Article

pubs.acs.org/Macromolecules

Soft Poly(butyl acrylate) Side Chains toward Intrinsically Stretchable

Polymeric Semiconductors for Field-Effect Transistor Applications
Han-Fang Wen,† Hung-Chin Wu,*,‡ Junko Aimi,∥ Chih-Chien Hung,§ Yun-Chi Chiang,‡
Chi-Ching Kuo,*,† and Wen-Chang Chen*,‡
†
Institute of Organic and Polymeric Materials, National Taipei University of Technology, Taipei 10608, Taiwan
‡
Department of Chemical Engineering and §Institute of Polymer Science and Engineering, National Taiwan University, Taipei 10617,
Taiwan
∥
Molecular Design & Function Group, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047,
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Japan
*
S Supporting Information
Downloaded via UNIV DE GUADALAJARA on October 26, 2022 at 21:33:01 (UTC).

ABSTRACT: Poly(butyl acrylate) (PBA) side chain equipped isoindigo-

bithiophene (II2T) conjugated polymers have been designed and synthesized
for stretchable electronic applications. The PBA segment possesses low glass
transition temperature and high softness, offering a great opportunity to improve
the mechanical property of semiconducting polymer thin films that typically
contain lots of rigid conjugated rings. Polymers with 0, 5, 10, 20 and 100% of PBA
side chains, named PII2T, PII2T-PBA5, PII2T-PBA10, PII2T-PBA20, and
PII2T-PBA100, were explored, and their polymer properties, surface morphology,
electrical characteristics, and strain-dependent performance were investigated
systematically. The series polymers showed a charge carrier mobility of 0.06−0.8
cm2 V−1 s−1 with an on/off current ratio over 105 dependent on different amounts
of PBA chains as probed using a top-contact transistor device. Moreover, we can
still achieve a mobility higher than 0.2 cm2 V−1 s−1 even if 10% of PBA side chains
were added (i.e., PII2T-PBA10). Such PII2T-PBA polymers, more attractive, exhibited superior thin film ductility with a low
tensile modulus down to 0.12 GPa (PII2T-PBA20) due to the soft PBA side chain. The more PBA segment was incroporated,
the lower modulus was reached. The mobility performance, at the same time, remained approximately 0.08 cm2 V−1 s−1 based on
PII2T-PBA10 films even under a 60% strain and could be simultaneously operated over 400 stretching/releasing cycles without
significant electrical degradations. The above results suggest that the rational design of soft PBA side chains provides a great
potential for next-generation soft and wearable electronic applications.

■ INTRODUCTION
Semiconducting polymers have been developed rationally in
recent years with their merits of low-cost processing, tunable
chemical structure, superior charge transport, and good
mechanical tolerance.1−4 Thin films based on such polymeric
semiconductors, additionally, are innovated to be deformable
and stretchable, leading to next-generation wearable electronics
that potentially can be biocompatible and possess distinct
functionalities with our body movement.5,6 Active layers in
stretchable field-effect transistors (FETs),7−12 light-emitting
diodes,13−15 photovoltaics,16−18 or digital data storage memo-
ries19−22 have been realized using semiconducting polymers by
several chemical or physical approaches, such as buckled and
wrinkled structures,23 polymer blends,24 and dynamic bonding
functionalization.8 Semiconducting layers that can be intrinsi-
cally stretched, in addition, are important to be created and
enable large functional area, uniform characteristics, and simple
processing integration under strain. However, it is still
challenging to maintain the electrical stability and durability
when applying forces on such intrinsically strained active layers.
Designing a semiconducting polymer system that possesses not
only superior electrical performance but also high thin film
ductility and stretchability is crucial for practical applications.
Side chain engineering has been focused on the field of
polymeric electronics very recently since it can greatly enhance
the device performances.25 Rational side chain design, more-
over, can also manipulate the solution processability, solid state
molecular stacking, and thin film morphology. From the view of
soft electronics, we should be able to achieve a flexible or
stretchable polymeric semiconducting active layer by control-
ling the interchain packing interaction and surface morphology
based on the side chain substituents. Several polymer side chain
modifications have been explored for the intrinsically
stretchable device applications, especially for the FETs. For
example, our group established an isoindigo-based donor−
acceptor polymer bearing long, branched carbosilane side
Received: April 26, 2017
Revised: June 13, 2017
Published: June 23, 2017

© 2017 American Chemical Society 4982 DOI: 10.1021/acs.macromol.7b00860

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Macromolecules
Scheme 1. Synthetic Route on Synthesizing the Studied Polymeric Semiconductors
chains, and a charge carrier mobility up to 1 cm2 V−1 s−1 was
reported even at strains as large as 60%;26 Bao and co-workers,
on the other hand, developed a diketopyrrolopyrrole-based
polymer with cross-linkable side chains, leading to a stretchable
thin film that could be stabilized under a 150% strain, and a
steady mobility ∼0.40 cm2 V−1 s−1 was obtained after 500
strain-and-release cycles of 20% strain.9 Although good charge
transport ability was obtained, we still need to involve new
synthetic pathway to customize specific side chains. It would be
efficient if a common soft and deformable component can be
directly incorporate into the conjugated polymer system,
facilitating superior mechanical properties in film state with
appropriate charge mobility.
