Directed Self‐Assembly of Liquid‐Crystalline Molecular Building Blocks for Sub‐5 nm Nanopatterning

The thin‐film directed self‐assembly of molecular building blocks into oriented nanostructure arrays enables next‐generation lithography at the sub‐5 nm scale. Currently, the fabrication of inorganic arrays from molecular building blocks is restricted by the limited long‐range order and orientation of the materials, as well as suitable methodologies for creating lithographic templates at sub‐5 nm dimensions. In recent years, higher‐order liquid crystals have emerged as functional thin films for organic electronics, nanoporous membranes, and templated synthesis, which provide opportunities for their use as lithographic templates. By choosing examples from these fields, recent progress toward the design of molecular building blocks is highlighted, with an emphasis on liquid crystals, to access sub‐5 nm features, their directed self‐assembly into oriented thin films, and, importantly, the fabrication of inorganic arrays. Finally, future challenges regarding sub‐5 nm patterning with liquid crystals are discussed.     

Cover Picture: Bistable Nematic Liquid Crystals with Self‐Assembled Fibers (Adv. Mater. 6/2005)

The cover shows a recording process using nematic liquid crystal alignment. On p. 692, Kato and co‐workers report that reversibly bistable states have been achieved for nematic liquid crystals incorporating a small amount of self‐assembled fibers. Homeotropic monodomains and non‐aligned multidomains can be fixed and switched by thermal treatment in electric fields. The technique is applied to the formation of rewritable light scattering patterns, as shown on the cover.     

A UV‐Responsive Multifunctional Photoelectric Device Based on Discotic Columnar Nanostructures and Molecular Motors

Orientation control of ordered materials would not only produce new physical phenomenon but also facilitate the development of fancy devices. Discotic liquid crystals (DLCs) form 1D charge transport pathway by self‐organizing into columnar nanostructures via π–π stacking. However, controlling the electrical properties in such nanostructures with some direct and instant way is a formidable task for their high viscosity and insensitivity to external stimuli. Herein, the arbitrary control over electrical conductivity of such columnar nanostructures is achieved with UV light by incorporating DLCs with molecular motors. Highly ordered DLC microstripe arrays are generated on desired substrate through a capillary bridge dewetting strategy. The conductivity of the microstripes could be continuously modulated by 365 nm light due to the influence of molecular motion under UV irradiation on the electron orbital overlap of columnar nanostructures. This is so because the disorder degree of the DLC molecules is associated with the intensity of UV light and the doping concentration of molecular motors. Moreover, the device shows memory effect and reversible conductivity change. The DLC microstripe arrays are very promising for the applications in UV detectors, memory devices, optical switches, and so on.     

Tuning Molecular Self‐Assembly on Bulk Insulator Surfaces by Anchoring of the Organic Building Blocks

Molecular self‐assembly constitutes a versatile strategy for creating functional structures on surfaces. Tuning the subtle balance between intermolecular and molecule‐surface interactions allows structure formation to be tailored at the single‐molecule level. While metal surfaces usually exhibit interaction strengths in an energy range that favors molecular self‐assembly, dielectric surfaces having low surface energies often lack sufficient interactions with adsorbed molecules. As a consequence, application‐relevant, bulk insulating materials pose significant challenges when considering them as supporting substrates for molecular self‐assembly. Here, the current status of molecular self‐assembly on surfaces of wide‐bandgap dielectric crystals, investigated under ultrahigh vacuum conditions at room temperature, is reviewed. To address the major issues currently limiting the applicability of molecular self‐assembly principles in the case of dielectric surfaces, a systematic discussion of general strategies is provided for anchoring organic molecules to bulk insulating materials.     

