Planar Anchoring of C70 Liquid Crystals Using a Covalent Organic Framework Template

The surface‐induced anchoring effect is a well‐developed technique to control the growth of liquid crystals (LCs). Nevertheless, a defined nanometer‐scale template has never been used to induce the anchored growth of LCs with molecular building units. Scanning tunneling microscopy results at the solid/liquid interface reveal that a 2D covalent organic framework (COF‐1) can offer an anchoring effect to template C₇₀ molecules into forming several LC mesophases, which cannot be obtained under other conditions. Through comparison with the C₆₀ system, a stepwise breakdown in ordering of C₇₀ LC is observed. The process is described in terms of the effects of molecular anisotropy on the epitaxial growth of molecular crystals. The results suggest that using a surface‐confined template to anchor the initial layer of LC molecules can be a modular and potentially broadly applicable approach for organizing molecular mesogens into LCs.     

Investigation of the liquid crystal alignment layer: effect on electrical properties

We investigate the electrical behavior of a symmetric liquid crystal (LC) cell: elecrode-silane-LC-silane-electrode. The silane (chlorodimethyloctadecyl-silane) layer induces a homeotropic orientation of the nematic liquid crystal (NLC) molecules. The wettability technique is used to detect the change of the surface energy of the electrode upon cleaning and silane layer deposition. We report on the dynamic impedance measurements of the nematic liquid crystal cell. It is found that the silane alignment layer has a blocking effect on the liquid crystal (LC) cell. We also study the relaxation behavior of the cell which is later assimilated as an electrical equivalent circuit.     

Investigation of the liquid crystal alignment layer: effect on electrical properties

Abstract

We investigate the electrical behavior of a symmetric liquid crystal (LC) cell: elecrode-silane-LC-silane-electrode. The silane (chlorodimethyloctadecyl-silane) layer induces a homeotropic orientation of the nematic liquid crystal (NLC) molecules. The wettability technique is used to detect the change of the surface energy of the electrode upon cleaning and silane layer deposition. We report on the dynamic impedance measurements of the nematic liquid crystal cell. It is found that the silane alignment layer has a blocking effect on the liquid crystal (LC) cell. We also study the relaxation behavior of the cell which is later assimilated as an electrical equivalent circuit.     

Scalable Synthesis of Switchable Assemblies of Gold Nanorod Lyotropic Liquid Crystal Nanocomposites

A new class of solvent free, lyotropic liquid crystal nanocomposites based on gold nanorods (AuNRs) with high nanorod content is reported. Application of shear results in switchable, highly ordered alignment of the nanorods over several centimeters with excellent storage stability for months. For the synthesis, AuNRs are surface functionalized with a charged, covalently tethered corona, which induces fluid‐like properties. This honey‐like material can be deposited on a substrate and a high orientational order parameter of 0.72 is achieved using a simple shearing protocol. Switching shearing direction results in realignment of the AuNRs. For a film containing 75 wt% of AuNRs the alignment persists for several months. In addition to the lyotropic liquid crystal characteristics, the AuNRs films also exhibit anisotropic electrical conductivity with an order of magnitude difference between the conductivities in direction parallel and perpendicular to the alignment of the AuNRs.     

Molecular Self‐Assembly on Graphene

The formation of ordered arrays of molecules via self‐assembly is a rapid, scalable route towards the realization of nanoscale architectures with tailored properties. In recent years, graphene has emerged as an appealing substrate for molecular self‐assembly in two dimensions. Here, the first five years of progress in supramolecular organization on graphene are reviewed. The self‐assembly process can vary depending on the type of graphene employed: epitaxial graphene, grown in situ on a metal surface, and non‐epitaxial graphene, transferred onto an arbitrary substrate, can have different effects on the final structure. On epitaxial graphene, the process is sensitive to the interaction between the graphene and the substrate on which it is grown. In the case of graphene that strongly interacts with its substrate, such as graphene/Ru(0001), the inhomogeneous adsorption landscape of the graphene moiré superlattice provides a unique opportunity for guiding molecular organization, since molecules experience spatially constrained diffusion and adsorption. On weaker‐interacting epitaxial graphene films, and on non‐epitaxial graphene transferred onto a host substrate, self‐assembly leads to films similar to those obtained on graphite surfaces. The efficacy of a graphene layer for facilitating planar adsorption of aromatic molecules has been repeatedly demonstrated, indicating that it can be used to direct molecular adsorption, and therefore carrier transport, in a certain orientation, and suggesting that the use of transferred graphene may allow for predictible molecular self‐assembly on a wide range of surfaces.     

