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The local, nanoscale organization of crystallites in conjugated polymers is often critical to determining the charge transport properties of the system. Block copolymer geometries, which offer controlled nanostructures with tethering of chains at interfaces, are an ideal platform to study the local organization of conjugated polymer crystallites. The model conjugated polymer poly(3-(2'-ethyl)hexylthiophene) (P3EHT) features a depressed melting temperature relative to the widely studied poly(3-hexylthiophene) (P3HT), which allows it to robustly form microphase-separated domains that confine the subsequent P3EHT crystallites. Importantly, P3EHT crystallization in confinement is coupled to a rubbery second block via interfacial tethering, mechanical properties, and chain stretching. Here, the impact of thermal processing on the diblock copolymer structure is examined to elucidate the key driving forces controlling the final coupled diblock copolymer and crystalline structures. Surprisingly, the diblock copolymer domain size is significantly impacted by the temperature at which the conjugated domain is crystallized. Decreasing amounts of domain extension are observed with increasing crystallization temperatures. This temperature-dependent domain structure appears to be correlated with the crystallization processes; these processes are inferred from precise changes in the lamellar structure across melting. By carefully tracking the changes in domain structure across melting, this work identifies three distinct regimes. We suggest a structural model of the conjugated block melting processes consisting of (I) excluded-chain relaxation, followed by (II) chain interdigitation during melt-recrystallization, and finally (III) complete melting that is independent of the initial crystallization conditions. These results suggest that P3EHT crystallization processes associated with temperature-dependent chain diffusion and nucleation are primarily responsible for the unexpected temperature-dependent crystallization behavior. They also emphasize that less perfect conjugated polymer crystals may actually be associated with a poorly interdigitated structure. Furthermore, this work demonstrates the utility of leveraging a diblock copolymer structure with a rubbery second block in order to precisely track changes in the crystallite structure. [ABSTRACT FROM AUTHOR]

Abstract: Rod–coil block copolymers are an increasingly important class of molecules for the self-assembly of functional polymer systems, many of which have rodlike chain conformations due to rigid secondary structures, extended π-conjugation, or aromatic groups along the polymer backbone. Examples of these polymers are helical proteins, polyisocyanates, main-chain semiconducting polymers, and aromatic polyesters, polyamides, or polyimines. Many hindered or liquid crystalline systems self-assembled from block copolymers, including dendronized polymers and mesogen-jacketed liquid crystalline polymers, also form rod–coil block copolymers. In these cases, steric crowding of the bulky or mesogenic side chains causes the polymer backbone to become quasi-linear. The incorporation of rigid rod polymers into the block copolymers results in extremely rich self-assembly behavior that differs markedly from that of traditional block copolymers due to the interplay between microphase separation of the rod and coil components and liquid crystalline alignment. The combination of these effects results in novel structures both in solution and melts. This review discusses in detail the self-assembly and thermodynamics of rod–coil diblock and triblock copolymers. After summarizing the applications of these materials, their aggregation and gelation in solution is discussed. Our knowledge of their bulk phase behavior is thoroughly reviewed both from the experimental and theoretical perspectives, and the self-assembly of these materials in thin film geometries that are critical to many applications in organic electronics and functional surface patterning is treated. Finally, the outlook for the future of these systems is summarized along with current knowledge gaps and exciting areas for the advancement of the field. [Copyright &y& Elsevier]

Abstract: The nanometer-scale architectures in thin films of self-assembling block copolymers have inspired a variety of new applications. For example, the uniformly sized and shaped nanodomains formed in the films have been used for nanolithography, nanoparticle synthesis, and high-density information storage media. Imperative to all of these applications, however, is a high degree of control over orientation of the nanodomains relative to the surface of the film as well as control over order in the plane of the film. Induced fields including electric, shear, and surface fields have been demonstrated to influence orientation. Both heteroepitaxy and graphoepitaxy can induce positional order on the nanodomains in the plane of the film. This article will briefly review a variety of mechanisms for gaining control over block copolymer order as well as many of the applications of these materials. Particular attention is paid to the potential of perfecting long-range two-dimensional order over a broader range of length scales and the extension of these concepts to functional materials and more complex architectures. [Copyright &y& Elsevier]

The article discusses the development in directing self-assembly of block copolymers. This study focused on the nanoscale features of block copolymers as means of turning a pattern media in microelectronic applications. Researches are under way for a new route to nanopatterning which is very significant in optical lithography. The semiconductor industry needs intrinsic technology to answer for the demands in high-density features for data storage and computing speed. New applications are tested for further developments.

