Liquid Crystalline Block Copolymers Research Articles

One-pot universal initiation-growth methods from a liquid crystalline block copolymer

The construction of hierarchical nanostructures with precise morphological and dimensional control has been one of the ultimate goals of contemporary materials science and chemistry, and the emulation of tailor-made nanoscale superstructures realized in the nature, using artificial building blocks, poses outstanding challenges. Herein we report a one-pot strategy to precisely synthesize hierarchical nanostructures through an in-situ initiation-growth process from a liquid crystalline block copolymer. The assembly process, analogous to living chain polymerization, can be triggered by small-molecule, macromolecule or even nanoobject initiators to produce various hierarchical superstructures with highly uniform morphologies and finely tunable dimensions. Because of the high degree of controllability and predictability, this assembly strategy opens the avenue to the design and construction of hierarchical structures with broad utility and accessibility.

Confined Self-Assembly Enables Stabilization and Patterning of Nanostructures in Liquid-Crystalline Block Copolymers

Various pathways have been utilized to manipulate microphase separation (MPS) of block copolymers, but the obtained MPS nanostructures are often suffering from poor thermal stability. Here, confined self-assembly is first adopted to thermally stabilize and conveniently pattern the MPS morphologies of an amphiphilic liquid-crystalline block copolymer (LCBC) composed of hydrophilic poly(ethylene oxide) (PEO) and hydrophobic azobenzene-containing polymethacrylate. The MPS nanostructures are thermally stabilized by top coating a layer of water-soluble polymer, sodium polystyrenesulfonate (PSSNa), as a result of coordination interaction between PEO and PSSNa. Interestingly, both thermal annealing and rubbing-treated polyimide film caused reorientation of mesogens in the PSSNa-coated LCBC film; however, the orientation of PEO nanocylinders remained unchangeable. This indicates that the PEO nanocylinders are selectively anchored by the PSSNa covering layer, regardless of the changes of mesogenic orientation. Thus, complicated hierarchical nanostructures can be fabricated effortlessly and preserved nondestructively by selected-area confined self-assembly or noncontact photopatterned technology due to the existence of photoresponsive azobenzene moieties.

Thin Film Self-Assembly of a Silicon-Containing Rod–Coil Liquid Crystalline Block Copolymer

The long-range ordering and directed self-assembly of thin films of a high interaction parameter rod–coil liquid crystalline block copolymer (LC BCP), poly(dimethylsiloxane)-b-poly{2,5-bis[(4-metho...

Liquid crystalline block copolymers as adaptive agents for compatibility between CdSe/ZnS quantum dots and low-molecular-weight liquid crystals

Liquid crystalline (LC) triblock copolymers were used either as (i) a nematic matrix, which can be loaded with 10 wt% of CdSe/ZnS QDs, or (ii) a compatibilizer, which allows more than 1 wt% of QDs to be introduced in low-molecular-weight cholesteric LCs.

Hierarchically ordered nanostructures of a supramolecular rod-coil block copolymer with a hydrogen-bonded discotic mesogen

Supramolecular liquid crystalline block copolymers prepared via hydrogen bonding exhibit hierarchical structures that can be tuned by varying the molar ratio of the discotic hydrogen-bonding acceptor to the block copolymer donor.

Self-assembly of a silicon-containing side-chain liquid crystalline block copolymer in bulk and in thin films: kinetic pathway of a cylinder to sphere transition.

