Progress in Polymer Science 100 (2020) 101181

Contents lists available at ScienceDirect

Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci

Intrinsically stretchable conjugated polymer semiconductors

in field effect transistors
Minoru Ashizawa, Yu Zheng, Helen Tran, Zhenan Bao ∗
Department of Chemical Engineering, Stanford University, USA

a r t i c l e i n f o a b s t r a c t

Article history: Stretchable electronics have increasingly gained interest both in the academic and industrial communities
Accepted 12 November 2019 owing to its potential to enable a wide variety of applications, especially wearable and implantable devices
Available online 14 November 2019 for biomedical applications. As the key component for electronic devices, the design of a suitable semicon-
ductor is essential, while the solution processability and structural tunability of polymer semiconductor
Keywords: make it a promising candidate. Along this line, it is important to consider the mechanical properties of
Conjugated polymers
polymer semiconductors in the design of flexible and stretchable devices placed on soft and curved sur-
Organic electronics
faces to accommodate the constant movement of the human body. However, achieving high mechanical
Field effect transistor
Stretchable conjugated polymers
deformability and high charge transport properties simultaneously in polymer semiconductors remains a
Charge transport major challenge. In this trend article, we survey various approaches in designing intrinsically stretchable
Stretchable electronics conjugated polymers, focusing on structure-property relationships from a molecular perspective, such
as molecular weight, regioregularity, backbone and side chain modifications. Understanding the influ-
ence of these molecular structure parameters on thin film morphology may provide general guidelines for
achieving desired microstructures that allow mechanical deformation without interrupting charge trans-
port. Beyond highlighting recent key work in this field, we will discuss future prospects of stretchable
conjugated polymers.
© 2019 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Polymer fundamental properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Molecular weight effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Regioregularity effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Polymer structural design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Incorporation of conjugation break spacers (CBs) into polymer backbone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2. Side chain engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4. Conclusions and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

Abbreviations: AFM, atomic force microscope; BHJ, bulk heterojunction; CB, conjugation breaking spacer; CNT, carbon nanotube; CP, ␲-conjugated polymer; Ð, polymer
dispersity; D-A, donor-acceptor; DPP, diketopyrrolopyrrole; DSC, differential scanning calorimetry; GIXD, grazing-incident X-ray diffraction; GRIM, Grignard metathesis; H-
bonding, hydrogen-bonding; Hf, enthalpy fusion; H–H, head-to-head; H–T, head-to-tail; LED, light-emitting diode; Mn, molecular weight; NP, nanoparticle; NW, nanowire;
OSC, organic solar cell; P3AT, poly(3-alkylthiophene); PBA, poly(butyl acrylate); P3BT, poly(3-butylthiophene); pBTTT, poly(3-alkylthiophene-2-yl)thieno[3,4-b]thiophene;
PCBM, [6,6]-phenyl-C61-butyric acid methyl ester; PCE, power conversion efficiency; PDCA, 2,6-pyridine dicarboxamide; P3ddT, poly(3-dodecylthiophene); PDPP-FT4,
poly(tetrathienoacene -diketopyrrrolopyrrole); p(DPP-TVT), poly(diketopyrrrolopyrrole-thiophene-vinylene-thiophene); P3HpT, poly(3-heptylthiophene); P3HT, poly(3-
hexylthiophene); PiI2T, poly(isoindigo-bithiophene); P3OT, poly(3-octylthiophene); TFT, thin-film transistor; Tm, melting temperature; T-T, tail-to-tail.
∗ Corresponding author.
E-mail address: [email protected] (Z. Bao).

https://doi.org/10.1016/j.progpolymsci.2019.101181
0079-6700/© 2019 Elsevier B.V. All rights reserved.
2 M. Ashizawa, Y. Zheng, H. Tran et al. / Progress in Polymer Science 100 (2020) 101181

