm with a higher extinction
IC in BDSeThCl and BDSePhCl, the LUMO energy levels can be coefficient of 2.14 × 105 M−1 cm−1. The thin film spectra of the NF-
changed significantly. The HOMO orbital of BDSePhCl mainly SMAs and donor PM7 were shown in Figure 1b, BDSeThCl and
distributed on the central core units. For BDSeThCl, its HOMO orbital BDSePhCl exhibit obviously red-shifted absorption band (550-900
not only distributed on the core units, but also on the thiophene ring. nm) with respect to their corresponding band in solutions, with
This is one of the reasons why the HOMO energy levels of BDSeThCl maximum absorption peak at 706 nm and 790 nm, respectively. In
are higher than that of BDSePhCl. The calculated energy levels were addition, the optical bandgap of BDSeThCl and BDSePhCl are
shown in Table S1. The results predict that transforming end-groups estimated from their absorption onset of the thin film to be 1.55 eV
from 2-chlorothienyl-based IC to monochlorinated phenyl-based IC and 1.41 eV, respectively. Furthermore, the wide bandgap polymer
will obvious change the energy levels and thus influence on the band PM7 can provide a suitable complementary absorption with our NF-
gap of NF-SMAs.
SMAs in thin films, in particular with BDSePhCl, which is the key to
achieve the following broad EQE response and high Jsc.
Table 2. Photovoltaic performances and charge carrier mobilities of the PSCs based on NF-SMAs/PM7 under standard AM 1.5G illumination, 100 mW cm−2
.
μe/μh
(10−4cm2V-1s-1)
EQE c)
NF-SMA
Voc a)[V]
Jsc a)[mA cm−2]
FF a)[%]
PCE a)[%]
Jsc
BDSeThCl
BDSeThClb)
BDSePhCl
BDSePhClb)
0.98(0.97±0.01)
0.97(0.96±0.01)
0.93(0.92±0.01)
0.92(0.91±0.01)
16.83(16.67±0.16)
17.85(17.71±0.14)
19.11(19.00±0.11)
20.35(20.25±0.10)
63.8(62.5±1.3)
68.8(67.7±1.1)
66.3(65.2±1.1)
73.1(72.1±1.0)
10.52(10.11±0.41)
11.91(11.51±0.40)
11.78(11.40±0.38)
13.68(13.29±0.39)
16.63
17.52
19.02
20.16
2.52/1.39
3.99/2.47
4.53/2.78
5.07/3.95
a)The values in parentheses are the average values calculated from >20 devices with standard deviation; b)With thermal annealing at 100 °C for 10 min; c) Calculated Jsc
values from the EQE spectrum.
The electrochemical property of BDSeThCl and BDSePhCl were electron-withdrawing terminal groups, the LUMO energy levels of
investigated by cyclic voltammetry in Table 1. As shown in Figure 1c, BDSeThCl upshifted dramatically in comparison with that of
BDSeThCl and BDSePhCl showed one quasi-reversible oxidation BDSePhCl. In addition, the HOMO and LUMO energy levels of two
wave and one irreversible reduction wave, and the potentials are NF-SMAs are consistent with the DFT results, and match well with
calibrated using Fc/Fc+ redox couple. According to the corresponding those of the donor polymer PM7 (Figure S3). When fabricating the
onset oxidation and reduction potentials (φox/red), the calculated devices with two NF-SMAs and PM7, respectively, the higher-lying
HOMO and LUMO energy levels of BDSeThCl and BDSePhCl are -5.58 LUMO energy levels of BDSeThCl is expected to achieve the higher
eV/-3.82 eV and -5.61 eV/-3.96 eV, respectively. BDSeThCl exhibited Voc of devices in comparison with that of BDSePhCl, while the energy
a similar HOMO energy levels with BDSePhCl. Owing to the more offsets of PM7 and BDSePhCl are larger than that of BDSeThCl and
electron-donating effect of the thienyl unit relative to phenyl units in
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PM7, which may be rewarding for the excitons dissociation, thus Figure 2a. The as-cast BDSeThCl:PM7-based devices exhibited a high
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resulting higher Jsc.