The self-assembly of a high-χ silicon-containing side-chain liquid crystalline block copolymer (LC BCP) in bulk and in thin films is reported, and the structural transition process from the hexagonally packed cylinder (HEX) to the body-centered cubic structure (BCC) in thin films was examined by both reciprocal and real space experimental methods. The block copolymer, poly(dimethylsiloxane-b-11-(4'-cyanobiphenyl-4-yloxy)undecylmethacrylate) (PDMS-b-P(4CNB11C)MA) with a molecular weight of 19.5 kg mol-1 and a volume fraction of PDMS 27% self-assembled in bulk into a hierarchical nanostructure of sub-20 nm HEX cylinders of PDMS with the P(4CNB11C)MA block exhibiting a smectic LC phase with a 1.61 nm period. The structure remained HEX as the P(4CNB11C)MA block transformed to an isotropic phase at ∼120 °C. In the thin films, the PDMS cylindrical microdomains were oriented in layers parallel to the substrate surface. The LC block formed a smectic LC phase which transformed to an isotropic phase at ∼120 °C, and the microphase-separated nanostructure transformed from HEX to BCC spheres at ∼160 °C. The hierarchical structure as well as the dynamic structural transition of the thin films were characterized using in situ grazing-incidence small-angle X-ray scattering and grazing-incidence wide-angle X-ray scattering. The transient morphologies from the HEX to BCC structure in thin films were captured by scanning electron microscopy and atomic force microscopy, and the transition pathway was described.

Topology and ground-state degeneracy of tetrahedral smectic vesicles.

Chemical design of block copolymers makes it possible to create polymer vesicles with tunable microscopic structure. Here we focus on a model of a vesicle made of smectic liquid-crystalline block copolymers at zero temperature. The vesicle assumes a faceted tetrahedral shape and the smectic layers arrange in a stack of parallel straight lines with topological defects localized at the vertices. We counted the number of allowed states at [Formula: see text]. For any fixed shape, we found a two-dimensional countable degeneracy in the smectic pattern depending on the tilt angle between the smectic layers and the edge of the tetrahedral shell. For most values of the tilt angle, the smectic layers contain spiral topological defects. The system can spontaneously break chiral symmetry when the layers organize into spiral patterns, composed of a bound pair of +1/2 disclinations. Finally, we suggest possible applications of tetrahedral smectic vesicles in the context of functionalizing defects and the possible consequences of the spiral structures for the rigidity of the vesicle.

Orientation and Morphology Control of the Liquid Crystalline Block Copolymer Thin Film by Liquid Crystalline Solvent.

The critical challenge to engineer the morphological structures in the strongly phase-segregated block copolymer thin film is to overcome the preferential wetting of the blocks at the interface and direct the self-assembly process. Herein, we utilize surface activity and selective solvation of a nematic (N) liquid crystalline (LC) solvent, 5CB, to facilely alter the LC anchoring and the orientation of the nanophase separated structures of the smectic-nematic (S-N) LC block copolymer thin film. For the neat S-N diblock copolymer thin film, the nanostructures are parallel aligned. In contrast, with continuous introduction of 5CB into the system, the orientations of the characteristic nanostructures and the morphologies of the LC thin film can be consequently changed, yielding the perpendicularly oriented lamellar or cylindrical structures with the feature size below 10 nm. The homeotropic alignment of the 5CB nematics near the air interface plays a critical role to induce this unique behavior in the S-N/5CB systems, which offers an opportunity to fine-tune the interfacial structures and the morphological patterning in the block copolymer thin film.

Hierarchical Self‐Assembly in Liquid‐Crystalline Block Copolymers Enabled by Chirality Transfer

AbstractHelical topological structures are often found in chiral biological systems, but seldom in synthesized polymers. Now, controllable microphase separation of amphiphilic liquid‐crystalline block copolymers (LCBCs) consisting of hydrophilic poly(ethylene oxide) and hydrophobic azobenzene‐containing poly(methylacrylate) is combined with chirality transfer to fabricate helical nanostructures by doping with chiral additives (enantiopure tartaric acid). Through hydrogen‐bonding interactions, chirality is transferred from the dopant to the aggregation, which directs the hierarchical self‐assembly in the composite system. Upon optimized annealing condition, helical structures in film are fabricated by the induced aggregation chirality. The photoresponsive azobenzene mesogens in the LCBC assist photoregulation of the self‐assembled helical morphologies. This allows the construction and non‐contact manipulation of complicated nanostructures.

Hierarchical Self-Assembly in Liquid-Crystalline Block Copolymers Enabled by Chirality Transfer.