1. Introduction reactivity and purity, leading to disparities in molecular weight

and dispersity from batch-to-batch reactions even in careful prepa-
Conjugated polymers enable the fabrication of lightweight, low- rations [35,36]. Chain-growth polymerization reactions affords
cost and large-area electronic devices, such as thin-film transistors well-controlled Mn and Ð values and regular regioregularity; how-
(TFTs) [1–4], light-emitting diodes (LEDs) [5–8], and organic solar ever, they are limited to the preparation of specific polymers (e.g.
cells (OSCs) [9–12]. In the past decade, research in both academia poly(3-hexylthiophene), P3HT) and are not applicable to many
and industry has shifted to wearable electronics, healthcare moni- commonly used high mobility D-A copolymers. In addition, Mn
toring devices, and electronic skin [13–15]. For these applications, is a relative molecular weight determined by gel permeation
high performance flexible and stretchable polymer semiconduc- chromatography, wherein the Mn value depends on the solvent,
tors with the ability to accommodate mechanical deformability concentration, temperature, and standard calibration materials
are needed to conform to the soft, dynamic and curvilinear human used for the measurements because conjugated polymers form
bodies. various degrees of aggregation depending on these conditions
Three types of approaches have been reported to achieve flex- [37–40]. In this section, we specifically discuss the influence
ible and stretchable electronic devices: (1) structural engineering, of (number-averaged) molecular weight and regioregularity on
(2) blending of semiconducting or conducting materials with an charge transport and mechanical properties.
elastomeric matrix and (3) development of intrinsically stretchable
polymer semiconductors [16]. In structural engineering, pre-strain 2.1. Molecular weight effect
elastomer [17], wrinkles [18], serpentine [19], kirigami-inspired
[20], horseshoe [21], interconnected rigid-islands [22], and mesh The impact of molecular weight contribution on charge car-
structures [23] have been developed. For example, Rogers et al. have rier mobility and thin film morphology has been well examined
demonstrated that waved or buckled configurations of silicon rib- in poly(3-hexylthiophene) (P3HT) based transistors, in which
bons on elastomeric substrates sufficiently dissipate strain energy P3HT has been widely studied as a solution-processable poly-
upon mechanical deformation [24,25]. In the blending approach, mer [41–44]. To explore the molecular weight contribution of
strain-independent electrical performance is observed for stretch- P3HT, low polydispersity Ð P3HTs (Ð = 1.0–2.0) with various num-
able composites comprised of elastomeric matrices and various ber averaged molecular weights were employed. Commonly used
materials, including metallic nanowires (NWs) [26], nanoparticles Donor-Acceptor (D-A) copolymers, on the other hand, exhibit dis-
(NPs) [27], carbon nanotubes (CNTs) [28], and ␲-conjugated semi- persity values Ð > 2.
conducting polymer nanofibers (CP) [29–33]. The AFM and X-ray diffraction results suggest that P3HT with Mn
In particular, the development of intrinsically stretchable semi- below 10 kDa forms highly crystalline nanostructures while P3HT
conducting polymers is an attractive approach because polymers with Mn over 30 kDa exhibits small ordered crystalline domains
offer potential for precisely controllable electronic properties, [41,45]. In low Mn P3HT TFTs, disconnected crystalline domains
relatively low tensile modulus below 1 GPa, and solution pro- and large grain boundaries result in low charge carrier mobility.
cessability for large-area printing. Additionally, semiconducting Meanwhile, the high mobility of TFTs fabricated with high Mn P3HT
polymers have shown skin-inspired properties such as self-healing has been attributed to tie chains that effectively connect crystalline
and biodegradability for high-density and biocompatible devices in regions and thus better facilitate effective charge transport [42]. It is
next-generation wearable and implantable electronics [13,14,34]. evident that the morphological differences in P3HT thin films have
However, concurrently achieving good electrical and mechan- a direct impact on its mechanical properties. Moreover, Peter et al.
ical properties for these semiconducting polymers remains a reported that low Mn P3HT showed higher elastic modulus than
persistent challenge. The intermolecular ␲-␲ stacking in conju- high Mn polymer upon comparison of P3HT tapes with various Mn ;
gated polymer often results in the formation of highly crystalline low Mn P3HT exhibited brittle fracture behavior, showing rupture
domains, which is beneficial for high charge carrier mobility in TFT strain at ␧ = 10 % whereas high Mn P3HT showed plastic deformation
applications. However, such semi-crystalline morphologies render behavior after the yield point, allowing the specimen to elongate up
conjugated polymer films to be brittle, which is not favorable for to 300 % strain (Fig. 1A) [45]. A similar result was demonstrated for
mechanical deformability. In this trend article, we survey selected, P3HT thin films by Rodriquez et al. (Fig. 1B). The improved ductility
recently reported approaches for designing intrinsically stretch- and decreasing tensile modulus of high Mn P3HT were attributed to
able polymer semiconductors that have primarily been utilized the increase of polymer chain entanglement and lower crystallinity,
as the active matrix in TFT applications, highlighting informative while the charge transport pathway is maintained by tie chain con-
structure-property relationships. For examples, we will discuss necting the crystalline domains. These results, when comparing
the impact of molecular design on the morphological distribution P3HTs bearing relatively low Ð values, indicate that the high Mn
of the crystalline and amorphous domains under strain. Specifi- conjugated polymers are better suited than the equivalent low Mn
cally, we review the effects of polymer fundamental properties (e.g. conjugated polymers to obtain superior mechanical and electrical
molecular weight and regioregularity), polymer structural designs, properties.
conjugation breakers and side-chain engineering. Finally, we will
conclude with our perspectives on the promising design parame- 2.2. Regioregularity effect
ters for future stretchable conjugated polymers.
The regioregularity of a polymer affects the thin film crys-
tallinity and in turn may influence its mechanical properties and
2. Polymer fundamental properties charge transport. The use of an asymmetrical monomer results in
regioregular and irregular monomer connections along the poly-
Compared with well-defined small semiconducting molecules, mer backbone. In case of 3-hexylthiophene, one monomer could
conjugated polymer properties may suffer from reproducibil- be linked with another monomer in a head-to-tail (H T), head-
ity issues owing to batch-to-batch variations in regioregularity, to-head (H H), and tail-to-tail (T T) configuration (Fig. 2A). The
(number-averaged) molecular weight (Mn ), and molecular weight H H and T T coupling configurations induce polymer backbone
dispersity (Ð). Commonly used high mobility Donor-Acceptor (D- twisting, whereas H T coupling leads to ordered interchain pack-
A) copolymers are often prepared via step-growth condensation ing [46–48]. To date, the majority of research has been focused
reactions, which are sensitive to reaction conditions, monomer on increasing the conjugated polymer backbone regioregular-
 M. Ashizawa, Y. Zheng, H. Tran et al. / Progress in Polymer Science 100 (2020) 101181 3

Fig. 1. Stress-strain curves obtained from (A) bulk tensile test of P3HT samples
with different molecular weight [45], Copyright 2013. Reproduced with permission
from Elsevier and (B) tensile test obtained using the film-on-water technique [43], Fig. 2. (A) Possible coupling modes of P3HT. (B) Mechanical properties and defor-
Copyright 2016. Reproduced with permission from the American Chemical Society. mation mechanism of P3HT polymer thin films as a function of RR [49], Copyright
2015. Reproduced with permission from the American Chemical Society.