The photovoltaic properties of BDSeThCl and BDSePhCl were
Voc of 0.98 eV, a Jsc of 16.83 mA cm−2, and fill fDaOctIo: 1r0(.F1F0)3o9/fC693T.8A0%31w7i7tDh
a PCE of 10.52%. The as-cast BDSePhCl:PM7-based devices exhibited
a PCE of 11.78% with a Voc of 0.93 eV, a Jsc of 19.11 mA cm−2, and FF
of 66.3%. After thermal annealing (TA) at 100 oC for 10 min, the
performance of BDSeThCl:PM7-based device was slightly increased
to 11.91% with a high Voc of 0.97 eV, a Jsc of 17.85 mA cm−2, and FF
of 68.8%. Meanwhile, compared with the TA treated BDSeThCl:PM7-
based devices, the TA treated BDSePhCl:PM7-based device
presented an obviously higher PCE of 13.68% with a higher Jsc of
20.35 mA cm−2, and higher FF of 73.1%. Such excellent PCE is the
highest value for monochlorinated end group functionalized A-D-A
type NF-SMAs based binary PSCs.
investigated by blending with PM7 as an electron donor to fabricate
PSCs with device structure of Glass/ITO/ZnO/active layer/MoO3/Ag.
After screening the D/A weight ratio, the amount of DIO additive, and
thermal annealing (TA) temperatures (see Figure S4 to Figure S6, and
Table S2 to Table S4), the optimized conditions for both
BDSeThCl:PM7 and BDSePhCl:PM7 blends are the D/A weight ratio
of 1:1 in chlorobenzene solution with 0.5% DIO additive and thermal
o
annealing (100 C) for 10 minutes. The performance of the optimal
devices are summarized in Table 2. The current density-voltage (J–V)
curves of BDSeThCl-and BDSePhCl-based devices are shown in
Figure 2. Characteristic J–V curves (a), the corresponding EQE spectra (b), Jph versus Veff curves (c), and light-intensity (P) dependence of Jsc curves (d) of BDSeThCl:PM7 and
BDSePhCl:PM7-based PSCs with/without thermal annealing under AM 1.5 G irradiation (100 mW cm−2).
The corresponding external quantum efficiency (EQE) spectra of 600-800 nm is slightly lower than that of BDSePhCl:PM7-based
PSCs based on BDSeThCl:PM7 and BDSePhCl:PM7 are revealed in devices. Such lower value in EQE may be due to the stronger self-
Figure 2b. The BDSePhCl:PM7-based devices exhibit wider aggregation of BDSeThCl with large phase separation in the blend of
photoresponse from 300 to 860 nm than that of BDSeThCl:PM7 (300- BDSeThCl and PM7, thus causing to be harmful to charge dissociation
800 nm), owing to the red-shifted and stronger absorption of and transportation. As shown in Table 2, the corresponding
BDSePhCl, resulting in the improvement of Jsc. It is worth noting that integrated Jsc from the EQE spectra with the AM 1.5G reference
the optimal BDSePhCl:PM7-based devices show over 70% EQE value spectrum is 17.52 mA cm-2 for the optimal BDSeThCl:PM7-based
from 516-783 nm and a maximum value of 80.3% at 612 nm. devices and 20.16 mA cm-2 for the optimal BDSePhCl:PM7-based
Although the optimal BDSeThCl:PM7-based devices also display over devices, respectively, corresponding to the Jsc values measured from
70% EQE from 502-730 nm and a maximum value of 80.1% at 592 nm, the J-V curves within a reasonable mismatch (the error is <5%).
the EQE value of BDSeThCl:PM7-based devices across the range of
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DOI: 10.1039/C9TA03177D
Figure 3. (a) PCE versus Eloss, (b) Voc versus Jsc, and (c) EQEmax versus Eloss in the binary PSCs based on A-D-A typed NF-SMAs/polymer donor in comparison with the optimal BDSeThCl
or BDSePhCl/PM7-based device. (d) The normalized EQEPV spectra in logarithmic scale of BDSeThCl- or BDSePhCl-based devices.