Helical topological structures are often found in chiral biological systems, but seldom in synthesized polymers. Now, controllable microphase separation of amphiphilic liquid-crystalline block copolymers (LCBCs) consisting of hydrophilic poly(ethylene oxide) and hydrophobic azobenzene-containing poly(methylacrylate) is combined with chirality transfer to fabricate helical nanostructures by doping with chiral additives (enantiopure tartaric acid). Through hydrogen-bonding interactions, chirality is transferred from the dopant to the aggregation, which directs the hierarchical self-assembly in the composite system. Upon optimized annealing condition, helical structures in film are fabricated by the induced aggregation chirality. The photoresponsive azobenzene mesogens in the LCBC assist photoregulation of the self-assembled helical morphologies. This allows the construction and non-contact manipulation of complicated nanostructures.

Cooperation of Amphiphilicity and Smectic Order in Regulating the Self-Assembly of Cholesterol-Functionalized Brush-Like Block Copolymers.

Nanoparticle morphology significantly affects the application of nanometer-scale materials. Understanding nanoparticle formation mechanisms and directing morphological control in nanoparticle self-assembly processes have received wide attention. Herein, a series of brush-like amphiphilic liquid crystalline block copolymers, PChEMA m- b-POEGMA n, containing cholesteryl mesogens with different hydrophobic/hydrophilic block ratios were designed and synthesized. The self-assembly behaviors of the resulting PChEMA m- b-POEGMA n block copolymers in different solvents (tetrahydrofuran/H2O, 1,4-dioxane/H2O, and N, N-dimethylformamide) were investigated in detail. Desirable micellar aggregates with well-organized architectures, including short cylindrical micelles, nanofibers, fringed platelets, and ellipsoidal vesicles with smectic micellar cores, were observed in 1,4-dioxane/H2O with an increasing hydrophobic block ratio. Although both amphiphilicity and smectic order governed the self-assembly, these two factors were differently balanced in the different solvents. This unique supramolecular system provides a new strategy for the design of advanced functional nanomaterials with tunable morphologies.

Random Planar Orientation in Liquid-Crystalline Block Copolymers with Azobenzene Side Chains by Surface Segregation.

Rodlike liquid-crystalline (LC) mesogens preferentially adopt a homeotropic orientation by excluded volume effects at the free surface in side-chain LC (SCLC) polymer films. The homeotropic orientation is not advantageous for in-plane LC alignment processes. Surface segregation of polymers is the phenomenon in which one component with a low surface free energy covers the surface in a mixture of two or more polymers or a block copolymer film. In SCLC block copolymer films, the surface segregation structure induces a random planar orientation due to the formation of a microphase-separated interface parallel to the substrate via the covering of one of the segregated polymer blocks. This feature article focuses on the unique, random planar orientation induced by the surface segregation of SCLC block copolymer films with the photoresponsive azobenzene (Az) mesogenic group. A transition moment of the Az mesogens is parallel to the molecular long axis, and light irradiation is conducted perpendicular to the film surface in general photoreaction processes. Therefore, the homeotropic molecular orientation in the SCLC polymer systems with Az mesogenic units inhibits efficient photoreaction reorientations in thin films. The random planar orientations by the surface segregation of a coil block in SCLC block polymers provide efficient in-plane photoreorientation and photoswitching with LC hierarchical mesostructures, such as microphase-separated structures of SCLC block copolymers and laminated LC polymer films. On the other hand, surface-segregated SCLC blocks form a high-density polymer LC brush layer with a random planar orientation by self-assembly, which exhibits efficient angular selective photoreactions. These approaches using the surface segregation of SCLC block copolymers are expected to offer new concepts for the LC photoalignment process for LC polymer devices.