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.     

Colloid‐in‐Liquid Crystal Gels that Respond to Biomolecular Interactions

This paper advances the design of stimuli‐responsive materials based on colloidal particles dispersed in liquid crystals (LCs). Specifically, thin films of colloid‐in‐liquid crystal (CLC) gels undergo easily visualized ordering transitions in response to reversible and irreversible (enzymatic) biomolecular interactions occurring at the aqueous interfaces of the gels. In particular, LC ordering transitions can propagate across the entire thickness of the gels. However, confinement of the LC to small domains with lateral sizes of ～10 μm does change the nature of the anchoring transitions, as compared to films of pure LC, due to the effects of confinement on the elastic energy stored in the LC. The effects of confinement are also observed to cause the response of individual domains of the LC within the CLC gel to vary significantly from one to another, indicating that manipulation of LC domain size and shape can provide the basis of a general and facile method to tune the response of these LC‐based physical gels to interfacial phenomena. Overall, the results presented in this paper establish that CLC gels offer a promising approach to the preparation of self‐supporting, LC‐based stimuli‐responsive materials.     

Orientation‐Dependent Strain Relaxation and Chemical Functionalization of Graphene on a Cu(111) Foil

Epitaxial graphene grown on single crystal Cu(111) foils by chemical vapor deposition is found to be free of wrinkles and under biaxial compressive strain. The compressive strain in the epitaxial regions (0.25–0.40%) is higher than regions where the graphene is not epitaxial with the underlying surface (0.20–0.25%). This orientation‐dependent strain relaxation is through the loss of local adhesion and the generation of graphene wrinkles. Density functional theory calculations suggest a large frictional force between the epitaxial graphene and the Cu(111) substrate, and this is therefore an energy barrier to the formation of wrinkles in the graphene. Enhanced chemical reactivity is found in epitaxial graphene on Cu(111) foils as compared to graphene on polycrystalline Cu foils for certain chemical reactions. A higher compressive strain possibly favors lowering the formation energy and/or the energy gap between the initial and transition states, either of which can lead to an increase in chemical reactivity.     

Layer‐by‐Layer Decoupling of Twisted Graphene Sheets Epitaxially Grown on a Metal Substrate

The electronic properties of graphene can be efficiently altered upon interaction with the underlying substrate resulting in a dramatic change of charge carrier behavior. Here, the evolution of the local electronic properties of epitaxial graphene on a metal upon the controlled formation of multilayers, which are produced by intercalation of atomic carbon in graphene/Ir(111), is investigated. Using scanning tunneling microscopy and Landau‐level spectroscopy, it is shown that for a monolayer and bilayers with small‐angle rotations, Landau levels are fully suppressed, indicating that the metal–graphene interaction is largely confined to the first graphene layer. Bilayers with large twist angles as well as twisted trilayers demonstrate a sequence of pronounced Landau levels characteristic for a free‐standing graphene monolayer pointing toward an effective decoupling of the top layer from the metal substrate. These findings give evidence for the controlled preparation of epitaxial graphene multilayers with a different degree of decoupling, which represent an ideal platform for future electronic and spintronic applications.     

