Unidirectional Alignment Research Articles

Unidirectional Macroscopic Alignment of Chlorobenzo[c]‐[1,2,5]thiadiazole‐Based Semiconducting Copolymers with Controlled Regiochemistry

AbstractSolution‐processable donor–acceptor‐type conjugated copolymers are considered one of the most promising alternatives to inorganic semiconductors. The introduction of strong electron‐withdrawing groups in the acceptor units of the copolymers has been shown to favor fast charge transport; however, the correlation among the halogen‐substituted molecular structure, solid‐state packing, and charge transport properties is unclear. In this study, new chlorine‐atom‐substituted donor–acceptor copolymers comprising chlorobenzo[c]‐[1,2,5]thiadiazole and 4,4‐dihexadecyl‐4H‐cyclopenta[1,2‐b:5,4‐b′]dithiophene are synthesized and their physicochemical properties are compared with those of their unsubstituted or nitrogen‐incorporated backbone analogs. In addition, the regioregularity of the synthesized copolymers is controlled to investigate the effects of regiochemistry on the polymer backbone alignment using the nanogroove method. The results demonstrate that different degrees of regioregularity in the main chains induce a substantially dissimilar effect of the nanogroove and capillary force on the orientation of the polymer backbone, long‐range crystalline order, and charge transport properties of the conjugated polymers.

Wafer-Scale Unidirectional Alignment of Supramolecular Columns on Faceted Surfaces.

The long-range alignment of supramolecular structures must be engineered as a first step toward advanced nanopatterning processes aimed at miniaturizing features to dimensions below 5 nm. This study introduces a facile method of directing the orientation of supramolecular columns over wafer-scale areas using faceted surfaces. Supramolecular columns with features on the sub-5 nm scale were highly aligned in a direction orthogonal to that of the facet patterning on unidirectional and nanoscopic faceted surface patterns. This unidirectional alignment of supramolecular columns is also observed by varying the thickness of the supramolecular film or by altering the dimensions of the facet pattern. The ordering behavior of the supramolecular columns can be attributed to the triangular depth profile of the bottom facet pattern. Furthermore, this directed self-assembly principle allows for the continuous alignment of supramolecular structures across ultralarge distances on flexible patterned substrates.

Uniformly aligned liquid crystal molecules on reformed poly(ethylene-co-vinyl acetate) layers driven by ion beam exposure

ABSTRACT The characteristics of a poly(ethylene-co-vinyl acetate) (PEVA) film formed by spin coating process and ion beam (IB) irradiation was investigated with irradiation times. A physicochemical analysis was used to analyse the suitability of the PEVA film as a uniform liquid crystal (LC) alignment layer. Atomic force microscopy (AFM) revealed an increased surface roughness after IB irradiation. X-ray photoelectron spectroscopy (XPS) analysis showed IB irradiation broke the polymer branches and increased the oxygen concentration and bonding on the surface. These derived the strong Van der Waals forces and dipole-dipole interactions between the PEVA surface and LCs. The IB irradiation generated surface anisotropy on the PEVA film and unidirectional LC alignment was achieved. Polarised optical microscopy (POM) and pre-tilt angle measurements were carried out to show the uniform LC alignment. The transmittance curve exhibited a high optical performance. These results show the promising capabilities of IB irradiated PEVA film as an alignment layer in LC displays.

Single-Crystal MoS2 Monolayer Wafer Grown on Au (111) Film Substrates.

Monolayer transition metal dichalcogenides (TMDCs) with high crystalline quality are important channel materials for next-generation electronics. Researches on TMDCs have been accelerated by the development of chemical vapor deposition (CVD). However, antiparallel domains and twin grain boundaries (GBs) usually form in CVD synthesis due to the special threefold symmetry of TMDCs lattices. The existence of GBs severely reduces the electrical and photoelectrical properties of TMDCs, thus restricting their practical applications. Herein, the epitaxial growth of single crystal MoS2 (SC-MoS2 ) monolayer is reported on Au (111) film across a two-inch c-plane sapphire wafer by CVD. The MoS2 domains obtained on Au (111) film exhibit unidirectional alignment with zigzag edges parallel to the <110>direction of Au (111). Experimental results indicated that the unidirectional growth of MoS2 domains on Au (111) is a temperature-guided epitaxial growth mode. The high growth temperature provides enough energy for the rotation of the MoS2 seeds to find the most favorable orientation on Au (111) to achieve a unidirectional ratio of over 99%. Moreover, the unidirectional MoS2 domains seamlessly stitched into single crystal monolayer without GBs formation. The progress achieved in this work will promote the practical applications of TMDCs in microelectronics.