Understanding the transport properties of water in self-assembled block copolymer morphologies is important for furthering the use of such materials as water-purifying membranes. In this study, we used coarse-grained dissipative particle dynamics simulations to clarify the influence of pore morphology on the self-diffusion of water in linear-triblock-copolymer membranes. We considered representative lamellar, cylindrical, and gyroid morphologies and present results for both the global and local diffusivities of water in the pores. Our results suggest that the diffusivity of water in the confined, polymer-coated pores differs from that in the unconfined bulk. Explicitly, in confinement, the mobility of water is reduced by the hydrodynamic friction arising from the hydrophilic blocks coating the pore walls. We demonstrate that in lamella and cylindrical morphologies, the latter effects can be rendered as a universal function of the pore size relative to the brush height of the hydrophilic blocks. [ABSTRACT FROM AUTHOR]

Tunability of polymer surface properties depends cruciallyon boththe chemical composition of the polymer and the physics of the chains(e.g., surface segregation, chain shape, etc.). Polypeptoids, whichare non-natural biomimetic polymers based on an N-substituted glycinebackbone, provide a flexible model system in which monomer sequence,chain shape, and self-assembled structure can easily be controlledto understand their influence on surface properties. We demonstratethe influence of the amount and sequence of hydrophobic monomers ina predominantly hydrophilic peptoid chain on the surface propertiesof a hybrid block copolymer, poly(peptoid-b-styrene).Just three fluorinated groups in peptoid sequences consisting of upto 45 hydrophilic monomers in length were needed to lower the surfaceenergy of the peptoid and allow for its maximal surface segregation.Positioning these fluorinated groups in the middle of a chain as opposedto the chain ends resulted in a change in chain conformation at thesurface as evidenced by near-edge X-ray absorption fine structurespectroscopy (NEXAFS). Surface reconstruction of polymers containingonly three fluorinated monomers occurred within seconds but couldbe slowed by an order of magnitude when five fluorinated monomerswere incorporated. [ABSTRACT FROM AUTHOR]

Controlling the self-assembly of block copolymers with variable chain shape and stiffness is important for driving the self-assembly of functional materials containing nonideal chains as well as for developing materials with new mesostructures and unique thermodynamic interactions. The polymer helix is a particularly important functional motif. In the helical chain, the traditional scaling relationships between local chain stiffness and space-filling properties are not applicable; this in turn impacts the scaling relationships critical for governing self-assembly. Polypeptoids, a class of sequence-defined peptidomimetic polymers with controlled helical secondary structure, were used to systematically investigate the impact of helical chain shape on block copolymer self-assembly in a series of poly(n-butyl acrylate)-b-polypeptoid block copolymers. Small-angle X-ray scattering (SAXS) of the bulk materials shows that block copolymers form hexagonally packed cylinder domains. By leveraging sequence control, the polypeptoid block was controlled to form a helix only at the part either adjacent to or distant from the block junction. Differences in domain size from SAXS reveal that chain stretching of the helix near the block junction is disfavored, while helical segments at the center of cylindrical domains contribute to unfavorable packing interactions, increasing domain size. Finally, temperature-dependent SAXS shows that helix-containing diblock copolymers disorder at lower temperatures than the equivalent unstructured diblock copolymers; we attribute this to the smaller effective N of the helical structure resulting in a larger entropic gain upon disordering. These results emphasize how current descriptions of rod/coil interactions and conformational asymmetry for coil polymers do not adequately address the behavior of chain secondary structures, where the scalings of space-filling and stiff--elastic properties relative to chain stiffness deviate from those of typical coil, semiflexible, and rodlike polymers. [ABSTRACT FROM AUTHOR]