Chemically Responsive Gels Prepared from Microspheres Dispersed in Liquid Crystals

Liquid‐crystalline materials are a promising class of stimuli‐responsive materials that have been demonstrated to undergo surface‐induced orientational ordering transitions that can be highly sensitive and specific to chemical species. However, past studies demonstrating surface‐induced transitions in liquid crystals (LCs) have employed thin films of low‐molecular‐weight LCs that are difficult to stabilize (due to dewetting of the LC on a surface). Here, it is reported that it is possible to prepare liquid‐crystalline gels using a mixture of polystyrene microspheres and nematic LCs that undergo changes in orientational order, and thus optical appearance, in response to exposure to specific chemical compounds. These colloid‐in‐liquid‐crystal (CLC) gels are mechanically stable and can be molded on chemically functionalized surfaces into thin films containing micrometer‐sized LC‐rich domains that span the two interfaces of the gels. In contrast to other reports of LC gels, where the presence of a polymeric or self‐assembled small‐molecule gelator network within a nematic LC frustrates ordering transitions from propagating through the gels over distances, it is demonstrated that thin films of CLC gels, when supported on chemically functionalized surfaces, do undergo easily visualized ordering transitions upon exposure to organophosphonate compounds. Because these optically responsive CLC gels are mechanically robust and can be molded, this class of composite LC material may be broadly useful for the design of chemically responsive LC devices.     

Adlayer‐Free Large‐Area Single Crystal Graphene Grown on a Cu(111) Foil

To date, thousands of publications have reported chemical vapor deposition growth of “single layer” graphene, but none of them has described truly single layer graphene over large area because a fraction of the area has adlayers. It is found that the amount of subsurface carbon (leading to additional nuclei) in Cu foils directly correlates with the extent of adlayer growth. Annealing in hydrogen gas atmosphere depletes the subsurface carbon in the Cu foil. Adlayer‐free single crystal and polycrystalline single layer graphene films are grown on Cu(111) and polycrystalline Cu foils containing no subsurface carbon, respectively. This single crystal graphene contains parallel, centimeter‐long ≈100 nm wide “folds,” separated by 20 to 50 µm, while folds (and wrinkles) are distributed quasi‐randomly in the polycrystalline graphene film. High‐performance field‐effect transistors are readily fabricated in the large regions between adjacent parallel folds in the adlayer‐free single crystal graphene film.     

Tunable Diffraction Gratings from Biosourced Lyotropic Liquid Crystals

Diffraction gratings are important for modern optical components, such as optical multiplexers and signal processors. Although liquid crystal (LC) gratings based on thermotropic LCs have been extensively explored, they often require expensive molecules and complicated manufacturing processes. Lyotropic LCs, which can be broadly obtained from both synthetic and natural sources, have not yet been applied in optical gratings. Herein, a facile grating fabrication method using a biosourced lyotropic LC formed by cellulose nanocrystals (CNCs), a material extracted from plants, is reported. Hydrogel sheets with vertically aligned uniform periodic structures are obtained by fixing the highly oriented chiral nematic LC of CNCs in polymer networks under the cooperative effects of gravity on phase separation and a magnetic field on LC orientation. The hydrogel generates up to sixth-order diffraction spots and shows linear polarization selectivity, with tunable grating periodicity controlled through LC concentration regulation. This synthesis strategy can be broadly applied to various grating materials and opens up a new area of optical materials from lyotropic LCs.     

Unconventional Atomic Structure of Graphene Sheets on Solid Substrates

The atomic structure of free‐standing graphene comprises flat hexagonal rings with a 2.5 Å period, which is conventionally considered the only atomic period and determines the unique properties of graphene. Here, an unexpected highly ordered orthorhombic structure of graphene is directly observed with a lattice constant of ≈5 Å, spontaneously formed on various substrates. First‐principles computations show that this unconventional structure can be attributed to the dipole between the graphene surface and substrates, which produces an interfacial electric field and induces atomic rearrangement on the graphene surface. Further, the formation of the orthorhombic structure can be controlled by an artificially generated interfacial electric field. Importantly, the 5 Å crystal can be manipulated and transformed in a continuous and reversible manner. Notably, the orthorhombic lattice can control the epitaxial self‐assembly of amyloids. The findings reveal new insights about the atomic structure of graphene, and open up new avenues to manipulate graphene lattices.     

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.     

Alignment of liquid crystals doped with nickel nanoparticles containing different morphologies

Uniform homeotropic and homogeneous alignment of liquid crystals (LCs) is facilely achieved by dispersing Ni nanoparticles (Ni NPs) into the LCs. The alignment mode depends on the morphology of the Ni NPs. The mechanism of NP-induced LC alignment is elucidated clearly, indicating that the perfect orientation arises from the adsorption of Ni NPs on the substrate.     