Asymmetric Fullerene Nanosurfactant: Interface Engineering for Automatic Molecular Alignments

Since the molecular self‐assembly of nanomaterials is sensitive to their surface properties, the molecular packing structure on the surface is essential to build the desired chemical and physical properties of nanomaterials. Here, a new nanosurfactant is proposed for the automatic construction of macroscopic surface alignment layer for liquid crystal (LC) molecules. An asymmetric nanosurfactant (C₆₀NS) consisted of mesogenic cyanobiphenyl moieties with flexible alkyl chains and a [60]fullerene nanoatom is newly designed and precisely synthesized. The C₆₀NS directly introduced in the anisotropic LC medium is self‐assembled into the monolayered protrusions on the surface because of its amphiphilic nature originated by asymmetrically programmed structural motif of LC‐favoring moieties and LC‐repelling groups. The monolayered protrusions constructed by the phase‐separation and self‐assembly of asymmetric C₆₀NS nanosurfactant in the anisotropic LC media amplify and transfer the molecular orientational order from surface to bulk, and finally create the automatic vertical molecular alignment on the macroscopic length scale. The asymmetric C₆₀NS nanosurfactant and its self‐assembly described herein can offer the direct guideline of interface engineering for the automatic molecular alignments.     

Effect of the shape of imprinted alignment layer on the molecular orientation of liquid crystal

The molecular alignment of liquid crystals was studied with three different imprinted patterns. The three different shapes of molds (square-, V- and U-shaped) replicated the microstructures with electroplating process was fabricated. Surfaces with three different microgrooved patterns were used as the alignment layer of the liquid crystal cell. The effect of the shape of imprinted alignment layer on the molecular orientation of LC was investigated. Among these patterns, U-shaped groove pattern resulted in a high performance of liquid crystal orientation, pretilt angle and anchoring energy, which are quite comparable to the conventionally rubbed layer. It clearly shows that the molecular orientation of liquid crystals is influenced by the shape of microgrooved patterns.     

Liquid Crystals for Charge Transport,Luminescence, and Photonics

Ordered molecular materials are increasingly used in active electronic and photonic organic devices. In this progress report we discuss whether the self‐assembling properties and supramolecular structures of liquid crystals can be tailored to improve such devices. Recent developments in charge‐transporting and luminescent liquid crystals are discussed in the context of material requirements for organic light‐emitting devices, photovoltaics, and thin film transistors. We identify high carrier mobility, polarized emission, and enhanced output‐coupling as the key advantages of nematic and smectic liquid crystals for electroluminescence. The formation of anisotropic polymer networks gives the added benefits of multilayer capability and photopatternability. The anisotropic transport and high carrier mobilities of columnar liquid crystals make them promising candidates for photovoltaics and transistors. We also outline some of the issues in material design and processing that these applications demand. The photonic properties of chiral liquid crystals and their use as mirror‐less lasers are also discussed.     

Supramolecular Polymers: Rigid Dimers Formed through Strong Interdigitated H‐Bonds Yield Compact 1D Supramolecular Helical Polymers (Small 3/2011)

Hierarchical self‐assembly of small abiotic molecular modules interacting through noncovalent forces is increasingly being used to generate functional structures and materials for electronic, catalytic, and biomedical applications. The greatest control over the geometry in H‐bond supramolecular architectures, especially in H‐bonded supramolecular polymers, can be achieved by using conformationally rigid molecular modules undergoing self‐assembly through strong H‐bonds. Their binding strength depends on the multiplicity of the H‐bonds, the nature of donor/acceptor pairs and their secondary attractive/repulsive interactions. Here a functionalized molecular module is described, which is capable of self‐associating through self‐complementary H‐bonding patterns comprising four strong and two medium‐strength H‐bonds to form dimers. The self‐association of these phenylpyrimidine‐based dimers through directional H‐bonding between two lateral pyridin‐2(1H)‐one units of neighboring molecules allows the formation of highly compact 1D supramolecular polymers by self‐assembly on graphite. A concentration‐dependent study by scanning tunneling microscopy at the solid–liquid interface, corroborated by dispersion‐corrected density functional studies, reveals the controlled generation of either linear supramolecular 2D arrays, or long helical supramolecular polymers with a high shape persistence.     

Template‐Free,Surfactant‐Mediated Orientation of Self‐Assembled Supercrystals of Metal–Organic Framework Particles

Mesoscale self‐assembly of particles into supercrystals is important for the design of functional materials such as photonic and plasmonic crystals. However, while much progress has been made in self‐assembling supercrystals adopting diverse lattices and using different types of particles, controlling their growth orientation on surfaces has received limited success. Most of the latter orientation control has been achieved via templating methods in which lithographic processes are used to form a patterned surface that acts as a template for particle assembly. Herein, a template‐free method to self‐assemble (111)‐, (100)‐, and (110)‐oriented face‐centered cubic supercrystals of the metal–organic framework ZIF‐8 particles by adjusting the amount of surfactant (cetyltrimethylammonium bromide) used is described. It is shown that these supercrystals behave as photonic crystals whose properties depend on their growth orientation. This control on the orientation of the supercrystals dictates the orientation of the composing porous particles that might ultimately facilitate pore orientation on surfaces for designing membranes and sensors.     

