A poly(3-hexylthiophene) block copolymer with macroscopically aligned hierarchical nanostructure induced by mechanical rubbing

Lim, Herman; Ho, Chun-Chi; Wu, Sheng-Hai; Tsai, Hung-Bin; Su, Wei‐Fang; Chao, Chi-Yang

doi:10.1039/c3cc43032d

Cited by 9 publications

(5 citation statements)

References 24 publications

(1 reference statement)

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“…The electrical properties of semiconducting polymers are intimately related to crystal orientation, which can be quantified by Hermans’ orientation factor, f H . Calculated from the first order alkyl stacking (1 0 0) peaks, these factors can range from −0.5 to +1, where 1 corresponds to perfectly oriented crystal planes perpendicular to the substrate (edge-on), −0.5 denotes a lattice plane strictly oriented parallel (face-on), and randomly oriented structures afford a value of 0.…”

Section: Resultsmentioning

confidence: 99%

“…The electrical properties of semiconducting polymers are intimately related to crystal orientation, which can be quantified by Hermans' orientation factor, f H . 40 Calculated from the first order alkyl stacking (1 0 0) peaks, these factors can range from −0.5 to +1, where 1 corresponds to perfectly oriented crystal planes perpendicular to the substrate (edge-on), −0.5 denotes a lattice plane strictly oriented parallel (face-on), and randomly oriented structures afford a value of 0. As shown in Table 1, compared with the other two patterned blade channel geometries, e.g., parallel and prismatic, the films obtained from the blade with wave-like channels provides for the highest f H at 0.64, suggesting a highly oriented microstructure with primarily edge-on orientation.…”

Section: ■ Resultsmentioning

confidence: 99%

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Conjugated Polymer Alignment: Synergisms Derived from Microfluidic Shear Design and UV Irradiation

Wang

Chu

et al. 2016

ACS Appl. Mater. Interfaces

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Solution shearing has attracted great interest for the fabrication of robust and reliable, high performance organic electronic devices, owing to applicability of the method to large area and continuous fabrication, as well as its propensity to enhance semiconductor charge transport characteristics. To date, effects of the design of the blade shear features (especially the microfluidic shear design) and the prospect of synergistically combining the shear approach with an alternate process strategy have not been investigated. Here, a generic thin film fabrication concept that enhanced conjugated polymer intermolecular alignment and aggregation, improved orientation (both nanoscale and long-range), and narrowed the π-π stacking distance is demonstrated for the first time. The impact of the design of shearing blade microfluidic channels and synergistic effects of fluid shearing design with concomitant irradiation strategies were demonstrated, enabling fabrication of polymer-based devices with requisite morphologies for a range of applications.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Resultsmentioning

confidence: 99%

Conjugated Polymer Alignment: Synergisms Derived from Microfluidic Shear Design and UV Irradiation

Wang

Chu

et al. 2016

ACS Appl. Mater. Interfaces

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“…Conjugated polymers tend to have high melting points, which are associated with close π-stacking which enables interchain charge transport. However, when these conjugated polymers are incorporated into diblock copolymer systems, these high melting points typically cause crystallization to dominate self-assembly. − Poly(3-(2′-ethyl)hexylthiophene) features accessible melting temperatures, while maintaining key features of the many more extensively studied conjugated polymers. − In particular, P3EHT in block copolymers leads to robust formation of microphase-separated morphologies and maintains them following crystallization . In lamellar diblock copolymer confinement, the P3EHT crystallite orientation is templated relative to the diblock interface.…”