As far as we know, the larger Eloss may cause the complicated increase of Jsc, so adjusting the balance between Voc and Jsc has great
processes to reduce the performance of PSCs based on NF-SMAs. So significance for the PSCs performance. For a more intuitive display,
it is very necessary to receive a high PCE with a low Eloss we pick out all the points of PCE > 13% and our work (13.68%) as a
simultaneously. Here, we summarized the plot of PCE versus Eloss in study case, the relationship between Voc and Jsc is finally given out by
this work and the other binary PSCs based on NF-SMAs with A-D-A a linear fitting function, given by: y = 1.54 – 0.03x (R = 0.96), where x
structure to demonstrate the advantage of our chlorinated NF-SMAs. and y are defined as Jsc and Voc, respectively. R is an indicator to
As shown in Figure 3a, although the PCE may be improved by the reflect the goodness of fitting, |R| ≤ 1. If the linear fitting function
proper strategy of reducing the Eloss, it is obvious that the most of the exihibits good fitting, the value of |R| will close to 1. Our Voc/Jsc data
excellent performance (PCE > 13%) A-D-A typed NF-SMAs showed an points were well located at the fitting function line, which indicated
Eloss of about 0.55-0.70 eV.[20, 25, 27, 41-45, 64, 68, 79-81] Thus, many of donor our chlorinated NF-SMAs/PM7 pairs have the suitable possible trade-
/A-D-A typed NF-SMAs blends with lower Eloss (<0.5 eV) only off between Voc and Jsc to boost PCE with low Eloss simultaneously.
exhibited moderate PCE (<12%). Excitingly, the optimal Moreover, we also summarized a plot of EQEmax against Eloss in our
BDSeThCl:PM7-based devices and BDSePhCl:PM7-based devices optimal devices in comparison with other binary PSCs based on
play small Eloss values of 0.58 and 0.49 eV owing to the high Voc and polymer donor/A-D-A-typed NF-SMAs. As shown in Figure 3c, It
the small bandgap, while these PCEs are 11.91% and 13.68%, notes that the Eloss values of 0.49 eV for the optimal BDSePhCl-based
respectively. To the best of our knowledge, the Eloss of 0.49 eV based PSCs is the smallest values for all the binary PSCs based on simple A-
on the optimal BDSePhCl:PM7 blend films is the lowest value D-A-structural NF-SMAs with EQEmax＞75%. Such results indicated
reported for NF-SMAs with simple A-D-A structure in binary PSCs that the BDSePhCl-based PSCs show better trade-off between the Jsc
with PCE >13% (Table S5). This result indicated the design strategy of and Voc owing to the rationally matching D/A pair.
modulating the chlorinated aromatic structure-based IC of NF-SMAs
To deeply clarify the low Eloss of the optimal devices, the ECT
can minimize Eloss and obtain high efficient PCE simultaneously,
(charge transfer state energy) and λ (reorganization energy) were
which provided a suitable adjustment for the trade-off between Jsc
investigated, which were obtained from equation (1), according to
the framework of Marcus theory.[82] Equation is given by:
and Voc. Therefore, as shown in Figure 3b, we also summarized the
relationship of Voc (0.5 V < Voc < 1.13 V) dependence on the Jsc (10 mA
cm−2 < Jsc < 28 mA cm−2) in binary PSCs based on NF-SMAs with simple
A-D-A structure. Obviously, the general trend is to decrease Voc with
푓
퐶푇+휆−퐸)
퐸√4휋휆푘푇 exp(−(퐸
)
(1)
( )
퐸
퐸푄퐸푃푉
=
4휆푘푇
6 | J. Name., 2012, 00, 1-3
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Journal of Materials Chemistry A
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Where k is Boltzmann’s constant and T is the absolute contributed to the higher Jsc and FF in the optimal device. In addition,
View Article Online
DOI: 10.1039/C9TA03177D
temperature, EQEPV is the photovoltaic EQE, f is the absorption to investigate the charge recombination properties in BDSeThCl/
strength of the charge-transfer state, proportional to the density of BDSePhCl-based devices, we measured the Jsc at different light
the donor/acceptor interfaces, E represents the photon energy and intensities (P). The equation of Jph ∝ Pα can induce the relationship
λ is the reorganized energy of the charge-transfer states. As shown between Jsc and P, where exponential factor (α) reflects the charge
in Figure 3d, the extracted values of ECT for the BDSeThCl:PM7 blends recombination degree. If the devices exhibit weaker bimolecular
is 1.46 eV, which is higher than that of BDSePhCl:PM7 blends (1.37 recombination, the value of α will more close to 1. As shown in Figure
