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Low boiling point solvent additives enable vacuum

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Cite this: DOI: 10.1039/c8ta09259a

drying-free processed 230 nm thick PTB7-
Th:PC71BM active layers with more than 10% power
conversion efficiency†
Jinxiang Chen, Feilong Pan, Yong Cao and Junwu Chen *

Received 24th September 2018
Accepted 19th December 2018
DOI: 10.1039/c8ta09259a
rsc.li/materials-a
In this work, three fast removable solvent additives o-chloroanisole (CBE), o-chlorobenzaldehyde (CBA),
and o-chloroacetophenone (CBK) with low boiling points (bp.) of 195, 212, and 230
C, respectively,
were applied for morphology control of PTB7-Th:PC71BM active layers. Without a vacuum drying
process, CBE, CBA, and CBK could work well as fast removable solvent additives in chlorobenzene (CB)
host solvent. Relative to the routine 1 : 1.5, a D/A ratio of 1 : 2 is more beneficial for device performances
with thicker active layers because of increased charge extraction rates and longer carrier lifetimes. At
a thickness of 100 nm, CBE, CBA, and CBK gave PCEs between 9.51% and 9.55% while for 230 nm
thick active layers, CBE, CBA, and CBK afforded PCEs of 10.12%, 9.90%, and 9.27%, respectively, well
demonstrating the advantage of low bp. solvent additives in vacuum drying-free processing of thick
active layers. Relative to the 100 nm level, an optimal PCE at the 200 nm level is more useful for
defining a larger processing window that can help fabrication of pin-hole free active layers during high
speed printing. Therefore, the fast removable solvent additive strategy has big potential to upgrade some
high efficiency active layer materials to a more roll-to-roll compatible level.

a solvent additive is an indispensable method in achieving

Introduction
Aiming at the sustainable development of human society, there
is a growing demand for renewable energy sources. Bulk hetero-
junction (BHJ) polymer solar cells (PSCs) are a promising
renewable energy technology because of their light weight,
exibility, and large area low-temperature solution
manufacturing that can be compatible with a continuous roll-
to-roll printing line.1,2 A BHJ active layer composed of
electron-donor and -acceptor phases possesses great advantage
in supplying large donor/acceptor interfaces for efficient charge
separations as well as a bicontinuous interpenetrating network
of the donor and acceptor phases for fast transports of holes
and electrons to electrodes in the mean-time.3,4 Along with the
great efforts in developing new donor and acceptor materials as
well as good control of the BHJ morphology, the power
conversion efficiencies (PCEs) of single junction BHJ PSCs are
continuously improved up to the state-of-the-art 14%.5–9
Thermal annealing,10 solvent vapor annealing (SVA)11–13 and use
of solvent additives14–17 are the typical methods for morphology
optimizations of BHJ active layers. It should be noted that using
Institute of Polymer Optoelectronic Materials & Devices, State Key Laboratory of
Luminescent Materials & Devices, South China University of Technology, Guangzhou
510640, P. R. China. E-mail: psjwchen@scut.edu.cn
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c8ta09259a
many record efficiencies for both fullerene and nonfullerene
based BHJ PSCs.17–26 At the eve of real application of PSCs,
developing promising solvent additives to meet roll-to-roll
compatibility becomes quite necessary.
Large area and high speed solution printing of organic active
layers toward scale-up manufacturing will encounter the
thickness variation issue.27 An ideal active layer should main-
tain high efficiency even when its thickness is largely varied.6,28
This concern has been called as the thickness tolerance of an
organic active layer, which is very important in dening a pro-
cessing window for PSCs with a qualied PCE on a roll-to-roll
printing line.29 During the past few years, increasing attention
has been paid to the thickness tolerance issue, and develop-
ment of new donors and acceptors with high carrier mobility
and good control of the nanoscale morphology of BHJ lms
have been demonstrated to be effective.6,9,28–34 Although
a 100 nm average thickness of the active layer has already shown
very high efficiency and is also benecial for saving materials
cost, the thickness is only suitable for dening a very small
processing window. For example, a thickness range of 100 
30 nm would signicantly limit the operating speed of a roll-to-
roll printing line. Low production capacity means high product
cost. Relative to a 100 nm average thickness, a thicker active
layer can also help suppressing of pin-holes inside the active
layer.28 Thus a thicker average thickness with an enlarged