Poly(butyl acrylate) (PBA) is an elastic compound with a
glass transition temperature of approximately −54 °C, which is
far below compared to the room temperature. We herein
introduce such soft PBA segment with varying amount onto
isoindigo-bithiophene backbone as side chains through random
copolymerization (Scheme 1). The polymer properties, surface
morphologies, molecular packing structures, electrical charac-
teristics, and mechanical endurances are investigated system-
atically. Linear siloxane-terminated side chain is used to
improve the electrical performance and act as a reference
polymer. A high modulus of 0.8 GPa is probed for the polymer
thin film based on only siloxane side chain. Once the PBA side
chain incorporated (i.e., 20%), the thin film tensile modulus can
be lowered to 0.12 GPa, demonstrating that the thin film
ductility and deformability can be efficiently improved by
directly adding soft and elastic component as polymer side
chains. This is the first example using such low glass transition
temperature element on polymer side chains for intrinsically
stretchable transistors, to the best of our knowledge. Stable and
reliable charge transport characteristics, more importantly, are
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obtained under stretching. A mobility of 0.08−0.1 cm2 V−1 s−1
was achieved under 0−60% strain levels, and such value can be
maintained under 400 simultaneous stretching/releasing cycles,
indicating our newly designed polymers via side chain
engineering possess great potentials for future electronic
applications.
■ EXPERIMENTAL SECTION
Materials. Magnesium sulfate, potassium carbonate, 6-bromosatin,
6-bromooxindole, 8-bromo-1-octene, trimethyltin chloride,
1,1,3,3,5,5,5-heptamethyltrisiloxane, 5,5′-dibromo-2,2′-bithiophene,
Karstedt’s catalyst, tri(o-tolyl)phosphine, tris(dibenzylideneacetone)-
dipalladium(0), common organic solvents (tetrahydrofuran, toluene,
acetic acid, and dimethylformamide) for synthesis, and anhydrous
solvents (i.e., chloroform) for device fabrication were purchased from
Aldrich (St. Louis, MO) and used as received. 5,5′-Bis-
(trimethylstannyl)-2,2′-bithiophene (2T)27 and (E)-6,6′-dibromo-
1,1′- bis(8-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)octyl)-[3,3′-biin-
dolinylidene]-2,2′-dione (IID-Si)28−30 were synthesized according to
the reported procedures. The poly(butyl acrylate) (PBA) homopol-
ymer, in addition, was prepared by atom transfer radical polymer-
ization (ATRP).10 The synthetic routes of studied materials with
different amount of PBA side chain are shown in Scheme 1, and the
details of monomer syntheses are summarized in the Supporting
Information.
General Procedures for Polymerization. The general synthetic
procedure to polymerize the studied polymers (PII2T, PII2T-PBA5,
PII2T-PBA10, PII2T-PBA20, and PII2T-PBA100) is described
below: dibromo-isoindigo with siloxane (IID-Si) and PBA (IID-
PBA) side chain, bithoiphene-ditin (2T), tri(o-tolyl)phosphine (16
mol % with respect to 2T), and tris(dibenzylideneacetone)-
dipalladium(0) (2 mol % with respect to 2T) were dissolved in a
microwave vessel using chlorobenzene (5 mL) in a nitrogen-filled
golvebox. A snap cap was then sealed the vessel, and the target
materials were polymerized by Stille coupling reaction at 180 °C for
180 min under the microwave heating. The end-capping process was
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then taken with 2-(tributylstannyl)thiophene and 2-bromothiophene
(both 1.1 equiv with respect to 2T and reacted at 185 °C for 10 min),
and then the mixture was cooled and precipitated into methanol to
form a crude polymer. Such crude polymer was finally purified by
Soxhlet apparatus with methanol, acetone, and hexane to remove the
oligomers and catalyst residues, and the final product was obtained
after drying in a vacuum oven at 40 °C for 16 h.
Synthesis of PII2T. Amounts of 197.30 mg (0.4 mmol) of 2T,
435.00 mg (0.4 mmol) of IID-Si, and 5 mL of chlorobenzene were
used to give a dark blue solid (398 mg, yield: 90%). 1H NMR (400
MHz, CDCl3), δ (ppm): 9.05−9.03 (br, Ar−H), 7.14−7.11 (br, Ar−
H), 6.89 (br, Ar−H), 3.71−3.67 (br, NCH2CH2), 1.39−1.20 (br,
CH2CH2CH2), 0.49−0.39 (br, SiCH3), 0.21−0.10 (br, SiCH3). Anal.
Calcd for [C54H90N2O6S2Si6]: C, 59.40; H, 7.94; N, 2.57; S, 5.87.
Found: C, 59.47; H, 7.68; N, 2.82; S, 5.82. Mn and PDI estimated from
gel permeation chromatography are 216 kDa and 1.7, respectively.
Synthesis of PII2T-PBA5. Amounts of 172.15 mg (0.35 mmol) of
2T, 360.91 mg (0.33 mmol) of IID-Si, 56.32 mg (0.0175 mmol) of
IID-PBA, and 5 mL of chlorobenzene were used to give a dark blue
solid (340 mg, yield 98%). 1H NMR (400 MHz, CDCl3), δ (ppm):
9.05−9.03 (br, Ar−H), 7.14−7.11 (br, Ar−H), 6.89 (br, Ar−H),
4.10−3.90 (br, OCH2CH2), 3.63−3.55 (br, NCH2CH2), 2.49−2.20
(br, CH2CH2CH), 2.10−1.95 (br, CH2CH2CH2), 1.39−1.20 (br,
CH2CH2CH2), 1.13−1.10 (br, CH3CH), 0.90−0.70 (br, CH3CH2),
0.49−0.39 (br, SiCH3), 0.21−0,10 (br, SiCH3). Anal. Calcd for
[C60H96N2O8S2Si6]: C, 59.73; H, 7.97; N, 2.48; S, 5.66. Found: C,
60.12; H, 7.57; N, 2.50; S, 5.66. Mn and PDI estimated from gel
permeation chromatography are 198 kDa and 1.8, respectively.