Persistent Formation of Self-Assembled Cylindrical Structure in a Liquid Crystalline Block Copolymer Constructed by Hydrogen Bonding

A series of supramolecular liquid crystalline block copolymers (SLCBCPs) were prepared by hydrogen-bonding interaction between poly(dimethylsiloxane)-b-poly(2-vinylterephthalic acid) (PDMS-b-PM1H) and [4-(4′-hexyloxy)styryl]pyridine (NC6). PDMS-b-PM1H serves as the hydrogen-bonding donor and NC6 as the hydrogen-bonding acceptor. The SLCBCPs are obtained by mixing the hydrogen-bonding acceptor and donor in pyridine. Through increasing the molar ratio of pyridine to carboxyl, the SLCBCPs can transform from coil–coil block copolymers (BCPs) to rod–coil ones. When the ratio of pyridine to carboxylic acid is 0.50 or lower, the SLCBCPs are coil–coil-like. However, when the ratio exceeds 0.50, the SLCBCPs behave like rod–coil BCPs because the supramolecular block PM1H(NC6) exhibits liquid crystalline (LC) behavior owing to the “jacketing” effect. Small-angle X-ray scattering and transmission electron microscopy experiments were employed to characterize the microphase-separated nanostructures of the SLCBCPs. Inte...

Self-assembly of liquid-crystalline block copolymers in thin films: control of microdomain orientation

Block copolymer (BCP) lithography, as one of the most promising techniques for the next-generation integrated circuits, has been extensively investigated in recent years. Among the diverse types of BCPs, liquid-crystalline BCPs (LC-BCPs) formed by incorporating LC moieties into the BCPs have become increasingly attractive because of the tunable alignment of the LC chains. This review highlights the control of the microdomain orientation of PEO-b-PMA(Az) thin films via novel and convenient processing methods, including micropore extrusion and the introduction of polydimethylsiloxane (PDMS). Meanwhile, the mechanisms of the microdomain alignment transition are clarified and are closely related to the soft shearing field and the change in the block surface energy. Furthermore, some new perspectives for future research on the self-assembly of LC-BCP thin films are outlined from the point of view of material design, orientation control, and technological innovation. The facile control of the microdomain orientation in the liquid-crystalline block copolymer (LC-BCP) thin films has been realized by means of micropore extrusion and introducing polydimethylsiloxane (PDMS), instead of complicated processes or costly apparatus. In extrusion process, the alignment can be recovered via ultrasonicating the extruded BCP solution or as-placing upon long-time thermal annealing.

Formation of Anisotropic Liquid Crystalline Nanoparticles via Polymerization-Induced Hierarchical Self-Assembly.

Polymeric nanoparticles (NPs) containing liquid crystalline (LC) mesogens with tunable anisotropic morphologies have applications in various fields, but their preparation typically suffers from tedious and low-throughput approaches. Here we present an efficient route to the preparation of anisotropic morphologies of azobenzene-containing block copolymers (BCPs) at high solids content via a polymerization-induced hierarchical self-assembly in ethanol. Various anisotropic NPs, including cuboids, short belts, lamellae, and ellipsoidal vesicles, have been obtained in a remarkably broad range of BCP compositions. The NPs exhibit a smectic phase with ordered stripes when observed under TEM. This internal LC ordering plays a significant role on the formation of these intriguing anisotropic morphologies. Morphological transitions from anisotropic to isotropic spheres can be obtained upon UV illumination due to the photoresponsive properties of the azobenzene mesogens. This work significantly expands the scope of accessible morphologies in PISA and suggests that the under explored LC BCPs may have an impactful role in the PISA field.

RAFT Polymerization-Induced Self-Assembly as a Strategy for Versatile Synthesis of Semifluorinated Liquid-Crystalline Block Copolymer Nanoobjects.

Polymerization-induced self-assembly is demonstrated as a powerful platform for the synthesis of block copolymers comprising a semifluorinated liquid-crystalline block. This strategy transforms the deficiency of polymer insolubility encountered in traditional homogeneous solution protocols to the strength for dispersion polymerization, thus, enabling direct access to polymorphic block copolymer nanoobjects at high concentrations and with quantitative conversions. The versatility of this strategy is highlighted by polymerizations in a wide selection of inexpensive solvents, from nonpolar to highly polar, to afford various block copolymers with distinct combinations of amorphous/crystalline or hydrophilic/hydrophobic/fluorinated segments. The utility of the nanoparticles is demonstrated as robust Pickering emulsifiers for commonly considered good solvents.