ity to obtain higher charge mobility. However, Kim et al. have

demonstrated that the ductility of P3HT can be tuned by sys- decreasing regioregularity will increase the stretchability for con-
tematically decreasing polymer regioregularity (Fig. 2 B) [49]. jugated polymers, however, it usually leads to the drop of electrical
The 3-hexylthiophene was randomly copolymerizing with various performance. Considering polymer fundamental properties in this
amounts of a H H coupled hexylthiophene dimer via Ni-mediated section, we need to find a balance between stretchability and charge
Grignard metathesis (GRIM) polymerization to precisely control carrier mobility. In addition, we consider that high Mn of conjugated
the Mn and Ð values. The synthesized P3HTs exhibited regioregular- polymers with low Ð values would have large impact on achieving
ity ranging from 64 % to 98 %. Polymer crystallinity decreased with superior stretchability and electronic properties.
decrease of regioregularity, as supported by grazing-incident X-
ray diffraction (GIXD) and differential scanning calorimetry (DSC; 3. Polymer structural design
melting temperature, Tm ; enthalpy fusion, Hf ). When tensile test-
ing on water utilizing 100 nm thickness P3HT films were examined, Beyond the monomeric level, the sequence of the monomers
a decrease of modulus and an increase of rupture strain were and overall polymer design plays a role on the macro-
observed in the P3HT films with lower regioregularity. The rup- scopic mechanical properties. For example, structural differences
ture strain of P3HT increased from 0.6 % to 5.3 % with decreasing between conjugated polymers P3HT and poly(3-alkylthiophene-
regioregularity from 98 % to 64 %. This was explained by the fact 2-yl)thieno[3,4-b]thiophene (pBTTT) leads to different mechanical
that an increase of the amorphous region in polymers with low properties (Fig. 3A and B), as first highlighted by DeLongchamp
regioregularity may prevent crystallization through steric conges- et al. [50]. The relationship between charge carrier mobility and
tion between the side chains. Upon applying strain, the amorphous mechanical properties was examined by comparing moderately
regions exhibited plastic deformation and polymer chains were crystalline P3HT and highly crystalline pBTTT. Thin films of P3HT
aligned along the strain direction, providing higher rupture strain form an edge-on type lamellar packing of polymer backbones seg-
and lower tensile modulus. The mechanical stability was evaluated regated by alkyl chain regions. This structural order, in which the
by measuring the current-voltage profiles with multiple bending ␲-stacking direction is parallel to the substrate, is favorable for two-
cycles. The polymer with low regioregularity exhibited constant dimensional charge transport in a TFT device. Meanwhile, in thin
currents even after 800 bending cycles. On the other hand, a rapid films of pBTTT, the alkyl chain interdigitation facilitates crystalline
decrease in current was observed for regioregular P3HT after just order up to three dimensions, resulting in larger crystal sizes and
50 bending cycles. Notably, the 64 % regioregular P3HT displayed fewer defects. The charge mobility and tensile modulus of pBTTT
a drop in charge mobility (4.84 × 10-8 cm2 V−1 s−1 ) owing to the was higher than those of P3HT due to the higher crystalline mor-
decrease of crystallinity and effective conjugation length. Thus, phology. A higher elastic modulus for pBTTT (E = 0.9 GPa) compared
4 M. Ashizawa, Y. Zheng, H. Tran et al. / Progress in Polymer Science 100 (2020) 101181

Fig. 3. Effect of interdigitation of side chains on polymer backbone packing of con-

jugated polymers (A) P3HT and (B) PBTTT [50], Copyright 2010. Reproduced with
permission from the American Chemical Society.

Fig. 4. (A) The polymer structures containing conjugation break spacers. (B) Tensile
to P3HT (E = 0.25 GPa) was calculated by buckling-based metrology. modulus, crack-onset strain, and lamellar full width at half-maximum (fwhm) vs
ratio of the conjugation breaker [66], Copyright 2016. Reproduced with permission
Indeed, the high crystallinity is also responsible for the low crack from John Wiley and Sons.
onset strain (␧ = 2.5 %) for pBTTT compared to P3HT (␧ = 150 %).
This observation appears to suggest that excellent electrical
performance and good mechanical compliance of semiconducting with DPP. The polymers containing 10−20 mol% CBs unexpectedly
polymers are mutually exclusive, wherein good charge transport maintained relatively high charge mobilities over 1.0 cm2 V−1 s−1 ,
properties requires high crystallinity and mechanical compli- suggesting the introduction of CBs has surprisingly not introduced
ance calls for an amorphous morphology. Similar observations much disorder to lamella structure in the thin films as evidenced
were made by other groups in developing stretchable materi- by Grazing-incidence X-ray diffraction (GIXD) measurements. In
als [29,49,51]. However, the discovery of low crystallinity and addition to incorporation of CBs into polymer backbone, the poly-
high charge mobility polymers in recent years have encouraged mer blending approach is also promising to impart the flexibility,
researchers to reevaluate and better understand charge transport which enabled the polymers to form melt-processable films origi-
processes in conjugated polymers [52–56]. For instance, Noriega nating from their lower melting points [62,63]. The hypothesis was
et al. proposed that long-range charge transport could be achieved that the introduction of such flexible spacers increases the entropy
by poorly ordered polymers with high molecular weights and of the melt phase and thus decrease the melting temperatures
well-overlapped intermolecular couplings in aggregates [56]. These compared to the fully conjugated systems. To date, complemen-
findings open new ways to develop semiconducting polymers tary semiconducting polymer blends have been reported [64,65],
that may satisfy both good electrical performance and mechani- however this blending approach is beyond the scope of polymer
cal deformability simultaneously. In this section, we describe how backbone modification in this section.
backbone engineering and side chain modification impact polymer By examining DPP-based polymers with various mole percent-
stretchability. age of CBs, Savagatrup et al. hypothesized that the flexible CB
segments provide deformability (Fig. 4A and B) [66]. The flexi-
3.1. Incorporation of conjugation break spacers (CBs) into ble non-conjugated DPP-100 formed the stiffest and most brittle
polymer backbone films, as was supported by comparing GIXD data. GIXD indicated
that DPP-100 had the smallest lamellar spacing compared to the
The conventional approach to achieve high charge carrier mobil- other DPP systems containing less percentages of CBs, which corre-
ity is to design fully conjugated polymer backbones with high sponds to the most compact interdigitated packing motif between
molecular weights. Accordingly, high charge mobility has been polymer backbones. This study highlights the dual influence of
achieved in D-A type polymers with highly ordered microstructure polymer backbone on macroscopic mechanical properties, wherein
in the thin films, which originates from electronic push-pull inter- it determines the flexibility of the isolated ␲-conjugated units and
actions and long conjugation lengths [57–59]. However, Mei and solid-state microstructure.
our group have introduced the concept of the conjugation break- The incorporation of energy dissipating mechanisms into a poly-
ing spacers (CBs) incorporated along the polymer backbone as an mer network has been demonstrated as an effective approach to
approach to impart stretchability. In these reports, CBs compose enable highly stretchable and tough hydrogels [67]. Our previous
of insulating alkyl chains into the ␲-flamework of DPP (diketopy- work demonstrated that the incorporation of multiple dynamic
rrolopyrrole) or isoindigo polymers by random copolymerization cross-linking sites on the polymer backbone provides multiple
[60,61]. A series of polymers were prepared (Fig. 4A), ranging from energy dissipation properties, which leads to the development of
a fully conjugated rigid DPP-0 to the flexible non-conjugated DPP- stretchable and self-healing elastomer [68]. In the same vein, func-
100 containing aliphatic propylene groups as every unit alternating tionalized CBs which can form dynamic non-covalent cross-linking
 M. Ashizawa, Y. Zheng, H. Tran et al. / Progress in Polymer Science 100 (2020) 101181 5