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Journal of Materials Chemistry A
processing window to meet a higher operating speed is more
attractive. It is worth noting that high efficiency and a wide
processing window from 100 to 600 nm based on an average
thickness at 300–400 nm has been realized, based on some high
mobility materials.29 A suitable average thickness should be
a compromise of operating speed, yield control, and materials
cost when transferred to an industrially feasible roll-to-roll line.
PTB7-Th (Fig. 1a) and PTB7 with the thieno[3,4-b]thiophene/
benzodithiophene backbone unit are two well-known low band
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gap polymer donors because of some record efficiency perfor-
mances reported in the past several years for single junction
BHJ PSCs.35,36 Unlike the alkyl substitutions for PTB7, PTB7-Th
comprises alkylthienyl pendants on the benzodithiophene
(BDT) unit, which afford PTB7-Th with higher PCEs than PTB7
in combination with a fullerene or a nonfullerene
acceptor.17,21,24,25,37–39 Recently, PTB7-Th based active layers
showing high short-circuit current densities (Jsc) in binary and
ternary PSCs with outstanding PCEs up to 14% have been
demonstrated,40,41 from which tandem PSCs with a record high
PCE of 17.29% can be achieved with the PTB7-Th based ternary
blend lm.42 Also, PTB7-Th based semitransparent PSCs with
9.77% PCE for an average visible transmittance of 36% have
been realized, which may promote the development of power
generating windows.43 These results clearly indicate the prom-
ising future of PTB7-Th based active layers. It should be noted
that the high efficiency BHJ active layers of PTB7-Th and PTB7
are typically processed with chlorobenzene (CB) as the host
solvent and small amount 1,8-diiodooctane (DIO) as the solvent
additive.17,42,44
There are several reports involving the evaluation of the
thickness tolerance of PTB7-Th and PTB7 based active layers. In
the report by Marks et al., CB/DIO processed PTB7:PC71BM
active layers showed very poor thickness tolerance, with PCEs of
7.98%, 6.63%, and 4.23% for 100, 195, and 300 nm active layer
Fig. 1 (a) Chemical structures of PTB7-Th and PC71BM. Chemical structures and boiling points (bp.) of (b) host solvent chlorobenzene (CB) and
(c) the three solvent additives o-chloroanisole (CBE), o-chlorobenzaldehyde (CBA), and o-chloroacetophenone (CBK).
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thicknesses, respectively.44 Relative to the device performance at
100 nm thickness, PTB7-Th also exhibited obviously decreased
PCEs for thicker active layers of 200 nm. In the report by Jen
et al., CB/DIO processed PTB7-Th:PC71BM active layers with a D/
A ratio of 1 : 1.5 displayed PCEs of 9.3%, 9.41%, and 8.01% for
100, 150, and 230 nm active layer thicknesses, respectively.34
For PTB7-Th:PC71BM active layers processed with a D/A ratio of
1 : 1.1 and a much lower DIO content of 0.5%, PCEs of 9.03%,
7.45%, and 6.50% were found for thicknesses of 100, 200, and
280 nm, respectively.45 For all-polymer PSCs with PTB7-Th as
the donor, the PCE showed a large decrease along with
increasing active layer thickness.46 Although untraditional spin-
coatings have been proposed for the modication of the thick-
ness tolerance of PTB7-Th based active layers, the lm-forming
processes are more complicated than the routine one.34,47 It
should be noted that DIO is still the solvent additive in modi-
cation of thickness tolerance.
DIO is a solvent additive with a very high boiling point (bp.)
of 332.5.14 There is DIO residue inside the active layer when the
host solvent has been removed during the solution process-
ing.48,49 A subsequent vacuum drying process is typically applied
to fully remove the DIO residue so as to maximize PCE, e.g. even
for a low DIO loading of 0.5%.45 However, toward full roll-to-roll
solution-processing of BHJ PSCs, the vacuum drying process to
remove a solvent additive with a very high bp., e.g. the DIO, is
unfavorable and should be avoided.49 Although removing DIO
via a solvent washing process is an alternative consideration,
the extra washing processing would increase cost.48 Very
recently, we demonstrated that o-chlorobenzaldehyde (CBA in
Fig. 1) with a bp. of 212
C was a higher efficiency solvent
additive for the morphology optimization of PTB7:PC71BM
active layers when compared with DIO.49 Due to its much lower
bp. relative to DIO, CBA can show the advantage of fast removal
in the absence of vacuum drying: being almost completely
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removed along the evaporation process of the CB host solvent
during spin-casting, and thus avoiding excessive SVA effects of
DIO residue in thick BHJ lms during vacuum drying. The CBA-
processed PTB7:PC71BM active layers of 100, 200 and 300 nm
could achieve PCEs of 9.11%, 8.24%, and 7.11%, respectively,
much higher than 7.53%, 5.71%, and 4.93% for corresponding
DIO control devices with vacuum drying. It should be noted
that, from 100 to 300 nm, the continuously decreased PCEs are
unideal in dening high efficiency processing windows.
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Therefore, there is a great demand to demonstrate that a fast
removable solvent additive can reverse the PCE decreasing
tendency with thicker blend lms, particularly for some prom-
ising material systems.
In this work, o-chloroanisole (CBE) and o-chlor-
oacetophenone (CBK), two new solvent additives with bp. values
of 195 and 230
C, respectively, were investigated in spin-
coating PTB7-Th:PC71BM active layers, in comparison to CBA
(Fig. 1). It was found that, without a vacuum drying process,
CBE, CBA, and CBK all could work well as fast removable solvent
additives in the CB host solvent. At a thickness level of 100 nm