Biopebble Containers: DNA‐Directed Surface Assembly of Mesoporous Silica Nanoparticles for Cell Studies

The development of methods for colloidal self‐assembly on solid surfaces is important for many applications in biomedical sciences. Toward this goal, described is a versatile class of mesoporous silica nanoparticles (MSN) that contain on their surface various types of DNA molecules to enable their self‐assembly into micropatterned surface architectures useful for cell studies. Monodisperse dye‐doped MSN are synthesized by biphase stratification and functionalized with an aptamer oligonucleotide that serves as gatekeeper for the triggered release of encapsulated molecular cargo, such as fluorescent dye rhodamine B or the anticancer drug doxorubicin. One or two additional types of oligonucleotides are installed on the MSN surface to enable DNA‐directed immobilization on solid substrates bearing patterns of complementary capture oligonucleotides. It is demonstrated that this strategy can be used for efficient self‐assembly of microstructured surface architectures, which not only promote the adhesion and guidance of cells but also are capable of affecting the fate of adhered cells through triggered release of their cargo. It is believed that this approach is useful for diverse applications in tissue engineering and nanobio sciences.     

A “Phase Separation” Molecular Design Strategy Towards Large‐Area 2D Molecular Crystals

2D molecular crystals (2DMCs) have attracted considerable attention because of their unique optoelectronic properties and potential applications. Taking advantage of the solution processability of organic semiconductors, solution self‐assembly is considered an effective way to grow large‐area 2DMCs. However, this route is largely blocked because a precise molecular design towards 2DMCs is missing and little is known about the relationship between 2D solution self‐assembly and molecular structure. A “phase separation” molecular design strategy towards 2DMCs is proposed and layer‐by‐layer growth of millimeter‐sized monolayer or few‐layer 2DMCs is realized. High‐performance organic phototransistors are constructed based on the 2DMCs with unprecedented photosensitivity (2.58 × 10⁷), high responsivity (1.91 × 10⁴ A W^?1), and high detectivity (4.93 × 10¹⁵ Jones). This “phase separation” molecular design strategy provides a guide for the design and synthesis of novel organic semiconductors that self‐assemble into large‐area 2DMCs for advanced organic (opto)electronics.     

Advances in Biological Liquid Crystals

Biological liquid crystals, a rich set of soft materials with rod‐like structures widely existing in nature, possess typical lyotropic liquid crystalline phase properties both in vitro (e.g., cellulose, peptides, and protein assemblies) and in vivo (e.g., cellular lipid membrane, packed DNA in bacteria, and aligned fibroblasts). Given the ability to undergo phase transition in response to various stimuli, numerous practices are exercised to spatially arrange biological liquid crystals. Here, a fundamental understanding of interactions between rod‐shaped biological building blocks and their orientational ordering across multiple length scales is addressed. Discussions are made with regard to the dependence of physical properties of nonmotile objects on the first‐order phase transition and the coexistence of multi‐phases in passive liquid crystalline systems. This work also focuses on how the applied physical stimuli drives the reorganization of constituent passive particles for a new steady‐state alignment. A number of recent progresses in the dynamics behaviors of active liquid crystals are presented, and particular attention is given to those self‐propelled animate elements, like the formation of motile topological defects, active turbulence, correlation of orientational ordering, and cellular functions. Finally, future implications and potential applications of the biological liquid crystalline materials are discussed.     