Surface modification of a poly(ethylene-co-vinyl acetate) layer by ion beam irradiation for the uniform alignment of liquid crystals

The post-processing of a poly(ethylene-co-vinyl acetate) (PEVA) film by ion-beam (IB) irradiation is described herein for use as a liquid crystal (LC) alignment layer. Various film curing temperatures are investigated in order to achieve a stable film prior to IB irradiation, and a uniform and homogeneous LC alignment with superior optical transparency is obtained at a curing temperature of 130 °C. The chemical and morphological effects of IB irradiation are further examined by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Although the surface morphology exhibits a random pattern, the IB irradiation is found to modify the chemical characteristics of the PEVA surface by simultaneously inducing van der Waals forces and strong dipole-dipole interactions with the LCs, thus leading to unidirectional LC alignment. In addition, LC cells are fabricated from the IB-irradiated PEVA films, and the LC alignment state is confirmed by polarized optical microscopy and pre-tilt angle measurements. Further, the high transparency of the deposited PEVA film compared to that of ITO-coated glass is demonstrated via transmittance measurement. In view of this superior performance, the IB-irradiated PEVA film is a promising alternative for advanced LC displays.

Shear-Rolling Process for Unidirectionally and Perpendicularly Oriented Sub-10-nm Block Copolymer Patterns on the 4 in Scale.

Shear alignment of the block copolymer (BCP) thin film is one of the promising directed self-assembly (DSA) methodologies for the unidirectional alignment of sub-10 nm microdomains of BCPs for next-generation nanolithography and nanowire-grid polarizers. However, because of the differences in the surface/interfacial energies at the top surface/bottom interface, the shear-induced ordering of BCP nanopatterns has been restricted to BCPs with spherical and cylindrical nanopatterns and cannot be realized for high-aspect-ratio perpendicular lamellar structures, which is essential for practical application to semiconductor pattern processes. It is still a difficult challenge to fabricate the unidirectional alignment in a short time over a large area. In this study, we propose an approach for combining the shear-rolling process with the filtered plasma treatment of BCP films for the fabrication of unidirectionally aligned and perpendicularly oriented lamellar nanostructures. This approach enables fabrication within 1 min on a 4 in scale. We treated filtered plasma on the BCP film for perpendicular orientation and executed the hot-rolling process with different roller and stage speeds. Large-scale shear was generated only at the location where the BCP film was in contact with both the roller and stage, effectively applying shear stress to a large area of the BCP film within a short time. The repeated application of this shear-rolling process can achieve a higher level of unidirectional alignment. Our aligned BCP vertical lamellae were used to fabricate a high-aspect-ratio sub-10-nm-wide metallic nanowire array via dry/wet processes. In addition, shear-rolling with chemoepitaxy patterns can achieve higher orientational order and lower defectivity.

Electric Field-Induced Polarization Responses of Noncentrosymmetric Crystalline Biopolymers in Different Frequency Regimes - A Case Study on Unidirectionally Aligned β-Chitin Crystals.

A dielectric medium containing noncentrosymmetric domains can exhibit piezoelectric and second-harmonic generation (SHG) responses when an electric field is applied. Since many crystalline biopolymers have noncentrosymmetric structures, there has been a great deal of interest in exploiting their piezoelectric and SHG responses for electromechanical and electro-optic devices, especially owing to their advantages such as biocompatibility and low density. However, exact mechanisms or origins of such polarization responses of crystalline biopolymers remain elusive due to the convolution of responses from multiple domains with varying degrees of structural disorder or difficulty of ensuring the unidirectional alignment of noncentrosymmetric domains. In this study, we investigate the polarization responses of a noncentrosymmetric crystalline biopolymer, namely, unidirectionally aligned β-chitin crystals interspersed in the amorphous protein matrix, which can be obtained naturally from tubeworm Lamellibrachia satsuma (LS) tube. The mechanisms governing polarization responses in different dynamic regimes covering optical (>1013 Hz), acoustic/ultrasonic (103-105 Hz), and low (10-2-102 Hz) frequencies are explained. Relationships between the polarization responses dominant in different frequencies are addressed. Also, electromechanical coupling responses, including piezoelectricity of the LS tube, are quantitatively discussed. The findings of this study can be applicable to other noncentrosymmetric crystalline biopolymers, elucidating their polarization responses.