Synthesis of PII2T-PBA10. Amounts of 172.15 mg (0.35 mmol)
of 2T, 341.91 mg (0.315 mmol) of IID-Si, 112.64 mg (0.035 mmol) of
IID-PBA, and 5 mL of chlorobenzene were used to give a dark blue
solid (335 mg, yield 98%). 1H NMR (400 MHz, CDCl3), δ (ppm):
9.05−9.03 (br, Ar−H), 7.14−7.11 (br, Ar−H), 6.89 (br, Ar−H),
4.10−3.90 (br, OCH2CH2), 3.63−3.55 (br, NCH2CH2), 2.49−2.20
(br, CH2CH2CH), 2.10−1.95 (br, CH2CH2CH2), 1.39−1.20 (br,
CH2CH2CH2), 1.13−1.10 (br, CH3CH), 0.90−0.70 (br, CH3CH2),
0.49−0.39 (br, SiCH3), 0.21−0,10 (br, SiCH3). Anal. Calcd for
[C66H105N2O10S2Si5]: C, 60.05; H, 8.01; N, 2.40; S, 5.48. Found: C,
60.38; H, 7.74; N, 2.44; S, 5.37. Mn and PDI estimated from gel
permeation chromatography are 133 kDa and 2.5, respectively.
Synthesis of PII2T-PBA20. Amounts of 172.15 mg (0.35 mmol)
of 2T, 303.92 mg (0.28 mmol) of IID-Si, 225.27 mg (0.07 mmol) of
IID-PBA, and 5 mL of chlorobenzene were used to give a dark blue
solid (213 mg, yield 74%). 1H NMR (400 MHz, CDCl3), δ (ppm):
9.05−9.03 (br, Ar−H), 7.14−7.11 (br, Ar−H), 6.89 (br, Ar−H),
4.10−3.90 (br, OCH2CH2), 3.63−3.55 (br, NCH2CH2), 2.49−2.20
(br, CH2CH2CH), 2.10−1.95 (br, CH2CH2CH2), 1.39−1.20 (br,
CH2CH2CH2), 1.13−1.10 (br, CH3CH), 0.90−0.70 (br, CH3CH2),
0.49−0.39 (br, SiCH3), 0.21−0,10 (br, SiCH3). Anal. Calcd for
[C79H124N2O14S2Si5]: C, 60.69; H, 8.08; N, 2.23; S, 5.09. Found: C,
61.40; H, 7.78; N, 2.11; S, 4.79. Mn and PDI estimated from gel
permeation chromatography are 49.6 kDa and 2.6, respectively.
Synthesis of PII2T-PBA100. Amounts of 191.82 mg (0.39 mmol)
of 2T, 820.00 mg (0.39 mmol) of IID-PBA, and 5 mL of
chlorobenzene were used to give a dark blue solid (161 mg, yield:
16%). 1H NMR (400 MHz, CDCl3), δ (ppm): 9.05−9.03 (br, Ar−H),
7.14−7.11 (br, Ar−H), 6.89 (br, Ar−H), 4.10−3.90 (br, OCH2CH2),
2.49−2.20 (br, CH2CH2CH), 2.10−1.95 (br, CH2CH2CH2), 1.39−
1.20 (br, CH2CH2CH2), 1.13−1.10 (br, CH3CH), 0.90−0.70 (br,
CH3CH2). Anal. Calcd for [C136H206N2O34S2]: C, 65.94; H, 8.38; N,
1.13. Found: C, 66.53; H, 7.10; N, 1.75. Mn and PDI estimated from
gel permeation chromatography are 6.9 kDa and 1.3, respectively.
Fabrication of Field-Effect Transistors with Pristine Polymer
Thin Films. A bottom-gate/top-contact device configuration was used
to explore field-effect transistors (FETs) using the studied polymers.
The gate dielectric layer was a 300 nm SiO2 layer (capacitance per unit
area = 10 nF cm−2) on highly n-doped Si (100) substrates. An
octadecyltrimethoxysilane (OTS) self-assembled monolayer was
modified onto the SiO2 layer according to the reported method to
improve the charge carrier performance.31 For the active layer, our
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PII2T-PBA polymers were dissolved in chloroform (3−5 mg mL−1) at
60 °C for 2 h first, and then the polymer thin films were deposited
onto the dielectric layer through spin-coating method at 1000 rpm for
60 s. An annealing process (200 °C under vacuum for 1 h),
additionally, was introduced to enhance the FET performance. Finally,
the top-contact source and drain electrodes (100 nm thick Au) were
defined by a regular shadow mask with a 50 μm channel length (L)
and a 1000 μm channel width (W).
Preparation of Field-Effect Transistors with Stretched
Polymer Films. To investigate the charge transport characteristics
of these PII2T-PBA polymer-based thin films under a distinct strain
ratio (0−100%). The polymer films were also deposited on an OTS-
modified SiO2/Si substrate via spin-coating and were annealed at 200
°C for 1 h. Next, such films were transferred onto an elastomeric
poly(dimethylsiloxane) (PDMS) (base: cross-linker = 20:1 w/w) slab.
Tensile strains (0−100%) were applied to the polymer/PDMS matrix,
so that the PII2T-PBA thin films were stretched along with the PDMS
slab for any distinct stretching levels. The stretched thin films,
afterward, were transferred back to a 300 nm SiO2-equipped Si
substrate to act as the active layer in FET devices.26,32 Similarly, the
top-contact source/drain Au contacts were defined by the regular
shadow mask with 50 μm channel length (L) and 1000 μm channel
width (W). It is worth to noting that the direction of Au electrodes
could be designed in parallel or perpendicular with respect to the
strain direction.