Fig. 5. (A) Chemical structures of polymers P1 to P7 and (B) general mechanism for enhancement of stretchability in conjugated polymers via dynamic bonding [69], Copyright
2016. Reproduced with permission from Springer Nature.

sites were reported by our group to analogously enhance stretch- moderate H-bonding strength formed between the PDCA units,
ability in polymer semiconductors [69]. The energy dissipating CB which serve as dynamic sacrificial bonds in the amorphous regions.
features a 2,6-pyridine dicarboxamide (PDCA) unit, which bears These bonds break with applied strain and hence release stress
moderate hydrogen bonding (H-bonding) strength. This CB was loaded on the polymer chains. To confirm this hypothesis, the
copolymerized to yield DPP polymers P2 to P4, which contain dif- amide groups in the PDCA unit were modified with methyl groups
ferent percentages of PDCA (Fig. 5A and B). Compared with the to exclude H-bonding and we re-evaluated the mechanical proper-
control polymer poly(diketopyrrrolopyrrole-thiophene-vinylene- ties of the polymer. Similarly, with P3, a decrease in elastic modulus
thiophene) p(DPP-TVT) which contains no PDCA units, the polymer was observed owing to reduced conjugation length, however, the
containing PDCA units exhibited a decrease in tensile modulus from crack on-set strain was much lower (␧ = 25 %). The AFM images of
1 to 0.25 GPa and an increase in crack on-set strain up to 120 % the broken film after stretching and recovered film after solvent and
(Fig. 6A). The decrease in tensile modulus was attributed to the thermal annealing show healing properties of the system (Fig. 6C
decrease of conjugation length along with rotational freedom of and D). Clear nanocracks were formed initially, but after the treat-
bulky PDCA units producing large free volume. When replacing the ment, cracks were no longer apparent and the charge mobility was
PDCA segment with linear hexyl alkyl spacer (P6) which does not completely recovered back to above 1.0 cm2 V−1 s−1 . This is the first
have an energy dissipation unit, the modulus was further reduced demonstration of a polymer semiconductor with healing capability.
by one order of magnitude in comparison with the control polymer
p(DPP-TVT) (Fig. 6A). Transistors fabricated from P3 films provided 3.2. Side chain engineering
a stable charge mobility over 1.0 cm2 V−1 s−1 even at strains up to
␧ = 100 %. The high cyclic durability of the polymer semiconduc- Our work regarding two rigid polymers, poly(tetrathienoacene
tor was confirmed after 100 cycles of repeated stretching-release -diketopyrrrolopyrrole) PDPP-FT4 [70] and poly(isoindigo-
cycles, where only a 26 % carrier mobility decrease was observed bithiophene) PiI2T [71], and Roth’s library of D-A polymers [72]
(Fig. 6B). This enhancement of stretchability originates from the suggest that the side chains of semiconducting polymers have a
6 M. Ashizawa, Y. Zheng, H. Tran et al. / Progress in Polymer Science 100 (2020) 101181

Fig. 6. (A) Influence of the hydrogen-bonding moiety amount on elastic modulus and crack formation strain. (B) Field-effect mobility versus number of stretching cycles
performed along the perpendicular to strain direction. AFM phase image for damaged (C) and healed (D) film of P3 [69] Copyright 2016. Reproduced with permission from
Springer Nature.

Fig. 7. (A) Chemical structures of PTDPPTFT4 and PII2T. (B) Field-effect mobilities of PTDPPTFT4 and PII2T measured by the soft-contact lamination films under various strains
[71], Copyright 2014. Reproduced with permission from the American Chemical Society. (C) Structurally modified structures of PTDPPTFT4 [70], Copyright 2016. Reproduced
with permission from John Wiley and Sons Inc.
 M. Ashizawa, Y. Zheng, H. Tran et al. / Progress in Polymer Science 100 (2020) 101181 7

Fig. 8. (A) Chemical structures of isoindigo-based polymers with various contents of PBA side chain. Field-effect mobilities of the studied polymers under various strains as
the stretching direction (B) parallel and (C) perpendicular to the channel direction [75], Copyright 2017. Reproduced with permission from the American Chemical Society.