Influence of fiber alignment on pseudoductility and microcracking in a cementitious carbon fiber composite material

This research examines the effect of fiber alignment on the performance of an exceptionally tough 3D-printable short carbon fiber reinforced cementitious composite material, the flexural strength of which can exceed 100 N/mm2. The material shows pseudoductility caused by strain-hardening and microcracking. An extrusion-based manufacturing process allows accurate control over the spatial alignment of the fibers’ orientation, since extrusion through a tight nozzle leads to nearly unidirectional alignment of the fibers with respect to the directional movement of the nozzle. Specimens were investigated using mechanical tests (flexural and tensile load), augmented by non-destructive methods such as X-ray 3D computed tomography and acoustic emission analysis to gain insight into the microstructure. Additionally, digital image correlation is used to visualize the microcracking process. X-ray CT confirms that about 70% of fibers show less than 10° deviation from the extrusion direction. Systematic variations of the fiber alignment with respect to the direction of tensile load show that carbon fibers enhance the flexural strength of the test specimens as long as their alignment angle does not deviate by more than 20° from the direction of the acting tensile stress. Acoustic emission analysis is capable of evaluating the spatiotemporal degradation behavior during loading and shows consistent results with the microstructural damage observed in CT scans. The strong connection of fiber alignment and flexural strength ties into a change from ductile to brittle failure caused by degradation on a microstructural level, as seen by complementary results acquired from the aforementioned methods of investigation.

Unidirectional Alignment of AgCN Microwires on Distorted Transition Metal Dichalcogenide Crystals.

Van der Waals epitaxy on the surface of two-dimensional (2D) layered crystals has gained significant research interest for the assembly of well-ordered nanostructures and fabrication of vertical heterostructures based on 2D crystals. Although van der Waals epitaxial assembly on the hexagonal phase of transition metal dichalcogenides (TMDCs) has been relatively well characterized, a comparable study on the distorted octahedral phase (1T' or Td) of TMDCs is largely lacking. Here, we investigate the assembly behavior of one-dimensional (1D) AgCN microwires on various distorted TMDC crystals, namely 1T'-MoTe2, Td-WTe2, and 1T'-ReS2. The unidirectional alignment of AgCN chains is observed on these crystals, reflecting the symmetry of underlying distorted TMDCs. Polarized Raman spectroscopy and transmission electron microscopy directly confirm that AgCN chains display the remarkable alignment behavior along the distorted chain directions of underlying TMDCs. The observed unidirectional assembly behavior can be attributed to the favorable adsorption configurations of 1D chains along the substrate distortion, which is supported by our theoretical calculations and observation of similar assembly behavior from different cyanide chains. The aligned AgCN microwires can be harnessed as facile markers to identify polymorphs and crystal orientations of TMDCs.

Alignment frustration in block copolymer films with block copolymer grafted TiO2 nanoparticles under soft‐shear cold zone annealing

AbstractBlock copolymers (BCPs) have received significant attention as promising candidates for sequestering nanoparticles and fabrication of aligned nanostructures with optimal optical or electrical properties. We investigate the influence of static and dynamic thermal field on the alignment of polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA) BCP morphology with the loading of novel poly(methyl methacrylate‐block‐Polystyrene) (PMMA‐b‐PS)‐grafted‐TiO2 nanoparticles (BCP‐g‐TiO2). Observation of characteristics IR peaks for PMMA and PS in BCP‐g‐TiO2 nanoparticles and Transmission Electron Microscopy (TEM) results of the outer coating of core nanoparticle, validate the grafting to approach in synthesizing BCP‐g‐TiO2. Here we report that under the sharp dynamic thermal field, at low loading of BCP‐g‐TiO2, there is good dispersion of nanoparticles in unidirectionally aligned BCP matrix in film interior probed by GISAXS, while, at high nanoparticle loading (~10 wt%), there is local frustration in the unidirectional alignment of the BCP matrix due to aggregation of BCP‐g‐TiO2 nanoparticles. However, Grazing incidence small angle X‐ray scattering (GISAXS) shows clearly that the BCP films remain largely locally ordered at the domain scale, despite these large perturbations to long‐range ordering even at high loading level, while bringing in new TiO2 functionality to the BCP films, such as UVO absorptivity or biofouling prevention, important to potential new applications of such membranes.