and D/A ratio of 1 : 1.5, CBE, CBA, and CBK gave PCEs between
9.12% and 9.66% while for a D/A ratio of 1 : 2, very limited
changing of PCE between 9.51% and 9.55% was observed.
Relative to CBA, the new additives CBE and CBK further chal-
lenge the lower and the higher bp. limits when used as effective
fast removable solvent additives. It should be noted that the bp.
for CBE is very close to the 180
C for o-dichlorobenzene (DCB),
a common solvent that has been widely used in the fabrication
of active layers. It was also found that a D/A ratio of 1 : 2 is
benecial for device performances of thicker active layers. For
230 nm thick active layers, CBE, CBA, and CBK afforded PCEs of
10.12%, 9.90%, and 9.27%, respectively, well demonstrating the
advantage of low bp. solvent additives in vacuum drying-free
processing of thick active layers. It is worth noting that
several CB/DIO-processed active layers of 100 nm thickness
have shown top PCEs over 13%.9,41 Our fast removable solvent
additive strategy would be a possible choice to upgrade some
high efficiency active layer materials to a more roll-to-roll
compatible level.
Results and discussion
In order to evaluate the photovoltaic performances of the PTB7-
Th:PC71BM active layers fabricated with CBE, CBA, and CBK as
the fast removable solvent additives in the CB host solvent, we
rst selected a D/A ratio of 1 : 1.5 for the active layers. It should
be noted that the blend ratio was the best as initially shown by
the PTB7:PC71BM based PSCs and then was widely utilized in
many reports for the PTB7-Th:PC71BM based PSCs. The device
conguration for the PTB7-Th based BHJ PSCs in this study is
ITO/PEDOT:PSS/active layer/PFN/Al, where an alcohol-soluble
polymer PFN lm (5 nm)50 is the electron selective layer for
the Al cathode. With a PTB7-Th concentration of 10 mg mL1
(or total concentration of 25 mg mL1) in the PTB7-Th:PC71BM
¼ 1 : 1.5 blend solution, 100 nm thick PTB7-Th:PC71BM active
layers could be obtained via spin-coating at 1400 rpm for 2 min.
Generally, the blend lms during spin-coating in the rst 30 s
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already displayed a slightly brownish-red color, very close to
a fully dried state, and then we further rotated the lms for
another 1.5 min to give fully solidied lms. This was
conrmed by immediate IR measurements of the spin-coated
blend lms (Fig. S1–S3 in the ESI†), which did not contain
any signals from CB and the solvent additives. It should be
noted that, on a roll-to-roll line, short-time blowing to the newly
developed blend lm may be needed to fully remove the solvent
and additive, due to lacking forced convection of the spin-
coating process. Relatively, among the three additives, CBE
with a bp. already close to the common solvent DCB may be the
best choice. Without the additional vacuum drying of the active
layers as applied for the CB/DIO case, the PFN layer was
subsequently coated and then started the Al cathode deposi-
tion. The measurements of the PSCs were carried out under
illumination of AM1.5G simulated solar light at 100 mW cm2.
The photovoltaic parameters are summarized in Table 1.
As a comparison, PSCs based on active layers without
a solvent additive were fabricated. The pure CB-processed PTB7-
Th:PC71BM ¼ 1 : 1.5 blend lm of 100 nm thickness exhibited
an open-circuit voltage (Voc) of 0.82 V, a Jsc of 10.08 mA cm2,
and a ll factor (FF) of 53.17%, corresponding to a PCE of
4.71%. With a 3% content of CBE in CB, device performances
were obviously improved. The PSC device showed an almost
comparable Voc of 0.81 V, but a largely elevated Jsc of 16.23 mA
cm2 and FF of 73.48%, giving a remarkably increased PCE of
9.66%. The results suggest that a solvent additive is quite
necessary to achieve a high performance PTB7-Th:PC71BM
active layer. PCS devices with the same 3% content for CBA and
CBK as the fast removable solvent additives were also
compared. The PSCs with the three additives showed similar J–V
curves (Fig. 2a), also with comparable curves for external
quantum efficiency (EQE) (Fig. 2b). The calculated PCEs for the
CBA- and CBK-processed PTB7-Th:PC71BM active layers are
9.43% and 9.12%, respectively. The integrated Jsc values based
on the EQE curves are 16.14, 16.01, and 15.90 mA cm2 for the
CBE-, CBA-, and CBK-processed active layers, respectively,
showing very small spectral mismatch less than 1%. The results
demonstrate that using the fast removable solvent additives can
supply PTB7-Th:PC71BM based PSCs with good PCEs, almost
comparable to that achieved with the high bp. DIO. However,
using a fast removable solvent additive can omit the vacuum
drying process of the active layers, supplying more compatible
processing to the roll-to-roll printing.
TEM images of PTB7-Th:PC71BM ¼ 1 : 1.5 blend lms
fabricated without and with the fast removable solvent additives
are shown in Fig. 2c. Without a solvent additive, large fullerene
agglomerates with sizes up to the 200 nm level could be found
from the blend lm. The severe agglomeration will deteriorate
the formation of a bicontinuous interpenetration network that
can result in decreased donor/acceptor interfaces (poor charge
separations) and unbalanced carrier transports (bimolecular
recombinations), nally giving a low Jsc of 10.08 mA cm2 and
FF of 53.17%. Similar observations were widely reported previ-
ously.47,49 The TEM images of the PTB7-Th:PC71BM ¼ 1 : 1.5
blend lms fabricated with the three fast removable solvent
additives are almost comparable. The fullerene agglomerations
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Table 1 Photovoltaic performances of PTB7-Th:PC71BM active layers with D/A ratios of 1 : 1.5 and 1 : 2 fabricated with the fast removable solvent
additives without a vacuum drying process

