Synthesis and Deformable Hierarchical Nanostructure of Intrinsically

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Synthesis and Deformable Hierarchical Nanostructure of Intrinsically Stretchable ABA Triblock Copolymer Comprised of Poly(3-hexylthiophene) and Polyisobutylene Segments Tomoya Higashihara, Seijiro Fukuta, Yuto Ochiai, Tomohito Sekine, Keisuke Chino, Tomoyuki Koganezawa, and Itaru Osaka ACS Appl. Polym. Mater., Just Accepted Manuscript • DOI: 10.1021/acsapm.8b00087 • Publication Date (Web): 09 Jan 2019 Downloaded from http://pubs.acs.org on January 11, 2019

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ACS Applied Polymer Materials

Synthesis and Deformable Hierarchical Nanostructure of Intrinsically Stretchable ABA Triblock Copolymer Comprised of Poly(3-hexylthiophene) and Polyisobutylene Segments Tomoya Higashihara*,1, Seijiro Fukuta1, Yuto Ochiai1, Tomohito Sekine1, Keisuke Chino2, Tomoyuki Koganezawa3, and Itaru Osaka4 1Department

of Organic Material Systems, Graduate School of Science and Engineering, Yamagata University, 4-3-16

Jonan, Yonezawa, Yamagata 992-8510, Japan 2Chemicals

R&D Group, HPM Research & Development Department, High performance Materials Company, JXTG Oil &

Energy Corporation, 8, Chidoricho, Naka-ku, Yokohama, Kanagawa 231-0815, Japan 3Japan

Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan

4Department

of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527, Japan *e-mail: [email protected] Keywords: nanostructure, block copolymer, poly(3-hexylthiophene), polyisobutylene, stretchable, self-assembly

ABSTRACT: A novel intrinsically stretchable ABA triblock copolymer can be synthesized where A and B are poly(3-hexylthiophene) (P3HT) and polyisobutylene (PIB) segments, respectively. The deformation of the self-assembled hierarchical nanostructure of the block copolymer thin film was clearly observed by grazing incidence small- and wide-angle X-ray scattering.

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Block copolymers containing -conjugated polymer segments have received attention due to the potential application to organic electronics, exploiting the self-assembled nanostructures of microphase separation as well as crystalline domain formation.1-6 Pursuing soft matter electronics such as E-skins, biosensors, and wearable devices, the bucking scaffold approaches were reported based on the fine modification of device processing.7,8 On the other hand, the intrinsically stretchable semiconducting materials have recently been developed and fabricated to a conventional device structure, employing a blended system of semiconducting and elastomeric polymers.9 Taking into consideration the thermodynamically unstable nanostructures derived from such a blended system, the design of a block copolymer would be preferable. A wide variety of well-defined block copolymers composed of -conjugated polymer segments such as P3HT have been reported.10-14 L. Qiu and coworkers designed a semiconductor–rubber–semiconductor ABA triblock polymer where A and B were P3HT and poly(methacrylate) (PMA) segments, respectively.15 It behaves as a semiconducting elastomer with a Young's modulus (E) of 6 MPa and an elongation at break of 140%, exhibiting a hole mobility of 9 × 10−4 cm2V−1s−1. There have also been previous studies on such block copolymer approach for applying to stretchable electronic devices.16,17 Based on a similar design concept, we reported all-conjugated ABA triblock copolymers where A and B were P3HT and siloxane-containing polythiophene segments, respectively.18,19 However, the detailed deformative phenomena of the self-assembled nanostructure still remains unknown in such block copolymers. Here, we report the synthesis and deformable self-assembled nanostructure of an intrinsically stretchable ABA triblock copolymer composed of P3HT and PIB segments (P3HT-b-PIB-b-P3HT) for the first time. The advantages of choosing the PIB segment include its excellent elastomeric and thermal properties as well as a simple all-hydrocarbon structure without any heteroatoms, which might bring a better understanding in a morphological study, not being affected by polymer 2 ACS Paragon Plus Environment

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interactions through heteroatoms. According to Scheme 1, the ABA triblock copolymer was synthesized by a combination of quasi-living Kumada-Tamao catalyst-transfer polycondensation20,21 and living carbocationic polymerization.22,23

Scheme 1. Synthetic routes for P3HT-b-PIB-b-P3HT; bis(1-chloro-1-methylethyl)-5-tert-butyl benzene (1), ,-bifunctional PIB with allyl chloride groups (2), and -functional P3HT terminated by a bromide group (3).