strong impact on polymer stretchability. In our study, by utilizing the side chain length, the polymers exhibited a decrease in tensile
a soft contact lamination method, PiI2T exhibited comparable modulus from 2.08 to 0.15 GPa and an increase in crack on-set
mechanical properties as P3HT but a higher charge mobility of strain from 6 to 65 %. The improved film ductility and decrease in
1.52 × 10−2 cm2 V−1 s−1 at 100 % strain (Figs. 7A and B). How- the glass transition temperature was attributed to the increased
ever, PDPP-FT4 showed poor stretchability despite superior charge flexibility of polymer backbone. However, the blended film with
transport. This prompted us to consider ways to impart stretchabil- PCBM for bulk heterojunction (BHJ) cells exhibited a drastic drop
ity on PDPP-F4, and the correlation between polymer packing order in Jsc and power conversion efficiency (PCE) with increase of the
(either edge-on or face-on) and mechanical compliance. A series alkyl chain length from hexyl to octyl chains. Savagatrup et al.
of PDPP-FT4 based polymers with various branched side chains have reported diblock copolymer P3HT-b-P3OT, a random copoly-
and additional thiophene spacers in the backbone were studied mer P3HT-co-P3OT, and poly(3-heptylthiophene) (P3HpT) [74].
(Fig. 7C) [70]. The introduction of branched alkyl side chains was Both copolymers displayed moderate elastic modulus (0.3 GPa)
found to reduce the tensile modulus and improve the ductility of and PCE (1.5 %), and these properties are intermediate between
polymer films by softening the amorphous regions. When adding those of P3HT and P3OT. Interestingly, P3HpT with intermediated
more thiophene spacers into the polymer backbone, the resulting side chain length showed a PCE of 2.16 %, tensile modulus of
polymer displayed a further delayed onset of crack propagation 0.07 GPa, and a crack on-set strain of 58 %. However, a com-
at ␧ = 40 % and maintained a charge mobility of 0.1 cm2 V−1 s−1 promise carrier mobility of 5 × 10−4 cm2 V−1 s−1 was obtained
even at 100 % strain. The use of additional thiophene spacers could in FET device.
contribute to better mechanical ductility by favoring the edge-on Wen et al. developed a series of isoindigo-based polymers
packing orientation in the crystalline regions, implying that the PiI2T with poly(butyl acrylate) (PBA) side chains (Fig. 8A) [75]. By
position of monomer spacer with alkyl side chain modifications is incorporating 20 mol% PBA side chains, PiI2T polymer displayed
well associated with the balance between polymer arrangement an increase in crack on-set strain from ␧ = 25–60% and a sharp
and mechanical deformability. Lipomi et al. reported a detailed decrease in elastic modulus from 0.8 to 0.12 GPa while main-
study regarding the effect of linear alkyl side chain length of taining the carrier mobility of 0.06-0.08 cm2 V−1 s−1 (Fig. 8B and
poly(3-alkylthiophene) (P3AT) on the mechanical and OSC device C). This improved ductility was attributed to the larger free vol-
properties of P3AT and [6,6]-phenyl-C61-butyric acid methyl ume of the PBA side chains that reduce interchain interactions
ester (PCBM) blend film [73]. They focused on four polymers between polymer backbones. This finding was consistent with the
of poly(3-butylthiophene) (P3BT), P3HT, poly(3-octylthiophene) observed increase in solubility and decrease in crystallinity exam-
(P3OT), and poly(3-dodecylthiophene) (P3ddT). Upon increasing ined by GIXD. In addition, the Mn of PBA side chains were 1.5 kDa,
8 M. Ashizawa, Y. Zheng, H. Tran et al. / Progress in Polymer Science 100 (2020) 101181