Poly(dimethylsiloxane) (PDMS)- and poly(ethylene oxide) (PEO)-based block copolymer coatings functionalized with amphiphilic, surface-active, and sequence-controlled oligomer side chains were studied to directly compare the effects of hydrophilicity, hydrogen bonding, and monomer sequence on antifouling performance. Utilizing a modular coating architecture, structurally similar copolymers were used to make direct and meaningful comparisons. Amphiphilic character was imparted with non-natural oligopeptide and oligopeptoid pendant chains made from oligo-PEO and surface-segregating fluoroalkyl monomer units. Surface analysis revealed rearrangement for all surfaces when moved from vacuum to wet environments. X-ray photoelectron spectroscopy (XPS) spectra indicated that the polymer backbone and oligomer interactions play key roles in the surface presentation. Biofouling assays using the macroalga Ulva linza showed that the presence of peptoid side chains facilitated the removal of sporelings from the PDMS block copolymer, with removal matching that of a PDMS elastomer standard. The lack of a hydrogen bond donor in the peptoid backbone likely contributed to the lower adhesion strength of sporelings to these surfaces. Both the initial attachment and adhesion strength of the diatom Navicula incerta were lower on the coatings based on PEO than on those based on PDMS. On the PEO coating bearing the blocky peptoid sequence, initial attachment of N. incerta showed no measurable cell density. [ABSTRACT FROM AUTHOR]

Elucidating the relationship between chemical structure, morphology, and ionic conductivity is essential for designing novel high-performance materials for electrochemical applications. In this work, the effect of lamellar domain spacing (d) on ionic conductivity (σ) is investigated for a model system of hydrated diblock copolymer based on a protic polymerized ionic liquid. We present a strategy that allows for the synthesis of a well-defined series of narrowly dispersed PS-b-PIL with constant volume fraction of ionic liquid moieties (fIL ≈ 0.39) and with two types of mobile charge carriers: trifluoroacetate anions and protons. These materials self-assemble into ordered lamellar morphologies with variable domain spacing (ca. 20-70 nm) as demonstrated by small-angle X-ray scattering. PS-b-PIL membranes exhibit ionic conductivities above 10-4 S/cm at room temperature, which are independent of domain spacing consistent with their nearly identical water content. The conductivity scaling relationship demonstrated in this paper suggests that a mechanically robust membrane can be designed without compromising its ability to transport ions. In addition, PIL-based membranes exhibit low water uptake (λ ≈ 10) in comparison with many proton-conducting systems reported elsewhere. The low water content of the materials described herein makes them promising candidates for electrochemical devices operating in aqueous electrolytes at low current densities where moderate ion conduction and low product crossover are required. [ABSTRACT FROM AUTHOR]

ABSTRACT Charge transport in poly(3-alkylthiophene)s (P3AT)s is closely linked to the nanoscale organization of crystallites. Block copolymer morphologies provide an ideal platform to study crystallization as the chain ends are tethered at a known interface in a well-defined geometry. The impact of soft versus hard confinement on P3EHT crystallization was studied using poly(3-(2′-ethyl)hexylthiophene) (P3EHT) containing diblocks with both rubbery poly(methyl acrylate) (PMA) and glassy polystyrene (PS) blocks. Here, P3EHT's lower melting point relative to the commonly studied poly(3-hexylthiophene) (P3HT) facilitated its confined crystallization and makes it an ideal model system. While transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) revealed well-ordered lamellar morphologies both in the melt and post-crystallization for both sets of diblocks, the glassy blocks inhibit confined crystallization of P3EHT relative to rubbery matrix blocks. Analysis of aligned diblocks by both SAXS and wide angle X-ray scattering (WAXS) revealed that the P3EHT chain axis aligns perpendicular to domain interfaces, allowing preferential growth of the alkyl-chain and π-π stacking directions parallel to lamellae. Finally, it was shown that following diblock self-assembly in the melt, crystallite growth drives expansion of microdomains to match the P3EHT contour length. It was concluded that P3EHT chains adopted an extended conformation within confined crystallites due to the rigid nature of polythiophenes relative to flexible chain crystalline polymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 205-215 [ABSTRACT FROM AUTHOR]

