Hierarchical Self-Assembly of Amphiphilic Semiconducting Polymers into Isolated, Bundled, and Branched Nanofibers

Kamps, Amanda C.; Fryd, Michael; Park, Soo‐Young

doi:10.1021/nn300385p

Cited by 141 publications

(190 citation statements)

References 58 publications

(85 reference statements)

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“…A variety of structurally diverse π-conjugated systems have been incorporated into RCPs including oligophenylene, 9 oligo(pvinylenephenylene), 10 oligo(p-benzamide), 11,12 polyfluorenes, 13,14 polythiophenes, 15,16 and poly(phenylquinolone). 17−19 Additionally, naturally occurring and synthetic helical macromolecules have been coupled with conventional random-coil polymers.…”

Section: ■ Introductionmentioning

confidence: 99%

Facile Synthesis of Rod–Coil Block Copolymers with Chiral, Helical Polycarbodiimide Segments via Postpolymerization CuAAC “Click” Coupling of Functional End Groups

et al. 2015

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Using the living nickel(II)-mediated polymerization of carbodiimides, the chiral (R)-or (S)-N-1-phenethyl-N′-methylcarbodiimide (PMC) monomers were polymerized with a new TIPS protected alkyne functional nickel initiator forming PPMC with an excess single-handed screw sense and the alkyne moiety covalently attached to the terminus of the polymer, as confirmed by 1 H NMR and MALDI-TOF MS. After deprotection, the alkyne end groups of rigid-rod PPMC-2 were coupled with azide-terminated, random-coil PS and PEG homopolymers forming a novel class of helical-b-coil block copolymers. In the thin-film, all synthesized diblock copolymers formed interesting nanofibular morphologies when subject to specific conditions. The triblock RCP-4, however, adopted unique macroporous morphology as identified by AFM and SEM with average pore diameters of ca. 832 ± 194 nm. The origin of this was found to be associated with the ordering of large, hollow vesicle aggregates upon solvent evaporation followed by the melting of these aggregates filling in the hollow interior forming the submicron pores observed. Furthermore, the size of these aggregates can be easily modulated in a linear fashion from 272 to 1648 nm simply by increasing the concentration of RCP-4 in THF. Finally, the three PPMC−PEG copolymers synthesized were found to adopt lyotropic cholesteric mesophases in concentrated toluene solutions (ca. 30 wt %). ■ INTRODUCTIONThe tunable self-assembly and microphase separation of conventional coil−coil block copolymer (CCP) have been studied and modeled extensively. 1,2 The ability to covalently bind polymers of varying composition and structure allows for the combination of polymer properties often with synergistic effects and expanded function. The self-assembly of these macromolecules is governed by a variety of noncovalent forces such as hydrophobic/hydrophilic interactions, electrostatic interactions, hydrogen bonding, and microphase separation. To date, directed block copolymer self-assembly remains as one of the most powerful, versatile methods of tailoring nanometer-size features.The synthesis of rigid rod-b-random coil block copolymers, however, has only recently attracted significant attention due to their unique capabilities to form stable supramolecular structures with a wide array of unique self-assembly behaviors observed in solution and the solid state. 3−6 The anisotropic nature of rigidrod blocks characteristically results in lyotropic/thermotropic liquid crystallinity with nematic or highly ordered smectic mesophases adopted in solution and/or in the melt. 7,8 Therefore, the assembly behaviors of rod−coil block copolymers (RCP) in solution and the solid state vastly differ from those of CCPs arising from a combination of microphase immiscibility of the two blocks and the self-organization behaviors of the rigid-rod block.

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Section: ■ Introductionmentioning

confidence: 99%

Facile Synthesis of Rod–Coil Block Copolymers with Chiral, Helical Polycarbodiimide Segments via Postpolymerization CuAAC “Click” Coupling of Functional End Groups

et al. 2015

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“…It was observed that the H4T1 amphiphilic diblock copolymer adopted random conformation in Figure 1a. 31 However, with increasing CH 3 OH solvent volume, the onedimensional nanofiber-like structure of H4T1 amphiphilic block copolymer with approximate 10 nm in width and length up to ∼500 nm (Figure 1b,c), and even a continuous, periodic lamellar structure ( Figure 1d) were observed. The bright and dark parts represented the P3HT-rich and P3TEGT-rich domains in the film respectively, driven by P3HT and P3TEGT crystallization for their different polarity of side chains and nanoscale phase separation.…”