D/A ratio Additive Content (%) Thickness (nm) Voc (V) Jsc (mA cm2) FF (%) PCEa (%)

1 : 1.5 No 0 100 0.82 10.08 53.17 4.71 (4.66)

CBE 3 100 0.81 16.23 73.48 9.66 (9.57)
CBA 3 100 0.82 16.08 71.54 9.43 (9.39)
CBK 3 100 0.81 15.78 71.31 9.12 (9.11)
CBE 5 100 0.81 16.14 73.12 9.56 (9.53)
CBA 5 100 0.82 16.24 70.54 9.39 (9.37)
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CBK 5 100 0.81 15.86 70.88 9.10 (9.08)

CBE 3 200 0.79 18.87 60.74 9.05 (9.02)
CBA 3 200 0.80 18.64 61.52 9.17 (9.05)
CBK 3 200 0.79 18.72 59.28 8.77 (8.72)
1:2 No 0 110 0.82 10.70 58.70 5.15 (5.04)
No 0 230 0.81 10.09 49.23 4.02 (3.89)
CBE 3 110 0.80 16.03 74.17 9.51 (9.45)
3 230 0.82 19.49 63.28 10.12 (10.03)
3 250 0.81 19.54 63.27 10.02 (9.96)
3 300 0.79 18.83 61.06 9.08 (8.94)
CBA 3 110 0.81 15.93 74.05 9.55 (9.48)
3 230 0.80 19.32 64.06 9.90 (9.85)
CBK 3 110 0.82 15.90 73.08 9.53 (9.46)
3 230 0.78 19.38 61.31 9.27 (9.20)
a
The averaged values are in parentheses (over 10 devices).

do not appear at all, corresponding to good phase separations of
the donor polymer and the fullerene acceptor. Thus the PSCs
can display good PCEs between 9.12% and 9.66%, due to
a much higher Jsc of around 16 mA cm2 and higher FF of more
than 71%.
It should be noted that the bp. difference (DTbp.) between
CBE and CB is as low as 63
C, further challenging the low DTbp.
limit of 80
C as reported for the CB/CBA case previously49 while
the corresponding DTbp. for CBK is 98
C, also challenging the
upper limit for a solvent additive with fast removable

Fig. 2 (a) J–V curves of PSCs based on PTB7-Th:PC71BM ¼ 1 : 1.5 blend films of 100 nm thickness fabricated without and with the fast removable
solvent additives (3% content in CB) and (b) EQE curves of the PSCs with the three solvent additives. (c) TEM images of PTB7-Th:PC71BM ¼ 1 : 1.5
blend films of 100 nm thickness fabricated without and with the fast removable solvent additives (3% content in CB).