First, isobutene was initiated with a bifunctional compound (1), followed by end-capping with 1,3-butadiene to to provide an ,-bifunctional PIB with allyl chloride groups (2).24,25 Then, the terminal allyl chloride groups were successfully transformed into azide groups by treatment with trimethylsilyl azide (TMS-N3, Mn = 41,800, ƉM = 1.27) and tetrabutylammonium fluoride (TBAF) to provide an ,-bifunctional PIB with azide groups (N3-PIB-N3). Second, an -functional P3HT 3 ACS Paragon Plus Environment


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terminated by a bromide group (3) was synthesized by Kumada-Tamao catalyst-transfer polycondensation of 2-bromo-5-chloromagnesio-3-hexylthiophene.26 Through the reaction of 3 with propargyl alcohol in the presence of potassium hydroxide, the -functional P3HT with a propargyl group (P3HT-Alkyne, Mn =13,700, ƉM = 1.10) was obtained. Third, the Huisgen cycloaddition reaction of N3-PIB-N3 and P3HT-Alkyne was conducted followed by HPLC fractionation to yield the desired comound P3HT-b-PIB-b-P3HT (Mn =65,500, ƉM = 1.53). All the SEC traces are shown in Figure S1. The chemical structure of P3HT-b-PIB-b-P3HT was confirmed by 1H NMR spectroscopy and the composition of P3HT was found to be 30 wt% (Figure S2). P3HT-b-PIB-b-P3HT showed high thermal stability (Td,1% = 365 °C) measured by thermogravimetric analysis (TGA) (Figure S3). Differential scanning calorimetry (DSC) displayed distinct transition temperatures for crystallizing and melting of the P3HT domains at 163 °C and 226 °C, respectively (Figure S4). In addition, the glass transition temperature (Tg) was observed at -67 °C attributable to the PIB domains. Thus, phase separation was revealed between the P3HT and PIB phases, although an exothermic peak was also found around 0 °C, probably suggesting the partly miscible domains of P3HT and PIB segments. The relative degree of crystallinity of the P3HT phase was calculated to be 63 wt% which is comparable to that of pristine P3HT.26 UV-vis absorption spectra of P3HT-b-PIB-b-P3HT and P3HT (Mn = 10,900, ƉM =1.11) were measured at thin film states (Figure S5). The spectrum of P3HT-b-PIB-bP3HT thin film showed two peaks at 522 nm and 550 nm with a shoulder at 598 nm, which was similar to that of P3HT. Notably, the shoulder peak possessed almost the same intensity as that of P3HT, implying comparable degree of crystallinity in the P3HT domain, which agreed well with the DSC results.

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Figure 1. (a) Tapping mode AFM phase image, (b) 2D GISAXS profile, (c) 1D IP GISAXS profile extracted from (b) along the qy direction, and (d) illustration of the phase-separated morphological image of the P3HT-b-PIB-b-P3HT thin film. To gain insight into the morphology of the P3HT-b-PIB-b-P3HT thin film, the tapping-mode atomic force microscope (AFM) was employed. Its phase image showed a nanofibrillar structure having a width of 25-30 nm (Figure 1(a)). The grazing incidence small-angle X-ray scattering (GISAXS) was also measured. The 2D profile of the GISAXS patterns for the P3HT-b-PIB-b-P3HT thin film shows distinct scattering spots only in the in-plane (IP) direction (Figure 1(b)). The 1D IP GISAXS profile shows well-defined scattering peak corresponding to a d-spacing of 28.3 nm, which was in good agreement with the domain width observed in AFM measurements (Figure 1(c)). The grazing incidence wide-angle X-ray scattering (GIWAXS) was also performed to identify the crystalline structure and its orientation (Figure S6). The results indicate that the P3HT-b-PIB-b5 ACS Paragon Plus Environment