eV), corresponding to the value of Voc for BDSeThCl:PM7-based 2d, the values of optimal/as-cast BDSePhCl:PM7 device are 0.99 and
devices is higher in comparison with that of BDSePhCl:PM7-based 0.98, respectively, which are larger than that of the optimal/as-cast
devices. Moreover, the energy losses of BDSeThCl:PM7-based BDSeThCl:PM7 based devices (0.98 and 0.97). Such results indicated
devices and BDSePhCl:PM7-based devices suffering from charge that effective charges transport along with a very weak bimolecular
transfer were 0.10 eV and 0.04 eV, respectively, calculating by Eg - recombination have occurred in those devices, in particular to the
ECT, which indicates the lower energy loss resulting from the charge optimal BDSePhCl:PM7 devices. To further study the trap-assisted
recombination in BDSePhCl:PM7-based devices than that of recombination losses, the plotting Voc as a function of light intensity
BDSeThCl:PM7-based devices.[83-85] In addition, the value of λ for (P) in a seminatural logarithm scale was measured. In general, the
BDSePhCl:PM7-based devices is 0.05 eV, which is smaller than that bias of the slope from the unity kT/q represents that trap assisted
of BDSeThCl:PM7-based devices (0.07 eV). The lower reorganized Shockley-Read-Hall recombination in the devices. As shown in Figure
energy indicates the less energetic disorder of charge transfer states S8, the slopes of Voc with light intensity changes for the as-
(CTs), leading to a smaller voltage loss in BDSePhCl:PM7-based cast/optimal BDSeThCl:PM7-based devices are 1.42 kT/q and 1.29
device.[86,87] In fact, the total Eloss in PSCs devices mainly include kT/q, which are higher than that of the as-cast/optimal
charge recombination and energetic disorder, therefore, the lower BDSePhCl:PM7-based devices (1.37 kT/q and 1.20 kT/q), respectively.
value of Eg-ECT and λ in BDSePhCl:PM7-based devices contribute to Such results demonstrated that the trap-assisted recombination
the total smaller Eloss with higher EQE.
shows a weaker role at open-circuit condition for the optimal
BDSePhCl:PM7-based device, leading to an improved Jsc.
The charge-carrier mobilities of the blend films were
investigated by the space charge-limited current (SCLC) method with
device
structures
of
Glass/Al/active
layer/Al
and
Glass/ITO/PEDOT:PSS/active layer/MoO3/Au, respectively (Figure
S7). The electron and hole mobilities of the as-cast blend film of
BDSePhCl:PM7 are 4.53 × 10−4 cm2 V−1 s−1and 2.78 × 10−4 cm2 V−1 s−1,
respectively, which is obviously higher than that of BDSeThCl:PM7
blend film (2.52 × 10−4 cm2 V−1 s−1 and 1.39 × 10−4 cm2 V−1 s−1). After
TA treatment, the electron and hole mobilities are obviously
enhanced, which might lead to higher Jsc and FF in optimal devices.
Moreover, the TA treatment blend of BDSePhCl:PM7 displayed
higher and more balanced carrier mobilities (5.07 × 10−4/3.95 × 10−4
cm2 V−1 s−1, with μe/μh=1.28) in comparison with those of
BDSeThCl:PM7 (3.99× 10−4/2.47 × 10−4 cm2 V−1 s−1, with μe/μh=1.61).
These results demonstrated the BDSePhCl:PM7-based devices could
suppress charge recombination, leading to high Jsc and FF.
To investigate the effect of the different chlorinated aromatic
ring-based IC of the NF-SMAs on the charge generate, transfer, and
the extracted properties, the plots of photocurrent (Jph) versus the
effective applied voltage (Veff) for the as-cast and optimal devices
were measured. Jph is defined as Jph = JL − JD, where JL and JD are the
photocurrent densities under illumination and in the dark,
respectively. Veff is defined as Veff = V0 − Va, where V0 is the voltage at
which Jph = 0 and Va is the applied bias. When Veff arrived at ca. 2 V,
the Jph value could reach saturation (Jsat), which is indicative of the
excitons were dissociated and the charge were almost collected by
the individual electrodes. The value of Jph/Jsat was calculated under
their short-circuit conditions. As shown in Figure 2c, the Jph/Jsat ratios
for the as-cast and optimal BDSePhCl:PM7-based devices are 0.93
and 0.95, respectively, which is higher than that of 0.92 and 0.94 for
the as-cast and optimal BDSeThCl:PM7-based devices, respectively.
The higher Jph/Jsat ratio of the optimal BDSePhCl:PM7 blend films
indicated a better charge dissociation efficiency in active layer and
Figure 4. GIXD patterns for the blend films of (a,b) BDSeThCl:PM7 without/with thermal
annealing treatment; (c-d) BDSePhCl:PM7 without/with thermal annealing treatment.