Polymerized ionic-liquids (PILs) are promising materialswhoseionic properties can be tuned based on their chemistry. By incorporatingPILs into block copolymer (BCP) structures, it is possible to providecomplementary functionality (i.e., structural stability) and transporttunability to ion-conducting materials. In this study, we describethe self-assembly and conductivity of novel poly(styrene-block-histamine methacrylamide) diblock copolymers (PS-b-PHMA) and the resulting PS-b-PIL derivatives obtainedafter treatment with trifluoroacetic acid (TFA). These materials self-assembleinto ordered BCP structures with tunable domain sizes as demonstratedby small-angle X-ray scattering (SAXS) and transmission electron microscopy(TEM). PS-b-PHMA membranes show conductivities upto 2 × 10–4S/cm at room temperature, whichincrease byan order of magnitude in the presence of acid. In addition, both PHMA-and PIL-based membranes exhibit lower water uptake (λ = 4–6and 8–10, respectively) in comparison with most proton conductingmembranes reported elsewhere. The low water content in these membranestranslates into a stronger effect of morphology on transport behavior,resulting in a measurable increase in ion conductivity as a functionof conducting channel size. [ABSTRACT FROM AUTHOR]

Abstract: Block copolymer thin films with distinct morphologies are prepared by spin casting a nominally lamellar assay of poly(styrene-block-ethylene oxide) from a variety of solvents with and without salt doping. The 3-D morphologies of free-standing thin-film regions, which are obtained by casting directly onto holey substrates, are investigated in detail using various energy-filtering transmission electron microscopy techniques and by electron tomography. Surface characterization is achieved by atomic force microscopy. Our results demonstrate that in order to fully characterize the unique 3-D morphologies of the block copolymer thin films, a multi-method approach is required. When casting from a binary solvent, an unexpected layered honeycomb-type morphology is revealed, which likely results from an expansion of the poly(ethylene oxide) phase. A dramatic effect of selective cation coordination on the morphology of the as-cast block copolymer films is also directly observed. [Copyright &y& Elsevier]

Block copolymers with tunable compositions offer theability todirectly control the interaction strength between the two blocks andtherefore polymer properties. The miscibility of an A–B blockcopolymer can be increased by introducing B or B-like comonomers intothe A block, and literature has shown that both the amount and thedistribution of these comonomers affect the compatibility of the twoblocks. Sequence-defined block copolymers in which one can exactlycontrol the composition and comonomer distribution provide a uniqueopportunity to control the overall strength of segregation. Here,sequence-defined block copolymers have been synthesized via azide–alkynecoupling using polystyrene and sequence-specific polypeptoids (N-substitutedglycines) with 2-methoxyethyl side chains. These polystyrene-polypeptoidblock copolymers readily self-assemble into hexagonally packed andlamellar morphologies. N-(2-phenylethyl)glycine residues,which have a styrene-like side chain, were introduced throughout thepolypeptoid block to increase the compatibility with the polystyreneblock. As the compatibility increased, the strength of segregationand therefore the block copolymer order–disorder transitionsdecreased. The polystyrene–polypeptoid block copolymers providea tunable platform for further studies on the effect of compositionand sequence design on self-assembly and block copolymer properties. [ABSTRACT FROM AUTHOR]

The aqueous self-assembly of a sequence-specific bioinspired peptoid diblock copolymer into monodisperse superhelices is demonstrated to be the result of a hierarchical process, strongly dependent on the charging level of the molecule. The partially charged amphiphilic diblock copolypeptoid 30-mer, [N-(2-phenethyl)glycine]15-[N-(2-carboxyethyl)glycine]15, forms superhelices in high yields, with diameters of 624 ± 69 nm and lengths ranging from 2 to 20 μm. Chemical analogs coupled with X-ray scattering and crystallography of a model compound have been used to develop a hierarchical model of self-assembly. Lamellar stacks roll up to form a supramolecular double helical structure with the internal ordering of the stacks being mediated by crystalline aromatic side chain-side chain interactions within the hydrophobic block. The role of electrostatic and hydrogen bonding interactions in the hydrophilic block is also investigated and found to be important in the self-assembly process. [ABSTRACT FROM AUTHOR]