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P3HT thin film possesses the P3HT crystalline domains aligning in edge-on rich orientation. Judging from the DSC, AFM, and grazing incidence X-ray scattering (GIXS), the P3HT-b-PIB-b-P3HT thin film creates a hierarchical nanostructure of vertically-aligned microphase separation in which P3HT crystalline domains align in an edge-on rich orientation (Figure 1(d)). To elucidate the deformation of such hierarchical nanostructure of the P3HT-b-PIB-b-P3HT thin film, it was transferred onto a poly(dimethylsiloxane) (PDMS) substrate from PEDOT:PSS-coated glasses using the reported method.27 The transferred films on PDMS substrates were then stretched at certain strains (ε = 0, 25, 50, 75, 100, and 200 %) and re-transferred onto a Si wafer for GIXS experiments. Figure 2(a) shows the 1D IP GISAXS profiles of the stretched samples with an X-ray beam parallel to the stretching direction extracted from the corresponding 2D profile (Figure S7(a)). When applying the strain from 0 to 200%, the scattering peak shifted to the high qy region (26.4 nm to 18.7 nm), which indicates that the d-spacing vertical to the strain direction decreased, probably due to the compressive force vertical to the strain direction. Note that there is a small gap between the d-spacings of phase-segregated domains before (28.3 nm) and after (26.4 nm at 0% strain) film transfer processes twice. On the other hand, when the stretched samples were irradiated by an Xray beam vertical to the stretching direction (Figure 2(b) and Figure S7(b)), the scattering peak split and one of the scattering peaks shifted to the low q region, indicating that the d-spacing parallel to the strain direction partly increased. This may be caused by the heterogeneous extension of the PIB domains to release the stress applied.


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Figure 2. GIXS data of the P3HT-b-PIB-b-P3HT thin film: 1D IP GISAXS profiles along the qy direction measured with an X-ray beam (a) parallel and (b) vertical to the strain direction, (c) 1D IP and (d) 1D OOP GIWAXS profiles along the qy direction measured with an X-ray beam parallel to the strain direction, (e) 1D IP and (f) 1D OOP GIWAXS profiles along the qy direction measured with an X-ray beam vertical to the strain direction.

The crystalline orientation of the P3HT phases of the P3HT-b-PIB-b-P3HT thin film was also influenced by the strain from 0 to 200% as measured by GIWAXS. Figures 2(c) and 2(d) show the 1D IP and out-of-plane (OOP) GIWAXS profiles of the stretched samples measured with an X-ray beam parallel to the stretching direction extracted from the corresponding 2D profiles (Figure S7(c)), 7 ACS Paragon Plus Environment