Simultaneous enhancement of dispersion and interfacial adhesion in Al matrix composites reinforced with nanoceramic-decorated carbon nanotubes

Simultaneously achieving homogeneous dispersion and appropriate interfacial adhesion is the foremost concern for designing high-performance carbon nanotube (CNT)/Al matrix composites. Herein, a strategy for surface modification was developed to fabricate uniform CNT/Al composites with enhanced interfacial strength. Small quantities of Al 2 O 3 nanoparticles were locally adhered to the surface of functionalized CNTs by electrostatic self-assembly, thereby promoting the adsorption of high concentrations of CNTs onto Al powders and hindering the agglomeration of CNTs. After densification, the CNTs retained their structural integrity and exhibited both individual distribution and unidirectional alignment in the matrix. As revealed by high-resolution transmission electron microscopy, the Al 2 O 3 nanoparticles promoted a large elastic buckling of the nanotube inner wall and formed a curved, stable contact with the CNTs, producing strong anchors at the CNT-Al interface. Consequently, the CNT-Al 2 O 3 /Al composites exhibited enhanced mechanical properties compared with the CNT/Al composites, while maintaining superior electrical conductivity. This work demonstrates the great potential of surface decoration in producing advanced CNT/metal composites in electrical applications. • Nanoceramic decoration was developed to simultaneously enhance CNT dispersion and CNT-Al interfacial adhesion. • Uniform, high-concentration CNT-Al 2 O 3 /Al powders were prepared. • Al 2 O 3 nanoparticles acted as strong anchors at CNT-Al interfaces. • The composites exhibited enhanced mechanical property and superior electrical conductivity.

A comprehensive review on the dispersion and survivability issues of carbon nanotubes in Al/CNT nanocomposites fabricated via friction stir processing

Aluminium metal matrix composites (AMMCs) are the fastest developing materials for structural applications due to their high specific weight, modulus, resistance to corrosion and wear, and high temperature strength. Carbon nanotubes (CNTs) is known as the material of the twenty-first century for its various applications in structural components for their high specific strength as well as functional materials for their exciting thermal and electrical characteristics. The present study comprise a systematic literature review of Al/CNT nanocomposites fabricated through a solid state friction stir processing. The present review is primarily focussed on the dispersion and survivability of CNTs in the Al matrix because these are the key factors in deciding the mechanical properties of the fabricated composite. Additionally, the formability, weldability and machinability of the FSPed fabricated composites reinforced with CNTs are also summarised here. Based on the detailed literature review, following research gaps are identified which require a critical and more focussed attention of the scientific community working in this research area: (i) the presence of agglomeration or clustering of CNTs in the composite, (ii) survivability and shortening of CNTs during FSP, (iii) interfacial reactions or the formation of reaction products (such as Al4C3) between Al matrix and CNTs, and (iv) the unidirectional alignment of CNTs in the fabricated composite. Important suggestions for further research in effective dispersion of CNTs with its preserved structure by FSP are also provided.

Structural Colors by Synergistic Birefringence and Surface Plasmon Resonance.

One-dimensional nanomaterials including cellulose nanocrystals (CNCs) and gold nanorods (GNRs) are widely used in optical materials due to their respective inherent features: birefringence with accompanying light retardation and surface plasmon resonance (SPR). Herein, we successfully combine these properties of both nanorods to generate synergistic and readily tunable structural colors in hybrid composite polymer films. CNCs and GNRs are embedded either in the same or in separate films after unidirectional alignment in dynamic hydrogels. By synergistically leveraging CNCs and GNRs with diverse amounts in hybrid films or stacked separate films, wide-ranging structural colors are obtained, far beyond those from films solely with aligned CNCs or GNRs. Higher GNR contents enhance light absorption at 520 nm with promoted magenta colors, while more CNCs affect the overall phase retardation with light absorption between 400 and 700 nm between crossed polarizers. Moreover, adjusting the angles between films solely with CNCs or GNRs via a stacking/rotating technique successively manipulates colors with flexible film combinations. By rotating the films with aligned GNRs (0-180°), light absorption can traverse from ∼500 to 650 nm. Thus, tuning the adjustable synergism of birefringence of CNCs and SPR of GNRs provides great potential for structural colors, which enlightens inspirations for designing functional optical materials.