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properties. We want to point out the advantage of challenging
the lower limit: a faster drying of the active layer is helpful for
more intimate equipment arrangement of a roll-to-roll line.
Also, further challenging of the upper limit would provide
a chance to nd more candidates that may be suitable for more
active layer materials. We have noticed that diphenyl ether
(DPE)16 and 1-chloronaphthalene (CN),15 two oen used solvent
additives, possess bp. values of 260
C; however, their poten-
tials as effective fast removable solvent additives are still
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unknown.
A higher content of 5% of the fast removable solvent addi-
tives in CB was also investigated. The CBE-, CBA-, and CBK-
processed PSCs displayed PCEs of 9.56%, 9.39%, and 9.10%,
respectively. The very limited variations of the three photovol-
taic parameters along the changing of the additive content
indicate that the 3% content for each additive is already suffi-
cient to modify the BHJ morphology. In the meantime, the
much higher content of 5% for each additive also does not give
any adverse effect. It should be noted that among the three
solvent additives, the 3% and 5% contents of CBE all afford
PSCs with the highest PCEs (>9.5%) and the highest FF (>73%).
The results suggest that CBE with the smallest DTbp. of 63
C is
optimal for a 100 nm thick active layer among the three
additives.
To evaluate the thickness tolerance of the PTB7-Th:PC71BM
active layers being processed with the three solvent additives,
we further investigated the photovoltaic performances of
thicker blend lms. Also with a D/A of 1 : 1.5 and a PTB7-Th
concentration of 10 mg mL1, 200 nm thick PTB7-Th:PC71BM
active layers were spin-coated at a lower rate of 460 rpm. In the
PSCs, the thicker active layers can contribute a higher Jsc of
around 18.7 mA cm2 due to more effective harvesting of solar
light, but resulting in a lower FF of about 60%. For the overall
effect, the CBE-, CBA-, and CBK-processed PSCs exhibit PCEs of
9.05%, 9.17%, and 8.77%, respectively. Although the efficien-
cies are all lower than those of PSCs with the corresponding
100 nm thick active layers, the PCE decrease extents of the
devices are quite limited, only between 2.8% and 6.3%. The
results suggest that using a fast removable solvent additive not
only supplies the convenience for roll-to-roll processing of PSCs,
but also shows potential to improve the thickness tolerance of
the PTB7-Th:PC71BM active layer.
A thicker active layer (e.g. 200 nm) showing lower efficiency is
a restriction to dene a large processing window as highly
efficient as possible. To our delight, it was found that the fast
removable solvent additive strategy demonstrated in this work
could reverse the tendency between the PCE and active layer
thickness when a D/A ratio of 1 : 2 was selected (Table 1). With
a D/A ratio of 1 : 2 and a PTB7-Th concentration of 10 mg mL1
(or total concentration of 30 mg mL1), the former spin-coating
conditions at 1400 and 460 rpm could afford slightly thicker
PTB7-Th:PC71BM active layers of 110 and 230 nm, respectively.
In the absence of a solvent additive, a D/A ratio of 1 : 2 also gave
a poor PCE of 5.15% for the 110 nm thick active layer and
further reduced the efficiency to 4.02% for the thicker active
layer of 230 nm. With 3% CBE as the solvent additive, the
110 nm thick active layer could show a nearly constant PCE of
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9.51%, based on a Voc of 0.80 V, Jsc of 16.03 mA cm2, and FF of
74.17%. Interestingly, the thicker active layer of 230 nm affor-
ded a higher PCE of 10.12%, based on a Voc of 0.82 V, Jsc of 19.49
mA cm2, and FF of 63.28%. Thus the higher efficiency for the
230 nm thick active layer results from the increased Jsc. The J–V
curves of the two devices are shown in Fig. 3a. The Jsc increase of
21.6% can exceed the decreasing percentage of 17.2% for the FF
if compared with the thin active layer, nally giving a higher
efficiency for the 230 nm thick active layer. The EQE curves for
PSCs based on the 110 and 230 nm active layers are shown in
Fig. 3b, and the 230 nm thick active layer can generate a largely
enhanced photo-response. The integrated Jsc for the two active
layers is 15.68 and 18.58 mA cm2, respectively, corresponding
to spectral mismatches of 2% and 5%.
With a D/A ratio of 1 : 2, the PCE of 10.12% achieved for the
CBE-processed 230 nm thick blend lm corresponds to a Jsc of
19.49 mA cm2 and FF of 63.28%, all higher than the Jsc of 18.87
mA cm2 and FF of 60.74% for the CBE-processed 200 nm thick
blend lm based on a D/A ratio of 1 : 1.5. The results indicate
that a D/A ratio of 1 : 2 is better for PTB7-Th:PC71BM based
thick-lm PSC devices when the low bp. CBE is used as the
solvent additive. However, traditional AFM and TEM observa-
tions did not nd obvious morphological differences between