Dynamic Spirals of Nanoparticles in Light‐Responsive Polygonal Fields

Nanoparticles tend to aggregate once integrated into soft matter and consequently, self‐assembling nanoparticles into large‐scale, regular, well‐defined, and ultimately chiral patterns remains an ongoing challenge toward the design and realization of organized superstructures of nanoparticles. The patterns of nanoparticles that are reported in liquid crystals so far are all static, and this lack of responsiveness extends to assemblies of nanoparticles formed in topological singularities and other localized structures of anisotropic matter. Here, it is shown that gold nanoparticles form spiral superstructures in polygonal fields of cholesteric liquid crystals. Moreover, when the cholesteric liquid crystals incorporate molecular photoswitches in their composition, the pitch of the nanoparticulate spirals follows the light‐induced reorganization of the cholesteric liquid crystals. These experimental findings indicate that chiral liquid crystals can be used as chiral and dynamic templates for soft photonic nanomaterials. Controlling the geometry of these spirals of nanoparticles will ultimately allow modulating the plasmonic signature of hybrid and chiral systems.     

Graphene Oxide Liquid Crystals: Discovery,Evolution and Applications

The discovery and relevant research progress in graphene oxide liquid crystals (GOLCs), the latest class of 2D nanomaterials exhibiting colloidal liquid crystallinity arising from the intrinsic disc‐like shape anisotropy, is highlighted. GOLC has conferred a versatile platform for the development of novel properties and applications based on the facile controllability of molecular scale alignment. The first part of this review offers a brief introduction to LCs, including the theoretical background. Particular attention has been paid to the different types of LC phases that have been reported thus far, such as nematic, lamellar and chiral phases. Several key parameters governing the ultimate stability of GOLC behavior, including pH and ionic strength of aqueous dispersions are highlighted. In a relatively short span of time since its discovery, GOLCs have proved their remarkable potential in a broad spectrum of applications, including highly oriented wet‐spun fibers, self‐assembled nanocomposites, and architectures for energy storage devices. The second part of this review is devoted to an exclusive overview of the relevant applications. Finally, an outlook is provided into this newly emerging research field, where two well established scientific communities for carbon nanomaterials and liquid crystals are ideally merged.     

Controllable Growth of Graphene on Liquid Surfaces

Controllable fabrication of graphene is necessary for its practical application. Chemical vapor deposition (CVD) approaches based on solid metal substrates with morphology‐rich surfaces, such as copper (Cu) and nickel (Ni), suffer from the drawbacks of inhomogeneous nucleation and uncontrollable carbon precipitation. Liquid substrates offer a quasiatomically smooth surface, which enables the growth of uniform graphene layers. The fast surface diffusion rates also lead to unique growth and etching kinetics for achieving graphene grains with novel morphologies. The rheological surface endows the graphene grains with self‐adjusted rotation, alignment, and movement that are driven by specific interactions. The intermediary‐free transfer or the direct growth of graphene on insulated substrates is demonstrated using liquid metals. Here, the controllable growth process of graphene on a liquid surface to promote the development of attractive liquid CVD strategies is in focus. The exciting progress in controlled growth, etching, self‐assembly, and delivery of graphene on a liquid surface is presented and discussed in depth. In addition, prospects and further developments in these exciting fields of graphene growth on a liquid surface are discussed.     

Modulating the Mechanical Performance of Macroscale Fibers through Shear‐Induced Alignment and Assembly of Protein Nanofibrils

Protein‐based fibers are used by nature as high‐performance materials in a wide range of applications, including providing structural support, creating thermal insulation, and generating underwater adhesives. Such fibers are commonly generated through a hierarchical self‐assembly process, where the molecular building blocks are geometrically confined and aligned along the fiber axis to provide a high level of structural robustness. Here, this approach is mimicked by using a microfluidic spinning method to enable precise control over multiscale order during the assembly process of nanoscale protein nanofibrils into micro‐ and macroscale fibers. By varying the flow rates on chip, the degree of nanofibril alignment can be tuned, leading to an orientation index comparable to that of native silk. It is found that the Young's modulus of the resulting fibers increases with an increasing level of nanoscale alignment of the building blocks, suggesting that the mechanical properties of macroscopic fibers can be controlled through varying the level of ordering of the nanoscale building blocks. Capitalizing on strategies evolved by nature, the fabrication method allows for the controlled formation of macroscopic fibers and offers the potential to be applied for the generation of further novel bioinspired materials.     