Shear-induced unidirectional deposition of bacterial cellulose microfibrils using rising bubble stream cultivation

In crystalline cellulose I, all glucan chains are ordered from reducing ends to non-reducing ends. Thus, the polarity of individual chains is added forming a large dipole within the crystal. If one can engineer unidirectional alignment (parallel packing) of cellulose crystals, then it might be possible to utilize the material properties originating from polar crystalline structures. However, most post-synthesis manipulation methods reported so far can only achieve the uniaxial alignment with bi-directionality (antiparallel packing). Here, we report a method to induce the parallel packing of bacterial cellulose microfibrils by applying unidirectional shear stress during the synthesis and deposition through the rising bubble stream in a culture medium. Driving force for the alignment is explained with mathematical estimation of the shear stress. Evidences of the parallel alignment of crystalline cellulose Iα domains were obtained using nonlinear optical spectroscopy techniques.

The effect of bimodal structure with nanofibers and normal precipitates on the mechanical and electrical properties of Cu[sbnd]Ni[sbnd]Si alloy

The discontinuous precipitation (DP) was known to mechanically detrimental mechanism compared to normal precipitation (continuous precipitation, CP), while the DP has the higher conductivity because of low solute content in matrix. To get the optimum balance of strength and conductivity, the bimodal-structured Cu-4Ni-1Si alloy composed of two regions with CPs and DPs was fabricated. Bimodal-structured alloy occupied by 50% of each region shows remarkable high strength and conductivity combination (1088 MPa / 38%IACS) beyond the expected values which summated in alloys with fully CP or DP. The accelerated strengthening of bimodal-structured alloy is caused by uni-directional alignment and enhanced plastic deformation of DPs in alloy after cold-working.

A Novel Role of Interleukin-6 as a Regulatory Factor of Inflammation-Associated Deterioration in Osteoblast Arrangement.

Inflammatory disorders are associated with bone destruction; that is, deterioration in bone cell activities are under the control of the innate immune system. Macrophages play a central role in innate immunity by switching their polarized phenotype. A disturbed immune system causes aberrance in the ordered bone matrix microarrangement, which is a dominant determinant of bone tissue functionalization. However, the precise relationship between the immune system and bone tissue organization is unknown. In this study, the controlled in vitro co-culture assay results showed that M1-polarized macrophages disrupted the osteoblast alignment, which directly modulate the oriented bone matrix organization, by secreting pro-inflammatory cytokines. Notably, interleukin-6 was found to be a key regulator of unidirectional osteoblast alignment. Our results demonstrated that inflammatory diseases triggered bone dysfunction by regulating the molecular interaction between the immune system and bone tissue organization. These findings may contribute to the development of therapeutic targets for inflammatory disorders, including rheumatoid arthritis.

Wafer-scale growth of single-crystal graphene on vicinal Ge(001) substrate

Wafer-scale single-crystal graphene with high carrier mobility is essential as a promising channel material for the next-generation two-dimensional nanoelectronics. However, direct synthesis of wafer-scale single-crystal graphene on complementary metal oxide semiconductor (CMOS) compatible substrates still remains a challenge. Herein, we demonstrate that single-crystal graphene film with high mobility can be synthesized on the 15° miscut Ge(001) surface by perfectly aligning all the graphene islands and this feat has never been achieved on the normal Ge(001) surface. Both experimental observations and theoretical calculations suggest unidirectional alignment of the graphene islands on the 15° miscut Ge(001) surface is caused by suppression of graphene nucleation along the miscut direction of the vicinal surface. Ex situ atomic force microscopy (AFM) verifies that no additional graphene island nucleates after the initial nucleation process and wafer-scale single-crystal graphene is formed by the seamless stitching of the preferentially oriented graphene islands. The obtained wafer-scale single-crystal graphene possesses an ultrahigh carrier mobility, opening an avenue toward scalable fabrication of two-dimensional nanoelectronic devices based on single-crystal graphene without grain boundaries.