the two blend lms. Previous reports indicated that transient
photovoltage (TPV) and transient photocurrent (TPC)
measurements were useful to compare charge recombination
dynamics and the charge extraction process, respectively, as
alternative proof.51 Thus the charge recombination dynamics
and the charge extraction process in the two devices were
compared. The TPV analysis is shown in Fig. 4a. The PSC device
with a D/A ratio of 1 : 1.5 showed a charge carrier lifetime of
4.49 ms. For a D/A ratio of 1 : 2, the lifetime was increased to 7.98
ms. The longer carrier lifetime was consistent with its higher FF
in the PSC device, indicating a reduced recombination process.
The TPC results are shown in Fig. 4b. For a D/A ratio of 1 : 1.5,
the charge extraction time of the device was 0.377 ms. For the
device with a D/A ratio of 1 : 2, the charge extraction time of the
device was decreased to 0.316 ms, meaning a faster extraction
rate. Relative to the D/A ratio of 1 : 1.5, the increased charge
extraction rate and longer carrier lifetime caused by the active
layer with a D/A ratio of 1 : 2 should be the major reasons that
contributed to its higher FF and Jsc, leading to higher PCE in
PSCs.
With a D/A ratio of 1 : 2, using CBE as the fast removable
solvent additive successfully reverses the PCE decreasing
tendency for thicker blend lm. This would be quite helpful for
the enlargement of a high efficiency processing window for
PTB7-Th:PC71BM active layers. Thicker active layers of 250 and
300 nm were also investigated, which were obtained by spin-
coating at 440 rpm with a blend solution of 10 mg mL1 poly-
mer concentration and 420 rpm with a blend solution of 11 mg
mL1 polymer concentration, respectively. With a CBE-
processed 250 nm thick active layer, the PSC device also
exhibited a high PCE of 10.02%, with a Voc of 0.81 V, Jsc of 19.54
mA cm2, and FF of 63.27%. On further increasing the active
layer thickness to 300 nm, the PSC device still displayed a good
PCE of 9.08%. It should be noted that the very thick active layer
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Fig. 3 (a) J–V and (b) EQE curves of PSCs based on the CBE-processed PTB7-Th:PC71BM ¼ 1 : 2 blend films of 110 and 230 nm thickness.
can still contribute a FF over 61%, a value hardly achieved by
other solvent additives. Thus the CBE-processed PTB7-
Th:PC71BM active layers can display PCEs more than 9% in the
thickness range from 100 to 300 nm, demonstrating a largely
improved thickness tolerance (Fig. 5a).
The hole and electron mobilities (mh and me) of the 3% CBE-
processed PTB7-Th:PC71BM ¼ 1 : 2 active layers with different
thickness were obtained from space charge limited current
(SCLC) measurements of hole-only and electron-only devices.
The CBE-processed thin active layer of 110 nm shows a mh and
me of 0.93  103 and 3.1  103 cm2 V1 s1, respectively,
giving a me/mh of 3.3. Changing the thickness from 110 to
300 nm thickness alters the mh of the active layers with limited
extent (Fig. 5b). For the thicker 230, 250, and 300 nm active
layers, the me values show a continuous increase up to 8.5 
103 cm2 V1 s1. The calculated me/mh values are 8.6, 8.4, and
9.6, respectively, showing enlarged deviations from balanced
hole and electron transports. This can be reected by the overall
tendency of decreasing FFs in PSCs based on an active layer
Fig. 4 (a) Transient photovoltage (TPV) and (b) transient photocurrent (TPC) of CBE-processed thick-film solar cells based on different D/A
ratios.
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thickness from 110 to 300 nm. In a previous report for thicker
PTB7:PC71BM blend lms, a larger unbalanced extent due to
decreasing of me causes monotonous decreasing of PCE.49
However, relative to the thin lm (110 nm) in this study, a much
higher Jsc of 19.49 and 19.54 mA cm2 could be achieved for the
CBE-processed 230 and 250 nm thick PTB7-Th:PC71BM active
layers, respectively. Therefore, more sufficient light harvesting
with a thicker CBE-processed active layer would be valuable,
which compensated FF decreasing and nally gave higher PCEs.
With a D/A ratio of 1 : 2, the as-cast PTB7-Th:PC71BM active
layers of 110 and 230 nm all display very poor photovoltaic
performances. However, with CBE as a fast removable solvent
additive, greatly improved efficiency and thickness tolerance
have been demonstrated. The results suggest that the CBE-
processed PTB7-Th:PC71BM thin and thick blend lms should
possess obviously improved nanoscale morphologies. AFM and
TEM measurements were carried out to compare PTB7-
Th:PC71BM thin and thick blend lms without and with CBE as
the solvent additive. As shown in Fig. 6a, the 110 nm thick blend
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Fig. 5 (a) PCE and (b) carrier mobility as a function of the active layer thickness for the CBE-processed PTB7-Th:PC71BM ¼ 1 : 2 blend films.