thus the large mass ratio of the side chain to the overall mass Acknowledgement
of polymer semiconductor dilutes the conjugated flamework con-
tent in the film. Approximately, 90 % mass for each isoindigo-PBA This work was financially supported by Air Force Office of Sci-
monomer came from the PBA side chains, resulting in the formation entific Research (grant no. FA9550-18-1- 0143).
of amorphous stretchable domains. This observation provides the
importance of tie chains connecting crystallites existing between
amorphous domains. In this section, based on both polymer back- References
bone modification and side-chain engineering, we consider that
designing deformable amorphous regions, which are continuously [1] Bao Z, Locklin JJ. Organic field-effect transistors. New York: CRC Press; 2007.
p. 640.
interconnected with inter- and intrachain charge transport through [2] Sirringhaus H. 25th anniversary article: organic field-effect transistors: the
semicrystalline aggregate junction, to be a practical route to obtain path beyond amorphous silicon. Adv Mater 2014;26:1x319–335.
appropriate thin film morphology displaying both the high stretch- [3] Wang C, Dong H, Hu W, Liu Y, Zhu D. Semiconducting ␲-conjugated systems
in field-effect transistors: a material odyssey of organic electronics. Chem Rev
ability and charge mobility. 2012;112:2208–67.
[4] Podzorov V. Organic single crystals: addressing the fundamentals of organic
electronics. MRS Bull 2013;38:15–24.
[5] Xiao L, Chen Z, Qu B, Luo J, Kong S, Gong Q, et al. Recent progresses on
4. Conclusions and perspectives
materials for electrophosphorescent organic light-emitting devices. Adv
Mater 2011;23:926–52.
Polymer semiconductors have emerged as great candidates [6] Friend RH, Gymer RW, Holmes AB, Burroughes JH, Marks RN, Taliani C, et al.
in flexible and stretchable electronics and various approaches Electroluminescence in conjugated polymers. Nature 1999;397:121–8.
[7] Wu H, Ying L, Yang W, Cao Y. Progress and perspective of polymer white
have been developed to improve both the electrical and mechan- light-emitting devices and materials. Chem Soc Rev 2009;38:3391–400.
ical properties of these conjugated polymers. In this trend [8] Baldo MA, O‘brien DF, You Y, Shoustikov A, Sibley S, Thompson ME, et al.
article, we have presented a survey of intrinsically stretchable Highly efficient phosphorescent emission from organic electroluminescent
devices. Nature 1998;395:151–4.
polymer semiconductors, focusing on structure-property relation- [9] Lu L, Zheng T, Wu Q, Schneider AM, Zhao D, Yu L. Recent advances in bulk
ships between molecular design and thin-film properties. The heterojunction polymer solar cells. Chem Rev 2015;115:12666–731.
general strategy to impart stretchability to polymer semicon- [10] Yang Y, Zhu R, Li G. Next-generation organic photovoltaics based on
non-fullerene acceptors. Nat Photonics 2018;12:131–42.
ductors is molecular engineering to realize optimized thin-film [11] Janssen RAJ, Neilson J. Factors limiting device efficiency in organic
microstructure, wherein balanced distribution of both crystalline photovoltaics. J Adv Mater 2013;25:1847–58.
and amorphous region is important. The introduction of appro- [12] Qiao Q. Organic solar cells: materials, devices, interfaces, and modelling. New
York: CRC Press; 2015. p. 446.
priate CBs to the polymer backbone can realize this thin film [13] Chortos A, Liu J, Bao Z. Pursuing prosthetic electronic skin. Nat Mater
microstructure, imparting stretchability via an energy dissipat- 2016;2:937–50.
ing mechanism and self-healing properties with H-bonding CBs. [14] McCoul D, Hu W, Gao M, Mehta V, Pei Q. Recent advances in stretchable and
transparent electronic materials. Adv Electron Mater 2016;2, 1500407/
To date, polymer films with crack on-set strains over ␧ = 100 %
1-51.
while maintaining charge carrier mobility above 1 cm2 V−1 s−1 have [15] Tran H, Feig VR, Liu K, Zheng Y, Bao Z. Polymer chemistries underpinning
been accomplished in DPP-based D-A polymers by incorporating materials for skin-inspired electronics. Macromolecules 2019:3965–74.
H-bonded PDCA CBs. Tuning interchain interactions of semicon- [16] Root SE, Savagatrup S, Printzs AD, Rodriquez D, Lipomi DJ. Mechanical
properties of organic semiconductors for stretchable, highly flexible, and
ducting polymers by modifying side-chains can also be an effective mechanically robust electronics. Chem Rev 2017;1117:6467–99.
approach to promote both carrier transport and mechanical flexi- [17] You I, Kong M, Jeong U. Block copolymer elastomers for stretchable
bility. electronics. Acc Chem Res 2019;52:63–72.
[18] Yu S, Ni Y, He L, Ye QL. Tunable formation of ordered wrinkles in metal films
In consideration of recent advances to provide semiconduct- with controlled thickness gradients deposited on Soft elastic substrates. ACS
ing polymer with deformability, it can be clearly seen that precise Appl Mater Interfaces 2015;7:5160–7.
morphological control is important for further advancement of [19] Zhang Y, Wang S, Li X, Fan JA, Xu S, Song YM, et al. Experimental and
theoretical studies of serpentine microstructures bonded to prestrained
intrinsically stretchable polymer semiconductors. In addition to the elastomers for stretchable electronics. Adv Funct Mater 2014;24:2018–37.
appropriate distribution of both crystalline and amorphous regions, [20] Wang Z, Zhang L, Duan S, Jiang H, Shen J, Li C. Kirigami-patterned highly
fibril and intertangled high Mn tie chains that interpenetrate the stretchable conductors from flexible carbon nanotube-embedded polymer
films. J Mater Chem C 2017;5:8714–22.
crystalline domains between deformable amorphous domains is [21] Huang X, Liu Y, Cheng H, Shin WJ, Fan JA, Liu Z, et al. Materials and designs for
important for efficient charge transport. Thin film morphology wireless epidermal sensors of hydration and strain. Adv Funct Mater
could be altered by tuning Mn and regioregularity in polymer 2014;24:3846–54.
[22] Lee J, Wu J, Ryu H, Liu Z, Meitl M, Zhang YW, et al. Stretchable semiconductor
properties and structural modifications of polymer backbone and
technologies with high areal coverages and strain-limiting behavior:
side chains. The advances in synthetic chemistry and processing demonstration in high-efficiency dual-junction GaInP/GaAs photovoltaics.
techniques should enable fine control of these parameters and con- Small 2012;8:1851–6.
tribute to the realization of practical devices. Recent priority field in [23] Song J, Huang Y, Xiao J, Wang S, Hwang KC, Ko HC, et al. Mechanics of
noncoplanar mesh design for stretchable electronic circuits. J Appl Phys
organic electronics is shifted to next-generation wearable and skin 2009;105, 123516/1-6.
electronics, which require precisely assembled high performance [24] Kim DH, Ahn JH, Choi WM, Kim HS, Kim TH, Song JZ, et al. Stretchable and
TFT arrays responding to subtle external signals. On the basis of foldable silicon integrated circuits. Science 2008;320:507–11.
[25] Khang DY, Jiang H, Huang Y, Rogers JA. A stretchable form of single-crystal
recent progress of hole-transporting polymers as described in this silicon for high-performance electronics on rubber substrates. Science
trend article, next target should move to be electron-transporting 2006;311:208–12.
and ambipolar stretchable polymers for the development of organic [26] Fan H, Li K, Li Q, Hou C, Zhang Q, Li Y, et al. Prepolymerization-assisted
fabrication of an ultrathin immobilized layer to realize a semiembedded
complementary circuits in flexible and mechanically robust elec- wrinkled AgNW network for a smart electrothermal chromatic display and
tronics. actuator. J Mater Chem C 2017;5:9778–85.
[27] Kim Y, Zhu J, Yeom B, Di Prima M, Su X, Kim JG, et al. Stretchable nanoparticle
conductors with self-organized conductive pathways. Nature
2013;500:59–63.
Declaration of Competing Interest [28] Lipomi DJ, Vosgueritchian M, Tee BCK, Hellstrom SL, Lee JA, Fox CH, et al.
Skin-like pressure and strain sensors based on transparent elastic films of
The authors declare that they have no known competing finan- carbon nanotubes. Nat Nanothchnol 2011;6:788–92.
[29] Choi D, Kim H, Persson N, Chu PH, Chang M, Kang JH, et al.
cial interests or personal relationships that could have appeared to Elastomer–Polymer semiconductor blends for high-performance stretchable
influence the work reported in this paper. charge transport networks. Chem Mater 2016;28:1196–204.
 M. Ashizawa, Y. Zheng, H. Tran et al. / Progress in Polymer Science 100 (2020) 101181 9