Grazing incident X-ray diffraction (GIXD) measurements were
performed to investigate the effect of the different chlorinated
aromatic ring-based IC on the molecular order and crystallinity of
pure BDSeThCl/BDSePhCl and blend films. As shown in Figure S9, the
neat BDSeThCl and BDSePhCl films showed amorphous population
with a hump-shaped lamellar and π-π stacking diffractions. While in
the neat donor polymer PM7, the sharp (100) diffraction peak at 0.31
Å-1 in plane (IP) direction and an obvious(010) diffraction peak at 1.68
Å-1 in out of plane (OOP) direction were observed. Thus neat PM7
film exhibited a predominant “face-on”orientation with the π-π
This journal is © The Royal Society of Chemistry 20xx
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stacking distance of 3.74 Å, which is consistent with the previous coherence length (CL) of BDSeThCl:PM7 in the OOPVdieiwreAcrttiicolenOwnlianes
reported results.[88] The GIXD of blend films for BDSeThCl:PM7 and reduced from 17.1 Å to 11.5 Å, which waDsOcIo: 1n0s.i1s0te39n/tC9wTiAth03A17F7MD
BDSePhCl:PM7 were presented in Figure 4 and The out-of plane images below, which was conducive to decrease charge
(dotted line) and in-plane (solid line) line-cuts in GIXD for the recombination and increase exciton dissociation probability. As for
corresponding blend films were shown in Figure S10. Interesting, the the blend films of BDSePhCl:PM7, the intensity of π-π and lamellar
as-cast BDSePhCl:PM7 blend film still kept a predominant “face- diffraction peaks both dramatically increase after TA treatment,
on”orientation by the strong π-π stacking in OOP direction, while the indicating the “face-on”orientation was enhanced, which was
as-cast BDSeThCl:PM7 blend film showed a mixed orientation that beneficial to the charge transportation, thus resulting a higher Jsc and
contains “face-on” and “edge-on” orientations by the evidence of FF. In details, in OOP direction, the as-cast/optimal blend films of
both the strong π-π stacking peaks in OOP and IP direction. Such BDSePhCl:PM7 show π-π stacking (010) peak at 1.82 Å−1 and 1.86 Å−1,
results implies that introduction of BDSeThCl into PM7 weakens the respectively, corresponding to the π-π stacking (010) distance of 3.45
predominant “face-on”orientation and crystallinity of PM7 due to Å and 3.37 Å, as well as coherence length of 14.0 Å and 14.1 Å,
over aggregation of BDSeThCl. In contrast, although the respectively. In IP direction, the as-cast/optimal blend films of
BDSePhCl:PM7 blend film exhibited relatively weak diffraction peak BDSePhCl:PM7 show lamellar (100) diffraction peak at 0.36 Å−1 and
compare to the neat donor polymer PM7, BDSePhCl and PM7 can be 0.37 Å−1, respectively, corresponding to a lamellar distance of 17.4 Å
fully blended without changing the predominant “face-on” and 16.9 Å, respectively. These results demonstrated the π-π
orientation. For the blend films of BDSeThCl:PM7, the π-π stacking stacking distance and lamellar distance for the blend films of
(010) peak in the OOP is at ca. 1.80 Å−1 and the lamellar (100) BDSePhCl:PM7 were slightly decreased after TA annealing. In
diffraction peak in the IP direction is at ca. 0.36 Å−1, corresponding to summary, the BDSePhCl:PM7 films shows smaller π-π stacking and
the π-π stacking distance of 3.48 A
̊
and lamellar distance of 17.4 A
̊
.
lamellar distances, stronger crystallinity, more predominant “face-on”
After thermal annealing, the location of π-π stacking (010) peak in orientation and longer CL in π-π stacking direction in comparison
the OOP and the lamellar (100) diffraction peak in the IP direction of with those of BDSeThCl:PM7. These features are beneficial to gain
BDSeThCl:PM7 were reduced to 1.69 Å−1 and 0.33 Å−1, respectively. higher charge mobilities and less charge recombination for the
Thus the π-π stacking distance and lamellar distance increased to BDSePhCl:PM7 based devices, and thus achieved a higher FF, Jsc, and
3.71 A and 19.0 A, respectively. Moreover, the corresponding PCE.
̊ ̊
Figure 5. AFM height images (a–d) and AFM phase images (e–h) of the as-cast/optimal PM7:BDSeThCl and PM7:BDSePhCl blend film, respectively. (i–l)TEM images of the as-
cast/optimal PM7:BDSeThCl and PM7:BDSePhCl blend film, respectively.