■
RESULTS AND DISCUSSION
Polymer Characterization. The studied isoindigo-bithio-
phene polymers were designed based on a linear siloxane-
terminated side chain (i.e., PII2T), which can facilitate
condense interchain packing structure and superior charge
transporting.29 Polymers with 5−20% of PBA side chain
(respect to siloxane side chain), in addition, were explored to
improve the mechanical endurance, named PII2T-PBA5,
PII2T-PBA10, and PII2T-PBA20. Note that the polymer
equipped only PBA side chain (i.e., PII2T-PBA100) was also
synthesized as a comparison. All the studied polymers were
successfully polymerized through the Stille coupling reaction
under a microwave heating (Scheme 1). 1H NMR was used to
confirm the chemical structures of the PII2T-PBA polymers, as
depictied in Figure 1 and Figure S2. The signal at
approximately 9.2 ppm (peak a) is attributed to the aromatic
proton of the benzene ring on isoindigo, and the signals in the
range of 6.8−7.4 ppm (peaks b−e) are assigned to the protons
on conjugated polymer backbone. For the protrons on side
chains, peaks g (ca. 3.8 ppm) and j (ca. 0−0.21 ppm) belong to
siloxane-terminated chains, while peaks f (ca. 4.0 ppm), h (ca.
2.20−2.49 ppm), and i (ca. 0.70−1.13 ppm) are represented for
PBA chains. The peak intensity changes of both siloxane and
PBA-related proton signals are clearly observed with the
manipulation of siloxane-to-PBA side chain ratio. It is worth
noting that the estimated integration values of the 1H NMR
signals for the aliphatic and aromatic protons are consistent
with the proposed polymer structures, and the elemental
analyses show a good agreement with the theoretical carbon,
hydrogen, nitrogen, and sulfur content, demonstrating that our
target semiconducting polymers were successfully synthesized.
The studied polymers (PII2T, PII2T-PBA5, PII2T-PBA10,
and PII2T-PBA20) possess the number-averaged molecular
weight in a range of 49.6−216 kDa with polydispersities
between 1.7 and 2.6, which are estimated from the size
exclusion chromatographic (SEC) measurement using tetrahy-
drofuran as eluent. Note that PII2T-PBA100 shows a relatively
low molecular weight of 6.9 kDa, owing to the bulky PBA side
chains diminishing the reactivity in the polymerization. The
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Figure 1. (a) 1H NMR spectrum of PII2T-PBA10 in CDCl3. (b)
TGA curves and (c) solid state UV−vis absorption spectra of the
studied polymers.
studied PII2T-PBA polymers can be generally dissolved in
common organic solvents (e.g., chloroform, chlorobenzene, and
tetrahydrofuran), and the polymer solubility is improved with
the increase of PBA chain content. The enhanced solubility
indicates that the incorporation of PBA chains enlarges the
polymer side chain bulkiness and weakens the interchain
interaction between the polymer backbones in organic
solvents.33 The strength of interaction between polymer chains,
moreover, is also highly related to the ductility and
deformability of polymer thin film, suggesting the mechanical
property of the semiconducting polymers in film state can be
also manipulated by tuning the side chain composition of the
copolymers.
The thermal decomposition temperature (Td, 5% weight
loss), based on the thermogravimetric analysis (TGA; Figure
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1b), of PII2T and PII2T-PBA100 was probed at approximately
295 and 396 °C, respectively. The bulky PBA side group is
more easily decomposed and vaporized under heating.
Although the Td decreased with increased PBA ratio, polymers
containing 5−20% PBA side chains (PII2T-PBA5, PII2T-
PBA10, and PII2T-PBA20) still possess stable thermal stability
with a Td higher than 350 °C. The thermal transitions, in
addition, are investigated using differential scanning calorimetry
(DSC; Figure S3a,b). There is no thermal transition that could
be observed under a scanning temperature from 0 to 260 °C
(Figure S3a) due to the conjugated polymer backbone being
rigid. More interestingly, the glass transition temperature (Tg)
can be detected in low temperature range (i.e., below −20 °C)
(Figure S3b). The PBA homopolymer presented a low Tg of
−57 °C. As inserting PBA onto the II2T polymer backbone as
side chains, we could observe a Tg at approximately −30 °C
when the amount of PBA side chain was larger than 10%. This
thermal transition is mainly contributed by the PBA side chain,
which provides the opportunity to reduce the overall polymer
thin film modulus and improve the mechanical deformability.
Optical and Electrochemical Properties. The solid state
UV−vis absorption spectra were recorded in order to realize
the effects of PBA side chains on the optoelectronic properties
of studied PII2T-PBA polymers, as depicted in Figure 1c. Two
distingushable absorption bands could be obtained for our
studied polymers, which is typical for the isoindigo-based
polymers:29,30,34 (1) the absorption located at approximately
410 nm is associated with the π−π* transitions, while (2) the
broad band in a range from 500 to 800 nm is facilitated by the
intramolecular charge transfer (ICT) between the electron-
donating thiophene rings and electron-accepting isoindigo
moieties on the polymer main chain. The relative intensity of
the vibrational peak at ∼720 nm, more interestingly, is slightly
reduced as the increasing the content of PBA side chain from 0
to 20%. This is mainly due to the soft and bulky PBA groups
leading to weaker interchain interactions, so that the polymers
form more disorder aggregation domains in the solid state.33
The absorbance of PII2T-PBA100 is also included to
demonstrate the effects of PBA side chain. The 720 nm signal,
as we expect, cannot be observed once we replace all the
polymer side chains into the PBA segment. The results again
imply that the PBA side chain can effectively manipulate the
solid state polymer characteristics. On the other hand, all
studied PII2T-PBA polymers possess a similar optical band gap
of 1.6 eV. This value is consistent with the isoindigo-
bithiophene-based polymers in the literature,26,34 indicating
that adding PBA groups on polymer side chain can still
maintain the polymer conjugations as compared to the classical
isoindigo polymers with alkyl side chains.