[30] Sun T, Scott JI, Wang M, Kline RJ, Bazan GC, O‘Connor BT. Plastic deformation [52] Zhang X, Bronstein H, Kronemeijer AJ, Smith J, Kim Y, Kline RJ, et al. Molecular
of polymer blends as a means to achieve stretchable organic transistors. Adv origin of high field-effect mobility in an
Electron Mater 2016;2, 1500388/1-10. indacenodithiophene–benzothiadiazole copolymer. Nat Commun 2014;4,
[31] Chu PH, Wang G, Fu B, Choi D, Park JO, Srinivasarao M, et al. Synergistic effect 2238/1-9.
of regioregular and regiorandom poly(3-hexylthiophene) blends for high [53] Son SY, Kim Y, Lee J, Lee GY, Park WT, Noh YY, et al. High-field-Effect mobility
performance flexible organic field effect transistors. Adv Electron Mater of low-crystallinity conjugated polymers with localized aggregates. J Am
2016;2, 1500384/1-12. Chem Soc 2016;138:8096–103.
[32] Xu J, Wang SH, Wang GJN, Zhu CX, Luo SC, Jin LH, et al. Highly stretchable [54] Venkateshvaran D, Nikolka M, Sadhanala A, Lemaur V, Zelazny M, Kepa M,
polymer semiconductor films through the nanoconfinement effect. Science et al. Approaching disorder-free transport in high-mobility conjugated
2017;355:59–64. polymers. Nature 2014;515:384–8.
[33] Wang Y, Zhu C, Pfattner R, Yan H, Jin L, Chen S, et al. A highly stretchable, [55] Terao J, Wadahama A, Matono A, Tada T, Watanabe S, Seki S, et al. Design
transparent, and conductive polymer. Sci Adv 2017;3, e1602076/1-10. principle for increasing charge mobility of ␲-conjugated polymers using
[34] Lee Y, Shin M, Thiyagarajan K, Jeong U. Approaches to stretchable polymer regularly localized molecular orbitals. Nat Commun 2013;4, 1691/1-9.
active channels for deformable transistors. Macromolecules 2016;49: [56] Noriega R, Rivnay J, Vandewel K, Koch FPV, Stingelin N, Smith P, et al. A
433–44. general relationship between disorder, aggregation and charge transport in
[35] Hendriks KH, Li W, Heintges GHL, Van Pruissen GWP, Wienk MM, Janssen RAJ. conjugated polymers. Nat Mater 2013;12:1038–44.
Homocoupling defects in diketopyrrolopyrrole-based copolymers and their [57] Kang I, Yun HJ, Chung DS, Kwon SK, Kim YH. Record high hole mobility in
eff ;ect on photovoltaic performance. J Am Chem Soc 2014;136:11128–33. polymer semiconductors via Side-Chain Engineering. J Am Chem Soc
[36] Wakioka M, Takahashi R, Ichihara N, Ozawa F. Mixed-ligand approach to 2013;135:14896–9.
palladium-catalyzed direct arylation polymerization: highly selective [58] Beaujuge PM, Fréchet MJ. Molecular design and ordering effects in
synthesis of ␲-conjugated polymers with diketopyrrolopyrrole units. ␲-Functional materials for transistor and solar cell applications. J Am Chem
Macromolecules 2017;50:927–34. Soc 2011;133:20009–29.
[37] Hu H, Zhao K, Fernandes N, Boufflet P, Bannock JH, Yu L, et al. Entanglements [59] Mei J, Kim DH, Ayzner AL, Toney MF, Bao Z. Siloxane-terminated solubilizing
in marginal solutions: a means of tuning pre-aggregation of conjugated side chains: bringing conjugated polymer backbones closer and boosting hole
polymers with positive implications for charge transport. J Mater Chem C mobilities in thin-film transistors. J Am Chem Soc 2011;133:20130–3.
2015;3:7394–404. [60] Zhao Y, Zhao X, Zang Y, Di C, Diao Y, Mei J. Conjugation-break spacers in
[38] Matthews JR, Niu W, Tandia A, Wallace AL, Hu J, Lee WY, et al. Scalable semiconducting polymers: impact on polymer processability and charge
synthesis of fused thiophene-diketopyrrolopyrrole semiconducting polymers transport properties. Macromolecules 2015;48:2048–53.
processed from nonchlorinated solvents into high performance thin film [61] Schroeder BC, Chio YC, Gu X, Zhou Y, Xu J, Lopez J, et al. Non-conjugated
transistors. Chem Mater 2013;25:782–9. flexible linkers in semiconducting polymers: a pathway to improved
[39] Li J, Zhao Y, Tan HS, Guo Y, Di CA, Gui Yu, et al. A stable solution-processed processability without compromising device performance. Adv Electron
polymer semiconductor with record high-mobility for printed transistors. Sci Mater 2016;2, 1600104/1-10.
Rep 2012;2, 754/1-9. [62] Zhao Y, Zhao X, Roders M, Gumyusenge A, Ayzner AL, Mei J. Melt-processing
[40] Zhang X, Richter LJ, DeLongchamp DM, Kline RJ, Hammond MR, McCulloch I, of complementary semiconducting polymer blends for high performance
et al. Molecular packing of high-mobility diketo pyrrolo-pyrrole polymer organic transistors. Adv Mater 2017;29, 1605056/1-7.
semiconductors with branched alkyl side chains. J Am Chem Soc [63] Zhao Y, Gumyusenge A, He J, Qu G, McNutt WW, Long Y, et al. Continuous
2011;133:15073–84. melt-drawing of highly aligned flexible and stretchable semiconducting