lm processed without an additive shows a large root-mean-
square (RMS) roughness of 3.48 nm. For the thicker blend
lm of 230 nm without an additive, the surface roughness is
further increased to 4.02 nm (Fig. 6b). When using 3% CBE as
the solvent additive, the 110 and 230 nm thick blend lms
exhibit very low RMS values of 1.04 and 1.09 nm, respectively
(Fig. 6c and d). Thus largely improved surface morphology can
be achieved in the mean time for the thin and thick active layers
by applying CBE as the solvent additive. For the TEM analysis,
the 110 nm thick blend lm processed without an additive
displays obvious fullerene agglomerations inside the BHJ blend
lm, giving very large phase separation (Fig. 6e). The poor BHJ
morphology results in a very low Jsc of 10.7 mA cm2 and FF of
58.7%. For the thicker blend lm of 230 nm without an additive,
some further enlarged fullerene agglomerates can be found
(Fig. 6f) and the PSC device shows a decreased Jsc of 10.09 mA
cm2 and FF of 49.03%. Thus increasing the active layer
thickness does not help the Jsc at all, suggesting the decreased
interface area between the donor and acceptor phases. There-
fore, in the absence of an additive, using a D/A ratio of 1 : 2 has
no positive effect on the photovoltaic performance. However,
applying CBE as the solvent additive signicantly improves the
phase separations for the both 110 and 230 nm thick active
layers, and fullerene agglomerations can all be greatly sup-
pressed (Fig. 6g and h). Therefore, CBE-processed PTB7-
Th:PC71BM active layers of 110 and 230 nm can show high PCEs
of 9.51% and 10.12%, respectively. Notably, increasing lm
thickness from 110 to 230 nm gives a Jsc increase of 21.6% that
can exceed the FF decreasing percentage of 17.2%. The overall
effect can give a higher PCE for the thicker active layer, from
which the thickness tolerance of the PTB7-Th:PC71BM active
layer can be improved.
With a D/A ratio of 1 : 2, PSC devices based on thin and
thicker active layers processed with CBA and CBK, two fast