The energy levels of the studied semiconducting materials
were further analyzed through cyclic voltammetry (CV; Figure
S3b). The highest occupied molecular orbital (HOMO) level,
estimated from the onset oxidation potentials in the CV curves,
is ranging from −5.16 to −5.27 eV, while the lowest
unoccupied molecular orbital (LUMO) level is approximately
−3.6 eV, calculated by the difference between the HOMO level
and optical band gap. The energy band gaps and energy levels
are mainly determined by the backbone structure of conjugated
polymers. The studied polymers, thus, possess similar electro-
chemical properties with the same II2T polymer skeleton.
Field-Effect Transistor Characteristics. The charge
transport properties of the pristine PII2T, PII2T-PBA5,
PII2T-PBA10, and PII2T-PBA20 thin films were characterized
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Figure 2. (a) Illustration of the studied top-contact/bottom-gate FET device configuration. (b) FET transfer characteristics of the studied polymers
and (c) output curves of PII2T-PBA10-based FET device.
Table 1. Charge Transport, Crystallographic, and Mechanical Properties of the Pristine (i.e., Nonstretched) Polymer Thin
Films
conventional FET
−1 −1
polymers μ (cm V
a 2
s ) Ion/Ioff Vth (V)
PII2T 0.78 8 × 105 −28
PII2T-PBA5 0.33 2 × 105 −29
PII2T-PBA10 0.22 8 × 104 −31
PII2T-PBA20 0.063 3 × 104 −30
PII2T-PBA100 <10−7 ∼101
a
All the FET characteristics was averaged from at least 20 devices from 3 different batches.
using a bottom-gate/top-contact FET device, as illustrated in
Figure 2a. A SiO2 dielectric layer (i.e., thickness of 300 nm)
with a highly n-doped silicon substrate was modified with a
dense crystalline octadecyltrimethoxysilane (OTS) self-assem-
bly monolayer to improve the polymer interchain packing and
enhance the electrical performance. Figure 2b shows the typical
p-type transfer characteristics of the studied polymers with 0−
20% PBA side chain, and their device performance parameters,
including mobility (μ), on/off current ratio (Ion/Ioff), and
threshold voltage (Vth), are summarized in Table 1. The
averaged charge carrier mobilities of PII2T, PII2T-PBA5,
PII2T-PBA10, and PII2T-PBA20-based FET annealed at 200
°C are 0.78, 0.33, 0.22, and 0.063 cm2 V−1 s−1, respectively,
with a Ion/Ioff of 104−106. Output characteristics, moreover, are
depicted in Figure 2c and Figure S4; a good current modulation
as well as well-defined linear and saturation regions were
probed. The mobility is level downed as the PBA ratio
increased, which may be owing to the PBA side chain
disturbing the polymer interchain interactions as well as
molecular packing organizations. Note that PII2T-PBA100
cannot exhibit effective charge transporting (Figure S5a); the
mobility was lower than 10−7 cm2 V−1 s−1, demonstrating the
influence of PBA side chain on the electrical performance.
Polymers with a PBA side chain incorporation ratio lower than
10%, nevertheless, still achieved a good hole carrier mobility
higher than 0.2 cm2 V−1 s−1.
Polymer Thin Film Morphologies. As described above for
our studied polymers, the polymer properties and their
electrical characteristics are highly related to the chemical
structures, especially the PBA side chain content. Atomic force
microscopy (AFM) analyses and grazing incidence X-ray
diffraction (GIXD), therefore, were performed of the studied
polymer thin films to further understand the relationships
between PBA contents and interchain packing structures as well
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X-ray diffraction buckling method
lamellar spacing (Å) π−π stacking distance (Å) Ef (GPa)
25.3 3.5 0.80
25.9 3.5 0.63
26.2 3.5 0.57
27.0 3.5 0.12
0.041
as surface morphologies (Figure 3, Figures S5 and S6). Figure
3a exhibits the AFM topographies of PII2T, PII2T-PBA5,
PII2T-PBA10, and PII2T-PBA20 thin film surfaces. Well-
organized packing structures with a nanofibrillar surface
morphology and interconnected networks can be observed on
low PBA content polymers (i.e., PII2T and PII2T-PBA5). On
the contary, the surface morphology of PII2T-PBA10 and
PII2T-PBA20 thin films becomes more disordered because of
the polymer interchain interactions being interrupted by the
PBA side chains. Note that only amorphous structures could be
scanned on the PII2T-PBA100 surface (Figures S5c) as this
material is fully functionalized with PBA segments.
Next, grazing-incidence X-ray diffraction (GIXD) was
introduced to deeply realize the molecular stacking structures
of our studied PII2T-PBA polymers. The 2D GIXD patterns
are shown in Figure S7 with distinguishable diffraction signals,
and the corresponding 1D profiles (integrated from both out-
of-plane and in-plane direction of the 2D pattern) and the
crystallographic properties (i.e., packing spacing) are summar-
ized in Figure 3 and Table 1, respectively. PII2T, without
inserting PBA side chain, possesses clear diffraction signals (i.e.,
(n00)) (Figure 3b) with a lamellar spacing of 25.3 Å, which is
the smallest value (i.e., the most compact packing structures)
among the studied polymers. The peak intensity of PII2T thin
film, in addition, is also the highest compared to other PII2T-
PBA series polymers, indicating a stronger stacking crystallinity.
This is not surprising that as the soft PBA side chains are added
into our polymer system, the interchain interactions as well as
molecular organizations are diminished. Reduced crystallinity
(i.e., lower intensity of the diffraction peaks) is thus exhibited as
the PBA side chain content increased. Note that for the PII2T-
PBA100-based polymer film even no diffraction signals could
be observed (Figure S5b), suggesting an amorphous nature of
this polymer. With the increasing content of PBA, not only the
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Macromolecules
Figure 3. (a) AFM topographies, (b) out-of-plane 1D X-ray scanning
profile, and (c) in-plane 1D scanning X-ray profile of PII2T, PII2T-
PBA5, PII2T-PBA10, and PII2T-PBA20. Note that the 1D X-ray
profiles are extracted from the 2D GIXD patterns. All the studied
polymer thin films are controlled as approximately 60 nm thick.