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respectively. There are distinct P3HT(100) and P3HT(010) scattering peaks around q = 3.85 nm-1 and q = 16.4 nm-1, respectively, both in all the IP and OOP GIWAXS profiles together with a broad amorphous halo from the PIB domains around q = 10 nm-1. It is obvious that the crystalline structure itself remains unchanged independent of the strain level because the scattering peaks never change their positions. Interestingly, the weak intensity of the P3HT(100) in the IP profiles increases by increasing the strain level, indicating the deformation of crystalline orientation from edge-on rich to bimodal. In sharp contrast, the 1D IP and OOP GIWAXS profiles of the stretched samples measured with an X-ray beam vertical to the stretching direction resulted in the opposite phenomenon, that is, the deformation of the crystalline orientation from edge-on rich to almost perfect edge-on, judging by the disappearance of the P3HT(100) scattering peak in the IP profile at 200% strain (Figures 2(e), 2(f), S7(d)). All the results of the GIXS experiments clearly revealed the deformation of both the microphase separated structure and the crystalline orientation of the P3HT-b-PIB-bP3HT thin film. The model for this deformation can be illustrated in Figure 3. In addition, the photograph of the bulk P3HT-b-PIB-b-P3HT film before and after stretching (Figure 3, upper left) shows a typical rubber-like behavior of repeatable expansion/contraction. To the best of our knowledge, this is the first report of the deformation of the hierarchical nanostructure of intrinsically-stretchable block copolymers containing poly(3-hexylthiophene) segments. The primitive results of organic thin film transistor (OTFT) characteristics based on the P3HT-b-PIB-b-P3HT thin film on a silicon substrate without applying the strain showed high charge carrier mobility of 3.0 x 10-3 cm2V−1s−1 with an on/oﬀ current ratio of 5,000 and a threshold voltage of -4.4 V, taking into consideration of 70% weight ratio of insulating PIB segment (Figure S8). When applying the surface strains of 0.5%, 1.0% and 1.5% to the flexible OTFT device onto a poly(ethylene terephthalate) (PEN) substrate28 using the P3HT-b-PIB-b-P3HT thin film, the drain current kept almost constant (Figure S9). These are indicative that the P3HT phase-separated domains form the networks for efficient charge transportation. The mechanical property of the bulk P3HT-b-PIB-b-P3HT film was 8 ACS Paragon Plus Environment

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examined by using the instrument of thermomechanical analysis (TMA) at room temperature. The film showed much lower tensile modulus of 1.14 MPa at the strain of 10% than that of typical pristine P3HT (rr ~98%) showing 930 M Pa.29 In conclusion, the novel ABA triblock copolymer where A and B are P3HT and PIB segments, P3HT-b-PIB-b-P3HT, was successfully synthesized by a combination of quasi-living KumadaTamao catalyst-transfer polycondensation and living carbocationic polymerization. The self-assembled hierarchical nanostructure of the P3HT-b-PIB-b-P3HT thin film with vertically-aligned microphase separation was clearly observed by DSC, AFM and GIXS experiments. In addition, it was turned out that some of PIB domains enlarged when applying the strain from 0 to 200% parallel to the polymer main chains, while the PIB domains shrinked with applying the strain vertical to the polymer main chains. On the other hand, P3HT crystalline orientation was also found deformable between bimodal and edge-on when applying the strain parallel and vertical to the polymer main chains, respectively. The detailed electronic performance when applying higher strain (>1.5%) onto poly(dimethylsiloxane) (PDMS) substrate is now under investigation.

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Figure 3. The photograph of the bulk P3HT-b-PIB-b-P3HT film before and after stretching (upper left) and the illustration of the model for the deformation of microphase separated structure and crystalline orientation of P3HT-b-PIB-b-P3HT thin film.

ASSOCIATED CONTENT Supporting Information Available: Experimental, SEC, 1H NMR, TGA, DSC, UV-vis spectroscopy, GIWAXS, and GISAXS of the P3HT-b-PIB-b-P3HT samples. These materials are available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author *Tomoya Higashihara, E-mail: [email protected] ACKNOWLEDGMENT This study was supported by Japan Society for the Promotion of Science (JSPS) (KAKENHI: Proposal No. 16H06049) and JXTG Oil & Energy Corporation. The synchrotron radiation experiments were performed at the BL46XU of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2015B1633, 2016B1572, and 2017A1767). S. Fukuta thanks Innovative Flex Course for Frontier Organic Material Systems (iFront) at Yamagata University for their financial support. We also thank Prof. Tsuyoshi Michinobu (Tokyo institute of technology) for HPLC fractionation. Valuable suggestions for the PIB synthesis with Prof. Rudolf Faust are gratefully acknowledged. We also thank Dr. Hiroaki Suzuki for discussing the mechanical property of the bulk polymer samples. REFERENCES 10 ACS Paragon Plus Environment

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Synthesis and Deformable Hierarchical Nanostructure of Intrinsically

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