Section: ■ Results and Discussionmentioning

confidence: 96%

“…Furthermore, the efficient PL quenching of H4T1 in DCB/CH 3 OH solvents was also indicative of tightly packed thiophene chains and strong interchain coupling in the polymer chains assemblies. 31 Earlier work on amphiphilic rod−rod diblock copolymers and their aggregation in mixtures of selective and nonselective solvents behavior was also processed in previous reports of Scherf. 33,34 A crucial requirement for high performance device was providing an efficient way to control the ordering of H4T1 amphiphilic block polymers with broadening optical absorbance in solid state.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

In Situ Fabricating One-Dimensional Donor–Acceptor Core–Shell Hybrid Nanobeams Network Driven by Self-Assembly of Diblock Copolythiophenes

et al. 2014

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In situ growth of cadmium sulfide (CdS) quantum dots (QDs) was achieved directly through solvent-assisted grafting in the self-assembled templates of amphiphilic all conjugated diblock copolythiophene, poly(3-hexylthiophene)-b-poly(3-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methylthiophene) (P3HT-b-P3TEGT) and gas−solid reaction. Such diblock polymer templates allowed a desired amount of cadmium sulfide salt (Cd(Ac) 2 ) to easily accomplish dispersion and self-assembly via controlled assembling block copolymers in selective solvents. After P3HT-b-P3TEGT polymer templates grafted with Cd 2+ precursor (P3HT-b-P3TEGT/Cd 2+ ) reacting in hydrogen sulfide (H 2 S) gas, one-dimensional core−shell nanobeams network P3HT-b-P3TEG/CdS (donor−acceptor) was formed with excellent phase separation between P3HT-b-P3TEGT crystalline domains and inorganic CdS QDs domains at nanoscales, which was driven by the interaction between oxygen atoms of ethylene oxide side chains and Cd 2+ ions, and the thermodynamic equilibrium between polymer chains deformation. The one-dimensional wire-like nanostructure were highly desirable for the active layers in photovoltaic devices as providing high carrier mobility, large interfacial area between electron donor and acceptor, and highly efficient transport pathways to improve the power conversion efficiency (PCE) of hybrid bulk heterojunction solar cells.

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“…insulating blocks as for example PMMA (P3HT-b-PMMA), [224] or poly(2-vinylpyridine) (P3HT-b-P2VP, [225][226][227][228][229] or P4VP (P3HT-b-P4VP), [230][231][232] or PEO (P3HT-b-PEO), [233][234][235][236][237][238][239][240][241][242] or polylactides (P3HT-b-PLA), [243] or polyacrylic acids (P3HT-b-PAA). [244,245] Also more special block copolymer with P3HT block were reported as for example azobenzene liquid crystalline mesogen, 6-(4-((4-methoxyphenyl)diazenyl)phenoxy)hexyl methacrylate (MMAZO) incorporated into a block copolymer with P3HT.…”

Section: Wwwadvancedsciencenewscommentioning

confidence: 99%

Hybrid Photovoltaics – from Fundamentals towards Application

Müller‐Buschbaum

Thelakkat

Fässler

et al. 2017

Advanced Energy Materials

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In hybrid photovoltaics, an organic and an inorganic semiconductor are combined in the active layer, with the advantages of both material classes in a single device. The organic component contributes towards the possibility for wet chemical device preparation with potentially low costs in combination with achieving flexible devices. From the inorganic component an increase in stability, as well as superior opto‐electronic properties, is added. Given the large diversity of organic and inorganic semiconductors, a large number of possible realizations of hybrid solar cells emerge. In the present review, we limit to hybrid solar cells which combine conjugated polymers with inorganic materials such as titanium dioxide, zinc oxide, silicon, germanium and quantum dots to keep focused. Particular emphasis is put on different routes to tailor nanostructures, such as the use of semiconductor block copolymers. The inorganic component is either synthesized directly in one of the blocks or added as a pre‐synthesized nanomaterial to form the hybrid material. Alternatively, the block copolymer is used as a structure‐directing template in a sol–gel synthesis approach to have tailored inorganic nanostructures, which are back‐filled with the organic component to fabricate the hybrid material. Hybrid solar cells based on crystalline Si are discussed for comparison.

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Hierarchical Self-Assembly of Amphiphilic Semiconducting Polymers into Isolated, Bundled, and Branched Nanofibers

Cited by 141 publications

References 58 publications

Facile Synthesis of Rod–Coil Block Copolymers with Chiral, Helical Polycarbodiimide Segments via Postpolymerization CuAAC “Click” Coupling of Functional End Groups

Facile Synthesis of Rod–Coil Block Copolymers with Chiral, Helical Polycarbodiimide Segments via Postpolymerization CuAAC “Click” Coupling of Functional End Groups

In Situ Fabricating One-Dimensional Donor–Acceptor Core–Shell Hybrid Nanobeams Network Driven by Self-Assembly of Diblock Copolythiophenes

Hybrid Photovoltaics – from Fundamentals towards Application

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