Section: Introductionmentioning

confidence: 99%

Confined Crystallization within Cylindrical P3EHT Block Copolymer Microdomains

Davidson

Segalman

2017

Macromolecules

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Confinement of crystallites within block copolymer microdomains is a promising approach to study conjugated polymer crystallization due to interfacial chain tethering and defined geometries. The nanoscale organization of crystallites is often critical to determining the charge transport properties of conjugated polymers. Here, a poly(3-(2′-ethyl)hexylthiophene)block-poly(methyl acrylate) (P3EHT-b-PMA) system is leveraged to study the impact of confinement within cylindrical microdomains. The crystalline P3EHT permits accessible melting temperatures and robust formation of traditional microphaseseparated morphologies, while the rubbery PMA allows the local deformations required to permit P3EHT crystallization. Crystallites form with chains perpendicular to the diblock interface, causing domain expansion; TEM reveals that this is accommodated in the cylindrical geometry via local deformation. Complementary SAXS/WAXS of aligned diblocks shows preferential orientation of the alkyl chain stacks down domains. Furthermore, cylindrically confined P3EHT demonstrates a smaller window of thermal control over crystalline perfection via isothermal crystallization conditions than homopolymer P3EHT or block copolymer P3EHT in lamellar confinement. This work demonstrates that postcrystallization annealing is an alternative route to generating uniformly high quality crystallites in cylindrically confined P3EHT. These results are important for considering routes to optimizing and controlling crystallinity in nanoscale confined geometries.

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“…Very limited works related to P3HT-PI BCPs have been reported which suggested that PI could potentially modulate the packing of P3HT toward better organization. For example, our previous work demonstrated polyisoprene- block -poly(3-hexylthiophene)- block -polyisoprene (PI- b -P3HT- b -PI) triblock copolymers would enhance π–π stacking of P3HT in the spin-coated thin film as compared to the pristine P3HT. , Deribew et al utilized P3HT- b -PI diblock copolymers as compatibilizers in P3HT/PCBM bulk heterojunction solar cells to alter the crystallization of P3HT, leading to improved photovoltaic performance . Hereby, we aimed to synthesize P3HT- b -PI diblock and PI- b -P3HT- b -PI triblock copolymers with various compositions and to systematically explore the assembly behaviors of these BCPs.…”

Section: Introductionmentioning

confidence: 99%

Modulating Crystallinity of Poly(3-hexylthiophene) via Microphase Separation of Poly(3-hexylthiophene)–Polyisoprene Block Copolymers

Lim

Chao

2015

Macromolecules

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A series of poly(3-hexylthiophene)-block-polyisoprene (P3HTb-PI) diblock copolymers (DBCP) and polyisoprene-block-poly(3-hexylthiophene)-block-polyisoprene (PI-b-P3HT-b-PI) triblock copolymers (TBCP) with accurately controlled molecular architecture were synthesized via highly efficient coupling reaction between aldehyde end-functionalized P3HT and living anionic polyisoprene. The self-assembly behaviors, considering morphology and crystallinity, of the thermal annealed bulk samples of these DBCPs and TBCPs containing various PI content were systematically investigated. The DBCPs behaved very differently from most published P3HT BCP systems, showing elongated fibers with preserved crystallinity regardless of the PI fraction. More noteworthy, with PI fraction less than 40 wt %, the DBCPs exhibited parallel straight fibers longer than several micrometers accompanied by concurrent enhanced crystallinity. The unique microstructure of the DBCPs might originate from moderate microphase separation between P3HT and PI as well as high flexibility of PI to conduct the packing of P3HT. The TBCPs, by contrast, exhibited highly curved interdomain boundaries with significant depressed crystallinity, resembling P3HT diblock copolymers in the strong phase segregation regime, as more pronounced entanglement of the two terminal PI segments would restrict the movement of P3HT.

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A poly(3-hexylthiophene) block copolymer with macroscopically aligned hierarchical nanostructure induced by mechanical rubbing

Cited by 9 publications

References 24 publications

Conjugated Polymer Alignment: Synergisms Derived from Microfluidic Shear Design and UV Irradiation

Conjugated Polymer Alignment: Synergisms Derived from Microfluidic Shear Design and UV Irradiation

Confined Crystallization within Cylindrical P3EHT Block Copolymer Microdomains

Modulating Crystallinity of Poly(3-hexylthiophene) via Microphase Separation of Poly(3-hexylthiophene)–Polyisoprene Block Copolymers

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