X-ray diffraction signals become weaker but also the lamellar
spacing is enlarged to be 25.9, 26.2, and 27.0 Å for PII2T-
PBA5, PII2T-PBA10, and PII2T-PBA20, respectively, due to
the PBA side chain providing the huge bulkiness between
polymer chains, affecting the interdigitation between polymer
chains. The π−π stacking diffraction peak, on the other hand,
can be observed in the in-plane direction (Figure 3c), indicating
that a edge-on packing orientation is facilitated in the studied
polymer thin film and can generate effective 2D charge
transport channels between the source and drain contacts in the
transistor device. The π−π stacking distance of all PII2T,
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PII2T-PBA5, PII2T-PBA10, and PII2T-PBA20 based thin
films is 3.5 Å. Again, PII2T possesses the strongest signal
intensity without the influences from the PBA side chains. The
above morphological results are consistent with the charge
transport characteristics; the stronger and more condensed
molecular packing structures reflect a higher carrier mobility.
Nevertheless, the studied polymers still exhibit good molecular
stacking with clear diffraction signals even when the polymer
containing 20% PBA side chains.
Strain-Dependent Properties of Polymer Thin Films.
We have systematically characterized our studied PII2T-PBA
polymers on rigid substrates and outlined the structure−
property relationships based on various PBA content ratios in
the above sections. Polymers containing 10% PBA group (i.e.,
PII2T-PBA10), as a result, can still maintain ordered molecular
packing and good charge carrier mobility although the bulky
PBA side groups weaken the interchain interactions. The main
reason for designing such a huge PBA side group, more
importantly, is to improve the mechanical properties of the
semiconducting polymer thin film based on its low Tg nature.
Intrinsically stretchable thin film based on polymeric semi-
conductors thus can be demonstrated for soft electronic
applications. The mechanical, morphological, and electrical
characteristics of the studied PII2T-PBA polymer films were
systematically explored under a strain from 0 to 100%, and such
stretched thin films were prepared using the second transfer
method.26,35
The optical microscopy (OM) images (Figure 4 and Figure
S7) clearly explore the importance of PBA side chains on the
mechanical tolerance based on the studied polymer thin films.
Thin film of the polymer without PBA chains, PII2T, presents
obvious cracks under a strain smaller than 10%, and such
microcracks propagate through whole film with high cracking
density at 25% strain. Once we introduce small amount of PBA
segment (i.e., 5%) onto polymer side chains (PII2T-PBA5),
interestingly, the thin film ductility is dramatically improved.
Only several nanoscale cracks can be found on the surface
under 25% strain with a crack onset strain at approximately
20%. As we further increase the PBA content ratio,
furthermore, the strain tolerance of PII2T-PBA10- and
PII2T-PBA20-based thin films kept enhancing with a crack
onset strain at ∼40 and 60%, respectively. Under an extremely
high stretching ratio of 100%, it is clear that thin film is less
damaged as the PBA side chain incorporated. Soft PBA
segments can dissipate energy during stretching; the more PBA
chains equipped, the better thin film ductility and stretchability
we achieved with lower cracking density and higher crack onset
strain. Similar morphological results can be further demon-
strated using AFM (Figure 5a) with higher resolution. Note
that for the PII2T-PBA100-based thin film a smooth surface is
maintained under a applied strain up to 100% (Figure S8). For
comparison, a physically blended thin film based on PII2T and
PBA homopolymer (90:10 w/w) is also investigated (Figure
S9). Poor thin film deformability, however, is explored due to
large phase separation as well as nonuniform surface
morphology.
OM and AFM images, however, can only give a general
guideline that the mechanical property of the semiconducting
thin film is improved by the PBA side chains. Specific values are
still needed to defined the thin film ductility precisely. Two
factors, dichroic ratio and tensile modulus, are typically used to
quantify the mechanical characteristics of the polymeric
semiconducting thin films.2 The dichroic ratio (R) is calculated
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Macromolecules
Figure 4. Optical microscopy images of PII2T, PII2T-PBA5, PII2T-PBA10, and PII2T-PBA20 thin films under various strain levels.
from the absorption intensity of UV−vis spectroscopy as the
incident light is polarized parallel or perpendicular to the strain
direction, which can correlate with the degree of polymer chain
alignment during stretching (Figure 5b). In general, stretched
polymer film with higher R value indicates better polymer chain
alignment by strain, suggesting a stronger mechanical tolerance
is achieved.8,10,26 The R value of the studied PII2T-PBA
polymers, as we expect, is enlarged from approximately 1.27
(PII2T) to 1.42 (PII2T-PBA20) as the PBA content increases,
leading to an improved thin film ductility. On the other hand,
the buckling method is introduced to analyze the tensile
modulus (Ef) of the studied polymer thin films in more detail,
as summarized in Table 1. The Ef value of PII2T, PII2T-PBA5,
PII2T-PBA10, and PII2T-PBA20 is 0.80, 0.63, 0.57, and 0.12
GPa, respectively. This result, again, proves that an enhanced
thin film ductility and deformability can be realized by the
design of PBA side chain, which possesses low glass transition
temperature as well as high softness. Note that the Ef value of
PII2T-PBA100 is 0.041 GPa as a reference, implying the
importance of the PBA chains. Our studied polymer thin films,
in addition, can be recognized as a ductile thin film in general
since their modulus is comparable to the other conjugated
polymer films (i.e., 0.25−0.8 GPa)3 in the research community.