[41] Kline RJ, McGehee MD, Kadnikova EN, Liu J, Fréchet JMJ, Toney MF. microfibers for organic electronics. Adv Funct Mater 2018;28, 1705584/1-9.
Dependence of regioregular poly(3-hexylthiophene) film morphology and [64] Zhao Y, Zhao W, Roders M, Qu G, Diao Y, Ayzner AL, et al. Complementary
field-effect mobility on molecular weight. Macromolecules 2005;38:3312–9. semiconducting polymer blends for efficient charge transport. Chem Mater
[42] Zen A, Pflaum J, Hirschmann S, Zhuang W, Jaiser F, Asawapirom U, et al. Effect 2015;17:7164–70.
of molecular weight and annealing of poly(3-hexylthiophene)s on the [65] Zhao X, Zhao Y, Ge Q, Butrouna K, Diao Y, Graham KR, et al. Complementary
performance of organic field-effect transistors. Adv Funct Mater semiconducting polymer blends: the influence of conjugation-break spacer
2004;14:757–64. length in matrix polymers. Macromolecules 2016;49:2601–8.
[43] Rodriques D, Kim JH, Root SE, Fei Z, Boufflet P, Heeney M, et al. Comparison of [66] Savagatrup S, Zhao X, Chan E, Mei J, Lipomi DJ. Effect of broken conjugation on
methods for determining the mechanical properties of semiconducting the stretchability of semiconducting polymers. Macromol Rapid Commun
polymer films for stretchable electronics. ACS Appl Mater Interface 2016;29:1623–8.
2017;9:8855–62. [67] Sun JY, Zhao X, IIIeperuma WRK, Chaudhuri O, Oh KH, Mooney DJ, et al. Highly
[44] Bao Z, Dodabalapur A, Lovinger AJ. Soluble and processable regioregular stretchable and tough hydrogels. Nature 2012;489:133–6.
poly(3-hexylthiophene) for thin film field-effect transistor applications with [68] Li CH, Wang C, Keplinger C, Zuo JL, Jin L, Sun Y, et al. A highly stretchable
high mobility. Appl Phys Lett 1996;69:4108–10. autonomous self-healing elastomer. Nat Chem 2016;8:618–24.
[45] Koch FPV, Rivnay J, Foster S, Müller C, Downing JM, Buchaca-Domingo E, et al. [69] Oh JY, Rondeau-Gagné S, Chiu Y, Chortos A, Lissel F, Wang GJN, et al.
The impact of molecular weight on microstructure and charge transport in Intrinsically stretchable and healable semiconducting polymer for organic
semicrystalline polymer semiconductors–poly(3-hexylthiophene), a model transistors. Nature 2016;539:411–5.
study. Prog Polym Sci 2013;38:1978–89. [70] Lu C, Lee WY, Gu X, Xu J, Chou HH, Yan H, et al. Effects of molecular structure
[46] Mazzio KA, Rice AH, Durban MM, Lusconbe CK. Eff ;ect of regioregularity on and packing order on the stretchability of semicrystalline conjugated
charge transport and structural and excitonic coherence in poly(tetrathienoacene-diketopyrrolopyrrole) polymers. Adv Electron Mater
poly(3-hexylthiophene) nanowires. J Phys Chem C 2015;119:14911–8. 2017;3, 1600311/1-13.
[47] McCullough RD, Lowe RD, Jayaraman M, Anderson DL. Design, synthesis, and [71] Wu HC, Benight SJ, Chortos A, Lee WY, Mei J, To WF, et al. A rapid and facile
control of conducting polymer architectures: structurally homogeneous soft contact lamination method: evaluation of polymer semiconductors for
poly(3-alkylthiophenes). J Org Chem 1993;58:904–12. stretchable transistors. Chem Mater 2014;26:4544–51.
[48] Loewe RS, Khersonsky SM, McCullough RD. A simple method to prepare [72] Roth B, Savagatrup S, de los Santos NV, Hagemann O, Carle JE, Halgesen M,
head-to-Tail coupled, regioregular poly(3-alkylthiophenes) using grignard et al. Mechanical properties of a library of low-band-gap polymers. Chem
metathesis. Adv Mater 1999;11:250–3. Mater 2016;28:2363–73.
[49] Kim JS, Kim JH, Kang TE, Lee W, Yu H, Kim HJ, et al. Tuning mechanical and [73] Savagatrup S, Makaram AS, Burke DJ, Lipomi DJ. Mechanical properties of
optoelectrical properties of poly(3-hexylthiophene) through systematic conjugated polymers and polymer-fullerene composites as a function of
regioregularity control. Macromolecules 2015;48:4339–46. molecular structure. Adv Funct Mater 2014;24:1169–81.
[50] O‘Connor B, Chan EP, Chan C, Conrad BR, Richter LJ, Kline RJ, et al. Correlations [74] Savagatrup S, Printz AD, Rodriquez D, Lipomi DJ. Best of both worlds:
between mechanical and electrical properties of Polythiophenes. ACS Nano conjugated polymers exhibiting good photovoltaic behavior and high tensile
2010;4:7538–44. elasticity. Macromolecules 2014;26:1981–92.
[51] Printz AD, Lipomi DJ. Competition between deformability and charge [75] Wen H, Wu H, Aimi J, Hung C, Chiang Y, Kuo C, et al. Soft poly(butyl acrylate)
transport in semiconducting polymers for flexible and stretchable electronics. side chains toward intrinsically stretchable polymeric semiconductors for
Appl Phys Rev 2016;3, 021302/1-17. field-effect transistor applications. Macromolecules 2017;50:4982–92.