Effect of inclusion on strength and conductivity of Cu-Ni-Si alloys with discontinuous precipitation

The effect of inclusion on the strength and conductivity of fully discontinuous precipitated Cu-Ni-Si alloys with and without inclusion was studied. No inclusions were observed in Cu-4.75Ni-1.13Si alloy, the Ni + Si content of which was close to the solubility limit, while they were formed in solution-treated Cu-6Ni-1.42Si alloy at 980 °C. The duration of aging for full discontinuous precipitation (DP) at 500 °C was found to be shorter in Cu-6Ni-1.42Si alloy than Cu-4.75Ni-1.13Si alloy. The strength/conductivity of Cu-6%Ni-1.42%Si alloy with inclusion was 1071 MPa/46% IACS, while it was 966 MPa/50% IACS for Cu-4.75Ni-1.13Si alloy without inclusion, after drawing to the strain of 4. The drawing-induced uni-directional alignment of fiber-like Ni2Si precipitates was believed to increase the conductivity of Cu-Ni-Si alloys by reducing the cross sectional area of lamellar precipitates for the passage of electrons. The increase in strength was possibly due the higher volume fraction of fiber-like Ni2Si precipitates, along with the smaller inter-distance between them, in Cu-6%Ni-1.42%Si alloy with inclusion, than Cu-4.75Ni-1.13Si alloy without inclusion.

A novel method to align cells in a cardiac tissue-like construct fabricated by cell sheet-based tissue engineering.

Fabrication of cardiac tissue from human induced pluripotent stem cell-derived cardiomyocytes (hiPS-CMs) has received great interest, but a major challenge facing researchers is the alignment of cardiomyocytes in the same direction to optimize force generation. We have developed a novel method of fabricating a cardiac tissue-like construct with aligned cells based on the unidirectional stretching of an hiPS-CM sheet. A square cell sheet was harvested from a temperature-responsive culture dish and placed on a silicone surface, and an extending force was imposed on the silicone to stretch the cell sheet along one direction. To enable evaluation of cardiomyocyte morphology in vitro, a cell sheet was constructed by coculture of hiPS-CMs and human adipose-derived stem cells. In separate experiments, a stretched double-layered cell sheet constructed from hiPS-CMs alone was transplanted onto the muscle of an athymic rat, and its features were compared with those of a nonstretched (control) cell sheet. Immediately after stretching, the stretched cell sheet was significantly longer than the control cell sheet. Immunohistological analysis revealed that the cardiomyocytes showed unidirectional alignment in the stretched cell sheet but random directionality in the control cell sheet. Two weeks after transplantation, immunohistology demonstrated that the stretched cell sheet had retained the unidirectionality of its myocardial fibers and had an orientation intensity that was higher than that of the control cell sheet after transplantation or the stretched cell sheet before transplantation. Our technique provides a simple method of aligning an hiPS-CM-derived cardiac tissue-like construct without the use of a scaffold.

Efficient Toughening of Short-Fiber Composites Using Weak Magnetic Fields.

Short fibers may serve as toughening agents of composite materials because of the high energy dissipated during fracture, associated with numerous fiber pullouts. An ongoing challenge is to improve their toughness even further, by directing and concentrating fibers near highly stressed structural regions. Weak magnetic fields are utilized to increase the fracture toughness of an epoxy matrix reinforced by short magnetized glass fibers by directing and concentrating fibers near highly stressed structural regions. The orientation and local concentration of the fibers are controlled by the vector components of the magnetic field, and by the gradient in field intensity, respectively. Optimized fracture toughness was achieved by using two pairs of permanent magnets, combining enhanced concentration of fibers in the crack-tip vicinity with alignment of the fibers along the load direction. This optimized value was well above the reference fracture-toughness measured for composites with the same filler content in the absence of a magnetic field, as well as above the value achieved by exploiting unidirectional alignment, without fiber translation, using a solenoid. The method suggested in this study—localized reinforcement using magnetic translation of fillers through the formation of magnetic gradients—enables efficient and controllable improvement in the composite’s overall resistance to fracture, without the involvement of additional phases or material.