Fig. 6 (a–d) AFM images (5  5 mm2) for additive-free (a) 110 nm and (b) 230 nm and CBE-processed (c) 110 nm and (d) 230 nm PTB7-Th:PC71BM
¼ 1 : 2 blend films. (e–h) TEM images for additive-free (e) 110 nm and (f) 230 nm and CBE-processed (g) 110 nm and (h) 230 nm PTB7-Th:PC71BM
¼ 1 : 2 blend films.

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removable solvent additives with higher bp. than CBE, were
investigated for comparison. The CBA- and CBK-processed
110 nm thick blend lms showed PCEs of 9.55% and 9.53%,
respectively, almost identical to the 9.51% for the thin active
layer with CBE. There is negligible difference among the three
additives for the thin active layers. For the CBA- and CBK-
processed thicker active layers of 230 nm, PSC devices exhibi-
ted PCEs of 9.90% and 9.27%, respectively. The efficiencies are
obviously higher than those of DIO-processed thick active layers
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obtained by conventional spin-coating in previous reports,34,45
well demonstrating the advantage of low bp. solvent additives.
The AFM and TEM images of the CBA- and CBK-processed
230 nm thick blend lms are shown in Fig. S4 in the ESI.†
The PTB7-Th:PC71BM blend lms of 230 nm thickness could
display fairly smooth surfaces and greatly suppressed fullerene
agglomeration.
Conclusions
In summary, three fast removable solvent additives CBE, CBA,
and CBK with low bp. of 195, 212, and 230
C, respectively, were
applied for BHJ morphology control of PTB7-Th:PC71BM active
layers. Photovoltaic performances based on D/A ratios of 1 : 1.5
and 1 : 2 were compared. It was found that without a vacuum
drying process CBE, CBA, and CBK could work well as fast
removable solvent additives in the CB host solvent, and thus the
new additives CBE and CBK could further challenge the lower
and upper bp. limits. At a thickness level of 100 nm and D/A
ratio of 1 : 1.5, CBE, CBA, and CBK gave PCEs between 9.12%
and 9.66% while for a D/A ratio of 1 : 2 very limited changing of
PCE between 9.51% and 9.55% was observed. It was also found
that a D/A ratio of 1 : 2 is more benecial for the device
performances of thicker active layers, and CBE-, CBA-, and CBK-
processed 230 nm thick active layers afforded PCEs of 10.12%,
9.90%, and 9.27%, respectively, well demonstrating the advan-
tage of low bp. solvent additives in vacuum drying-free pro-
cessing of thick active layers. More importantly, from 100 to
300 nm, the CBE-processed active layers can establish a thick-
ness window with PCE > 9%, especially with the 10.12% PCE at
230 nm thickness. Relative to the average thickness of the
100 nm level, an optimal PCE at the 200 nm level is bene-
cial for dening a larger processing window that can help pin-
hole free active layers at high speed. Therefore the fast remov-
able solvent additive strategy as demonstrated in this work can
show big potential for vacuum drying-free fabrication of the
PTB7-Th based active layers with improved thickness tolerance,
thus facilitating future application.
Conflicts of interest
There are no competing interests.
Acknowledgements
We acknowledge the nancial support of the National Natural
Science Foundation of China (U1401244, 21225418, 51521002,
and 91633301), the National Basic Research Program of China
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(973 program 2014CB643505 and 2013CB834705), the Natural
Science Foundation of Guangdong Province (2016A030312002),
and GDUPS (2013).
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