Patterning of Lyotropic Chromonic Liquid Crystals by Photoalignment with Photonic Metamasks

Controlling supramolecular self‐assembly in water‐based solutions is an important problem of interdisciplinary character that impacts the development of many functional materials and systems. Significant progress in aqueous self‐assembly and templating has been demonstrated by using lyotropic chromonic liquid crystals (LCLCs) as these materials show spontaneous orientational order caused by unidirectional stacking of plank‐like molecules into elongated aggregates. In this work, it is demonstrated that the alignment direction of chromonic assemblies can be patterned into complex spatially‐varying structures with very high micrometer‐scale precision. The approach uses photoalignment with light beams that exhibit a spatially‐varying direction of light polarization. The state of polarization is imprinted into a layer of photosensitive dye that is protected against dissolution into the LCLC by a liquid crystalline polymer layer. The demonstrated level of control over the spatial orientation of LCLC opens opportunities for engineering materials and devices for optical and biological applications.     

Self‐Assembled α‐Cyanostilbenes for Advanced Functional Materials

In the specific context of condensed media, the significant and increasing recent interest in the α‐cyanostilbene (CS) motif [? Ar? CH?C(CN)? Ar? ] is relevant. These compounds have shown remarkable optical features in addition to interesting electrical properties, and hence they are recognized as very suitable and versatile options for the development of functional materials. This progress report is focused on current and future use of CS structures and molecular assemblies with the aim of exploring and developing for the next generations of functional materials. A critical selection of illustrative materials that contain the CS motif, including relevant subfamilies such as the dicyanodistyrylbenzene and 2,3,3‐triphenylacrylonitrile shows how, driven by the self‐assembly of CS blocks, a variety of properties, effects, and possibilities for practical applications can be offered to the scientific community, through different rational routes for the elaboration of advanced materials. A survey is provided on the research efforts directed toward promoting the self‐assembly of the solid state (polycrystalline solids, thin films, and single crystals), liquid crystals, nanostructures, and gels with multistimuli responsiveness, and applications for sensors, organic light‐emitting diodes, organic field effect transistors, organic lasers, solar cells, or bioimaging purposes.     

Negative‐Tone Block Copolymer Lithography by In Situ Surface Chemical Modification

Negative‐tone block copolymer (BCP) lithography based on in situ surface chemical modification is introduced as a highly efficient, versatile self‐assembled nanopatterning. BCP blends films consisting of end‐functionalized low molecular weight poly(styrene‐ran‐methyl methacrylate) and polystyrene‐block‐Poly(methyl methacylate) can produce surface vertical BCP nanodomains on various substrates without prior surface chemical treatment. Simple oxygen plasma treatment is employed to activate surface functional group formation at various substrates, where the end‐functionalized polymers can be covalently bonded during the thermal annealing of BCP thin films. The covalently bonded brush layer mediates neutral interfacial condition for vertical BCP nanodomain alignment. This straightforward approach for high aspect ratio, vertical self‐assembled nanodomain formation facilitates single step, site‐specific BCP nanopatterning widely useful for various substrates. Moreover, this approach is compatible with directed self‐assembly approaches to produce device oriented laterally ordered nanopatterns.     

Stimuli‐Driven Control of the Helical Axis of Self‐Organized Soft Helical Superstructures

Supramolecular and macromolecular functional helical superstructures are ubiquitous in nature and display an impressive catalog of intriguing and elegant properties and performances. In materials science, self‐organized soft helical superstructures, i.e., cholesteric liquid crystals (CLCs), serve as model systems toward the understanding of morphology‐ and orientation‐dependent properties of supramolecular dynamic helical architectures and their potential for technological applications. Moreover, most of the fascinating device applications of CLCs are primarily determined by different orientations of the helical axis. Here, the control of the helical axis orientation of CLCs and its dynamic switching in two and three dimensions using different external stimuli are summarized. Electric‐field‐, magnetic‐field‐, and light‐irradiation‐driven orientation control and reorientation of the helical axis of CLCs are described and highlighted. Different techniques and strategies developed to achieve a uniform lying helix structure are explored. Helical axis control in recently developed heliconical cholesteric systems is examined. The control of the helical axis orientation in spherical geometries such as microdroplets and microshells fabricated from these enticing photonic fluids is also explored. Future challenges and opportunities in this exciting area involving anisotropic chiral liquids are then discussed.