Direct Synthesis of Few‐Layer Graphene on NaCl Crystals

Chemical vapor deposition is used to synthesize few‐layer graphene on micro crystalline sodium chloride (NaCl) powder. The water‐soluble nature of NaCl makes it convenient to produce free standing graphene layers via a facile and low‐cost approach. Unlike traditional metal‐catalyzed or oxygen‐aided growth, the micron‐size NaCl crystal planes play an important role in the nucleation and growth of few‐layer graphene. Moreover, the possibility of synthesizing cuboidal graphene is also demonstrated in the present approach for the first time. Raman spectroscopy, optical microscopy, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy are used to evaluate the quality and structure of the few‐layer graphene along with cuboidal graphene obtained in this process. The few‐layer graphene synthesized using the present method has an adsorption ability for anionic and cationic dye molecules in water. The present synthesis method may pave a facile way for manufacturing few‐layer graphene on a large scale.     

Drop‐on‐Demand Inkjet Printing of Thermally Tunable Liquid Crystal Microlenses

In this letter, the authors demonstrate Drop‐on‐Demand printing of variable focus, polarization‐independent, liquid crystal (LC) microlenses. By carefully selecting the surface treatment applied to a glass substrate, the authors are able to deposit droplets with a well‐defined curvature and contact angle, which result in micron‐sized lenses with focal lengths on the order of 300–900 µm. Observations with an optical polarizing microscope confirm the homeotopic alignment of the LC director in the droplets, which is in accordance with the polarization independent focal length. Results show that microlenses of different focal lengths can be fabricated by depositing successive droplets onto the same location on the substrate, which can then be used to build up programmable and arbitrary arrays of microlenses of various lens sizes and focal lengths. Finally, the authors utilize the thermal dependency of the order parameter of the LC to demonstrate facile tuning of the focal length. This technique has the potential to offer a low‐cost solution to the production of variable focus, arbitrary, microlens arrays.

     

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.     

Patterned Growth of Graphene over Epitaxial Catalyst

Rectangle‐ and triangle‐shaped microscale graphene films are grown on epitaxial Co films deposited on single‐crystal MgO substrates with (001) and (111) planes, respectively. A thin film of Co or Ni metal is epitaxially deposited on a MgO substrate by sputtering while heating the substrate. Thermal decomposition of polystyrene over this epitaxial metal film in vacuum gives rectangular or triangular pit structures whose orientation and shape are strongly dependent on the crystallographic orientation of the MgO substrate. Raman mapping measurements indicate preferential formation of few‐layer graphene films inside these pits. The rectangular graphene films are transferred onto a SiO₂/Si substrate while maintaining the original shape and field‐effect transistors are fabricated using the transferred films. These findings on the formation of rectangular/triangular graphene give new insights on the formation mechanism of graphene and can be applied for more advanced/controlled graphene growth.     

Surface alignment of liquid crystal multilayers evaporated on photoaligned polyimide film observed by surface profiler

The investigation of the surface alignment of liquid crystal (LC) multilayers evaporated on photoaligned polyimide vertical alignment (PI-VA) film was carried out by means of the novel three-dimensional (3D) surface profiler. We report the first use of the surface profiler to visualize a microscopic image of the monolayer arrangement of LC molecules in contact with the surface of photo-treated PI-VA film. The photoinduced anisotropy of partially UV-exposed PI-VA film can be visualized as a topological image of LC multilayers. It seems that the topology of LC multilayers is indicating the orientational distribution of LC molecules on the treated film. It was found that the periodically photoaligned PI-VA film surface can align an adsorbed LC monolayer and the LC molecular alignment can be extended to the bulk via the epitaxylike LC–LC interaction, i.e. a short-range molecular interaction. With regard to the unexposed PI-VA film surface, noticeable anisotropy in the monolayer alignment was not observed, indicating that the long-range elastic interaction may be responsible for the bulk alignment. The appearance of small droplets in the masked region may be presumably related to the dewetting phenomena.