In our polymer design, not only the improvement of
mechanical property but also the superior charge transport
performance under strain is considered. Typically, the electrical
characteristics are highly related to the molecular packing
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structures inside the polymer film. The GIXD technique thus is
used to explore the interchain organization in molecular level of
the studied polymer films under strain. Figure 5c depicts the
2D GIXD patterns of the studied polymers under a 60% strain
with the incident X-ray beam that was controlled to be
perpendicular or parallel to the stretching direction, and the
detailed relevant crystallographic parameters are listed in Table
S1. The lamellar d-spacing of these PII2T-PBA polymers
remains in a range of 25−27 Å in both directions with the
applied strain up to 80%, while the π−π stacking distance is
maintained as well at 3.5−3.6 Å. Note that the intensity
difference (i.e., crystallinity difference) is due to the PBA
content in the polymers, as discussed in the previous section. It
seems that the π−π packing distance between the polymer
chains would not be affected by the stretching forces, meaning
that the applied strains do not break the crystalline region in
the polymer films. The charge transporting channels, thus, may
still be facilitated effectively after stretching. More interesting,
as we compared the GIXD patterns between the parallel and
perpendicular direction, the π−π stacking (010) signal was not
observed in all patterns. For PII2T and PII2T-PBA5-based
thin films, no matter whether the incident X-ray beam is parallel
or perpendicular to the strain direction, the π−π stacking peak
is always detected, indicating the polymer chains distribute
isotropically and the crystalline domains separate randomly in
the polymer films under strain. On the contrary, the (010)
signal from the PII2T-PBA10 and PII2T-PBA20 films is only
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Macromolecules
Figure 5. (a) AFM topographies of the studied polymer thin films under a 60% strain. (b) Dichroic ratio of the stretched polymer films. (c) 2D
GIXD patterns of the PII2T-PBA polymer thin films under a 60% strain. Note that the incident X-ray light was controlled to be parallel or
perpendicular to the stretching direction.
exhibited when the X-ray beam is parallel to the stretching
direction, meaning that the polymer chains tend to be aligned
to the strain direction. The reason why those crystalline
domains in the polymer films can be reorientated by the
stretching force may due to such 10−20% of PBA side chains
provide the softness of the polymer chains. This observation
also suggests the higher the PBA ratio is provided, the better
thin film ductility may have. From the above microscopy
images (i.e., OM and AFM), mechanical parameters (i.e., R and
Ef value), and molecular packing structures (i.e., GIXD), we can
thus demonstrate the functionality of PBA side chains, which
can effectively improve the thin film ductility as well as
stretchability for the soft electronic applications.
Charge Transport Characteristics under Stretching.
To evaluate the charge transport behaviors of the PII2T-PBA
thin films under strain, FETs were fabricated by the transfer
method, as illustrated in Figure 6a. Carrier transport parallel or
perpendicular to the stretching direction was characterized.
Figure 6b exhibits the transfer curves of the studied polymer
thin film-based devices at 60% strain, and the relationship
between charge carrier mobility (both parallel and perpendic-
ular direction) and strain strength is organized in Figures 6c,d.
The detailed electrical parameters of these stretched polymer
films, moreover, are summarized in Table 2. Among the studied
polymers, PII2T-PBA10 exhibits a stable electrical property
upon applying a strain up to 100%. The mobility of PII2T-
PBA10-based device can be maintained of 0.08 cm2 V−1 s−1
(0.1 cm2 V−1 s−1 at 0% strain) when the strain is applied in a
perpendicular direction. In contrast, PII2T and PII2T-PBA5-
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based devices degraded significantly after strain was applied; the
mobility is lower than 0.03 cm2 V−1 s−1 at 60% strain. Note that
the FET based on PII2T-PBA20 also shows stable electrical
performance under stretching (mobility change from 0.021
(0%) to 0.014 (60%) cm2 V−1 s−1), but its relatively low
mobility is due to the nature of low crystallinity. The main
difference of the charge transport ability under strain is owing
to the soft PBA segments on the polymer side chain that allows
the polymer film possesses better ductility to resistant
stretching forces. A similar mobility trend of the stretched
PII2T-PBA film-based FETs can be found in the parallel
direction in general. The field-effect mobility of the studied
polymers in this direction decreased modestly, which is
comparable to the study of other donor−acceptor conjugated
polymer-based devices under strain. Note that with increasing
amount of PBA, the anisotropic charge transport behaviors
(difference between perpendicular and parallel directions)
become clearer due to the enhanced thin film ductility and
deformability with higher degree of polymer chain alignment.
We not only probed the charge transport characteristics
under a single time stretching but also evaluated the FETs
under continuous 400 stretching/releasing cycles at a strain
level of 60% using PII2T-PBA10 thin films (Figure 7). Stable
electrical characteristics of mobility, on/off ratio, and threshold
voltage were obtained without significant changes during the
testing. The charge transport performances, in addition, are
comparable to the values before the cycling operation
commenced, demonstrating that our studied polymer thin
films possess a reliable and reproducible property under a
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Macromolecules Article

Figure 6. (a) Illustration of the top-contact FET device structure with stretched polymer thin film as active layer. (b) FET transfer characteristics of
PII2T, PII2T-PBA5, PII2T-PBA10, and PII2T-PBA20 thin films under a 60% strain. Note that the strain direction is perpendicular to the charge
transport direction. Averaged FET mobility of the studied polymer thin film under a strain from 0 to 100% as the stretching force (c) parallel and (d)
perpendicular to the charge transport direction.