Formation of ordered nanostructures in liquid-crystalline block copolymers with side-chain semiconductor materials

ABSTRACTWe developed a novel block copolymer composed of poly(ethylene oxide) (PEO) and polymethacrylate functionalized with liquid–cryst-alline oligothiophene by using the atom transfer radical polymerization (ATRP), aiming at application to organic photovoltaic (OPV) cells. Thermal investigation showed that the resultant polymer exhibits liquid–crystalline phases both on heating and cooling. Morphologies of the thin films of the block copolymer were investigated by atomic force microscopy (AFM). Microphase separation with a small size of almost 10 nm (nano-phase-separated structures) was observed upon annealing.

Hydrogen Bond Induces Hierarchical Self-Assembly in Liquid-Crystalline Block Copolymers.

Microphase-separated structures of block copolymers (BCs) with a size of sub-10 nm are usually obtained by hydrogen-bond-induced self-assembly of BCs through doping with small molecules as functional additives. Here, fabrication of hierarchically self-assembled sub-10 nm structures upon microphase separation of amphiphilic liquid-crystalline BCs (LCBCs) at the existence of hydrogen bonds but without any dopants is reported. The newly introduced urethane groups in the side chain of the hydrophobic block of LCBCs interact with the ether groups of the hydrophilic poly(ethylene oxide) (PEO) block, leading to imperfect crystallization of the PEO blocks. Both crystalline and amorphous domains coexist in the separated PEO phase, enabling a lamellar structure to appear inside the PEO nanocylinders. This provides an elegant method to fabricate controllable sub-10 nm microstructures in well-defined polymer systems without the introduction of any dopants.

Controlling orientational order in block copolymers using low-intensity magnetic fields

The interaction of fields with condensed matter during phase transitions produces a rich variety of physical phenomena. Self-assembly of liquid crystalline block copolymers (LC BCPs) in the presence of a magnetic field, for example, can result in highly oriented microstructures due to the LC BCP's anisotropic magnetic susceptibility. We show that such oriented mesophases can be produced using low-intensity fields (<0.5 T) that are accessible using permanent magnets, in contrast to the high fields (>4 T) and superconducting magnets required to date. Low-intensity field alignment is enabled by the addition of labile mesogens that coassemble with the system's nematic and smectic A mesophases. The alignment saturation field strength and alignment kinetics have pronounced dependences on the free mesogen concentration. Highly aligned states with orientation distribution coefficients close to unity were obtained at fields as small as 0.2 T. This remarkable field response originates in an enhancement of alignment kinetics due to a reduction in viscosity, and increased magnetostatic energy due to increases in grain size, in the presence of labile mesogens. These developments provide routes for controlling structural order in BCPs, including the possibility of producing nontrivial textures and patterns of alignment by locally screening fields using magnetic nanoparticles.

Thermotropic and Lyotropic Transitions of Concentrated Solutions of Liquid Crystalline Block Copolymers in a Liquid Crystalline Solvent

Rich phase structures and evolutions of the blends of smectic–nematic (S–N) liquid crystalline (LC) diblock copolymers and a nematic solvent (5CB) are investigated in a concentrated regime. These types of fully LC systems are macroscopically homogeneous with ordered phase-separated structures on the nanometer scale. By varying the temperature as well as the content of 5CB, the phase diagram of the blends is constructed, where the order-to-order transition (OOT) between lamellar and cylindrical nanostructures can be induced either lyotropically or thermotropically. The temperature and concentration dual-responsive properties are found to be closely related to the selectivity and distribution of 5CB, in addition to its phase transformation at the nematic–isotropic transition. As inferred from the miscibility and phase behaviors of its blends with the respective smectic and nematic homopolymers, the partition of 5CB in the S–N diblock copolymers and its influence on the phase structures reveal the important ...