8 | J. Name., 2012, 00, 1-3
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JPolueransael odfoMnaotetraiadljsuCshtemmairsgtriynsA
Journal Name
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View Article Online
DOI: 10.1039/C9TA03177D
To investigate the effect of different chlorinated aromatic ring- with that of BDSeThCl in thin films. Moreover, the optimal
based IC on the surface and bulk morphologies of these blend films, BDSePhCl PM7 blend films exhibited better phase separation
atomic force microscopy (AFM) and high-resolution transmission morphology, more balanced charge transport properties, and
electron microscopy (TEM) were used to study the surface and bulk weaker charge recombination than that of BDSeThCl PM7
morphologies. As displayed in Figure 5a-h, all of blend films based blend films, enabling higher Jsc, FF, and PCE in
presented relatively uniform and smooth surface with root-mean- BDSePhCl PM7 based PSCs. The optimal BDSePhCl PM7 based
:
:
-
:
:
square roughness (Rq) of about 2-4 nm. The as-cast PM7:BDSeThCl device achieved a maximum PCE of 13.68%, which is the highest
blend film showed slightly larger aggregation and a higher RMS value for binary PSCs with monochlorinated end group based A-
roughness of 3.0 nm than that of PM7:BDSePhCl blend film (2.6 nm), D-A type NF-SMAs. Moreover, such high efficient
whereas larger phase separation and aggregation domains were BDSePhCl:PM7 based device showed a quite low energy loss of
exhibited in the phase image of PM7:BDSeThCl blend film. After 0.49 eV, which is among the smallest value reported to date for
thermal annealing treatment, although the Rq of the PM7:BDSeThCl A-D-A-type NF-SMAs based binary PSCs with efficiency >13%.
film is slightly increased to 3.8 nm and the Rq of the PM7:BDSePhCl Different from the most of reported focused on reduction of
film is slightly decreased to 2.1 nm, the corresponding phase images Eloss by enhancement of electron-rich core unit of NF-SMAs
showed the better fibrous feature and proper phase separation, solely, our results provide an original insight for the modulation
which contributed to enhance the charge separation. As shown in of PCE and Eloss by tailoring the monochlorinated aromatic ring-
Figure 5i-l, the TEM images of as-cast PM7:BDSeThCl blend film also based IC of NF-SMAs with A-D-A structure to boost PCE>13.5%
display relative slightly larger phase separation and aggregation and Eloss< 0.50 eV simultaneously. In addition, the flexibility of
domains in comparison with that of PM7:BDSePhCl. The undesired our strategy (tune the properties of A-D-A structural NF-SMAs
bulk morphology of PM7:BDSeThCl blend film was caused by an by adjustment of monochlorinated other aromatic ring-based IC
excessively aggregation tendency due to the 2-chlorothienyl-based might allow us to further improve the PCE and reduce the Eloss
.
IC as end-group induced stronger intermolecular π–π interactions.
Such uneven morphology results in a lower charge collection
probability and thus moderate PCE. After thermal annealing, the
Acknowledgements
better nanoscale interpenetrating fibrils structure and suitable phase
separation of these blend films were achieved, which may be
attributed to improve charge separation and enhanced PCE in
comparison with these of as-cast films. These results reveal that the
modulation of aromatic backbone in chlorinated end-capping group
can effectively control the extent of phase separation and the surface
morphology.
This work was financially supported by the grants from the Natural
Science Foundation of China (No. 21472012, 21672023). J.-L.W. was
supported by the Thousand Youth Talents Plan of China and Beijing
Natural Science Foundation (2152027). The authors are grateful for
having been able to use the beamline BL14B1 (Shanghai Synchrotron
Radiation Facility) for 2D GIXD experiments. The authors thank
Analysis & Testing Center, Beijing Institute of Technology for NMR
and TGA experiments. The authors thank Prof. Peng-Fei Li (Beijing
Institute of Technology) for the helping on the DFT calculations
experiment.The authors also thank Prof. Jian Pei (Peking University)
for the helping on the elementary analysis and ESI MS experiment.
Conclusions
In conclusion, we have reported a synergistic strategy via
using an electron-rich core units and simple end-group
modification to rationally modulate the properties of NF-SMAs
to achieve an excellent PCE and a very low Eloss of PSCs
Notes and references
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TOC Figure
A PCE of 13.68% with Eloss of 0.49 eV is obtained, which is the highest in binary PSCs with monochlorinated NF-SMAs.
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