Table 2. Averaged Electrical Characteristics of the Studied Polymer Thin Films under Various Strain Levelsa
PII2T PII2T-PBA5 PII2T-PBA10 PII2T-PBA20
strain μ Vth μ Vth μ Vth μ Vth
(%) direction (cm2 V−1 s−1) Ion/Ioff (V) (cm2 V−1 s−1) Ion/Ioff (V) (cm2 V−1 s−1) Ion/Ioff (V) (cm2 V−1 s−1) Ion/Ioff (V)
0 0.15 7 × 106 −24 0.14 7 × 105 −34 0.10 1 × 107 −28 0.021 1 × 106 −39
10 parallel 0.090 8 × 105 −23 0.085 9 × 106 −19 0.11 7 × 106 −38 0.020 9 × 105 −36
10 perpendicular 0.077 1 × 107 −26 0.082 8 × 106 −24 0.080 5 × 105 −32 0.013 5 × 105 −25
20 parallel 0.079 7 × 105 −17 0.075 4 × 106 −27 0.10 1 × 107 −37 0.022 8 × 106 −39
20 perpendicular 0.082 1 × 106 −25 0.073 8 × 105 −25 0.052 1 × 107 −17 0.0093 2 × 106 −26
40 parallel 0.066 6 × 106 −18 0.067 1 × 106 −20 0.071 2 × 106 −33 0.017 3 × 106 −40
40 perpendicular 0.037 5 × 105 −22 0.031 3 × 104 −26 0.038 1 × 107 −21 0.0080 1 × 106 −31
60 parallel 0.035 4 × 105 −21 0.020 5 × 105 −26 0.075 3 × 106 −35 0.014 4 × 106 −32
60 perpendicular 0.017 6 × 105 −18 0.018 7 × 105 −28 0.017 1 × 105 −24 0.0052 1 × 104 −25
80 parallel 0.025 2 × 105 −22 0.018 2 × 106 −22 0.042 9 × 105 −26 0.0091 2 × 106 −36
80 perpendicular 0.0086 4 × 104 −24 0.0079 3 × 105 −27 0.021 2 × 105 −23 0.0028 2 × 105 −26
100 parallel 0.014 5 × 105 −22 0.014 5 × 104 −23 0.020 7 × 105 −22 0.0081 4 × 104 −33
100 perpendicular 0.0026 3 × 105 −26 0.0034 2 × 105 −29 0.0094 3 × 105 −20 0.0012 2 × 106 −24
a
All the FET characteristics were averaged from at least 20 devices from 3 different batches, and the FETs were fabricated using a transferred
semiconducting thin film with various strain levels.

tensile strain as high as 60%. The above electrical results

suggest that our newly designed isoindigo-bithiophene
polymers with PBA side chains can achieve a stable and
superior charge transport under a strain up to 60%, which is
tolerable to most of the strain based on our body movement
(mostly <50%), showing that the rational design of soft side
chain in conjugated polymer systems provides a significant
potential to develop high-performance wearable electronics.
4990
■ CONCLUSION
Rational design of ATRP-polymerized soft PBA side chains on
conjugated polymer backbone is herein described with various
ratios (i.e., 0, 5, 10, 20, and 100%) for achieving organic
semiconducting thin films with superior charge transport, good
ductility, and stable electrical/mechanical performance under
tensile strains. The PBA segments generate impacts on polymer
processability, solid-state molecular packing, and thin film
ductility directly, leading to low elastic modulus and good
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Macromolecules
Figure 7. Mechanical endurance of PII2T-PBA10-based thin film under a 60% strain for 400 stretching/releasing cycles. (a) Transfer curves of the
film were tested through 1, 50, 100, 200, and 400 cycles as the charge transport direction is controlled to be perpendicular to the strain direction. (b)
Relationship between mobility, on/off ratio or threshold voltage, and stretching/releasing cycles. Stable electrical properties were obtained in both
parallel and perpendicular strain directions, which are relative to the charge transport direction.
charge carrier transporting under an applied tensile strain up to
100% of our PII2T-PBA semiconducting thin films. Among the
studied polymers, PII2T-PBA10 presents a stable and reliable
charge carrier mobility of 0.08−0.1 cm2 V−1 s−1 under 0−60%
strain, and such polymer film also exhibits reliable and
reproducible electrical endurance under 400 simultaneous
stretching/releasing cycles. This type of low Tg and bulky
acrylate side chain, to the best of our knowledge, is first time to
be designed on conjugated polymer system for intrinsically
stretchable transistors. The experimental results indeed suggest
our studied PII2T-PBA polymers are the promising candidates
for next-generation soft electronic applications.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.macro-
mol.7b00860.
Experimental characteristics, 1H NMR spectrum of the
studied PII2T-PBA monomers and polymers; DSC
traces, CV curves, 2D GIXD patterns, and FET output
curves of the studied polymers; strain-dependent proper-
ties (i.e., optical microscopy images, GIXD patterns, and
transistor characteristics) of the studied polymer thin
films under applied strain levels (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: hungchinwu@ntu.edu.tw (H.-C.W.).
*E-mail: kuocc@mail.ntut.edu.tw (C.-C.K.).
*E-mail: chenwc@ntu.edu.tw (W.-C.C.).
ORCID
Hung-Chin Wu: 0000-0001-6492-0525
Chi-Ching Kuo: 0000-0002-1994-4664
Wen-Chang Chen: 0000-0003-3170-7220
Author Contributions
H.-F.W. and H.-C.W. contributed equally to this work.
Notes
The authors declare no competing financial interest.
4991
Article
■ ACKNOWLEDGMENTS
The financial support from Ministry of Science and Technology
of Taiwan is highly appreciated (MOST104-2221-E-002-128-
MY3; MOST105-2119-M-002-008). The authors acknowledge
National Synchrotron Radiation Research Center of Taiwan for
facilitating the GIXD experiments.
■
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4992 DOI: 10.1021/acs.macromol.7b00860

Macromolecules 2017, 50, 4982−4992