Aligned Films Research Articles

The combined effects of electrolyte addition and mechanical shearing on cellulose nanocrystal alignment

AbstractThis research explored the impact of four different electrolytes on the orientation of cellulose nanocrystals (CNCs) in shear-cast films prepared from aqueous CNC gels. Changes in the aqueous CNC gels’ rheological properties with electrolyte addition were correlated to the orientation and optical properties of dried CNC films. Film alignment was qualitatively assessed using cross-polarized optical microscopy and quantified by order parameters computed by UV–Vis transmission spectroscopy. Electrolyte addition resulted in an increased alignment in dried CNC films. For pure CNCs, the film order parameters remained constant at approximately 0.3 for shear rates from 20 s−1 to 100 s−1. However, higher order parameters were achieved in the presence of electrolytes. Notably, an order parameter of 0.88 was achieved at a shear rate of only 20 s−1. In addition, films produced from dispersions containing electrolytes exhibited improved clarity and haze. The results of this work highlight that electrolyte addition can enable higher order parameters at lower shear rates and facilitate the development of aligned CNC films for applications such as polarizers, clear coatings, and piezoelectric materials. Graphical abstract

Self – assembled aligned single – walled carbon nanotubes as an anisotropic polarizer and saturable absorber in erbium-doped femtosecond fiber laser

We report the production of a saturable absorber (SA) based on aligned single-walled carbon nanotubes SWCNTs by the self-assembly method. The ultrafast saturation behavior of prepared aligned and random nanostructures shows an increase of modulation depth by 6% due to the alignment method. We also observed the dependence of aligned SWCNTs loss on the polarization direction of laser radiation. All-fiber Er-doped hybrid mode-locked fiber laser was demonstrated based on the aligned /random SWCNTs-based SAs. We achieved the generation of stable stretched pulses with a pulse duration of 490/569 fs and an average output power of 20.7/18.25 mW. We also investigated the advantages of using aligned SWCNTs compared to the typical structure with random tube distribution. We show that the use of aligned SWCNTs film increased the SNR by 24.5, decreased the mode-locking threshold power by 42 mW, and decreased the RIN level by (20-25) dB in the frequency range [∼ 0 Hz- 100 kHz] and ∼ 8 dB in the range [100 kHz – 1 MHz].

Gate-tunable optical anisotropy in wafer-scale, aligned carbon nanotube films

Gate-tunable optical anisotropy in wafer-scale, aligned carbon nanotube films

The effects of side-chain flexibility on the photosensitivity of polyimide alignment film

ABSTRACT To examine the impact of side-chain flexibility on the photosensitivity of polyimide liquid crystal (LC) alignment films, two polyimides (OD-HAB-CA and OD-HAB6-CA) were synthesised. OD-HAB6-CA contains flexible hexamethylene side chains. This study demonstrates that the OD-HAB-CA alignment film can induce LC molecular alignment after 80 min of non-polarised ultraviolet light (NPUVL) irradiation. In contrast, the OD-HAB6-CA alignment film can achieve the same result after only 35 min of irradiation. This suggests that the flexibility of the side-chain can significantly improve the photosensitivity of the alignment film and shorten the required irradiation time. In addition, OD-HAB-CA and OD-HAB6-CA exhibit good thermal stability and light transmittance properties. The resulting LC cell have pretilt angles of 0.2° and 0.5°, respectively, which are suitable for in-plane switching mode LCDs.

Anisotropic, free-standing anodic films with aligned anatase-bronze TiO2-integrated graphene for high-capacity lithium-ion batteries

The composition modification and structure manipulation of carbon-based battery electrodes is becoming an increasingly urgent need for safer, more reliable, and effective electric vehicles. Herein, we fabricate a free-standing hybrid anatase-bronze TiO2-grafted reduced graphene oxide (TiO2-rGO) through a one-pot solvothermal procedure. The TiO2-rGO composite was transformed into a film with an anisotropic alignment and assembled as an anode into lithium-ion batteries (LIBs) to enhance its performance. Our previously developed “Pulse Freezing” process, with modifications including: (1) dimensional and structural optimization for larger and faster film production and (2) optimal microfluidic condition for vertical porous alignment, is utilized for assembling this nanocomposite anodic film. During the microfluidic assembly process, we achieved the desirable flowrate, flow patterns, and alignments of the integrated TiO2-rGO layers while forming porous microstructures through freeze drying. The porous and aligned TiO2-integrated rGO film exhibits a significantly enhanced specific capacity of 400 mAh/g at 0.2 A/g, which is a drastic increase compared to traditional TiO2 and carbon black electrodes possessing <50 mAh/g capacity, attributed to the anisotropic alignment and porous microstructure of rGO in combination with TiO2 grafting. The developed TiO2-rGO composite film provides a promising application of Ti-based electrodes in LIBs for commercial battery industries.

A facile spinning approach towards the continuous production of aligned nanocellulose films

In this work, we present an alternative approach to cellulose nanofibril film (CNF) production, taking inspiration from the wet spinning of fibers to wet spin films. During the spinning process, a CNF suspension is injected into a coagulation bath, where the partially aligned CNF network is locked. The CNF alignment of the dry films is then detected by wide angle X-ray scattering (WAXS). The comparison between the ultimate strengths and strengths at breaks of the films produced with different process parameters, including the suspension injection rate, bath pH, and bath flow rate, indicated no significant change in mechanical properties, suggesting a reliable and constant outcome for large-scale film fabrication. Furthermore, the produced films demonstrated high total light transmittance of 93 % at the wavelength of 550 nm, making them suitable for optoelectronic applications. Polarized optical microscopy revealed that even a low degree of CNF alignment can lead to anisotropic optical properties. Moreover, an anisotropic response to humidity was observed, in which the films preferentially bend in the perpendicular direction of the CNF orientation, thus opening a way for humidity-driven actuators.

Interfacial-Assembly-Induced In Situ Transformation from Aligned 1D Nanowires to Quasi-2D Nanofilms.

As the dimensionality of materials generally affects their characteristics, thin films composed of low-dimensional nanomaterials, such as nanowires (NWs) or nanoplates, are of great importance in modern engineering. Among various bottom-up film fabrication strategies, interfacial assembly of nanoscale building blocks holds great promise in constructing large-scale aligned thin films, leading to emergent or enhanced collective properties compared to individual building blocks. As for 1D nanostructures, the interfacial self-assembly causes the morphology orientation, effectively achieving anisotropic electrical, thermal, and optical conduction. However, issues such as defects between each nanoscale building block, crystal orientation, and homogeneity constrain the application of ordered films. The precise control of transdimensional synthesis and the formation mechanism from 1D to 2D are rarely reported. To meet this gap, we introduce an interfacial-assembly-induced interfacial synthesis strategy and successfully synthesize quasi-2D nanofilms via the oriented attachment of 1D NWs on the liquid interface. Theoretical sampling and simulation show that NWs on the liquid interface maintain their lowest interaction energy for the ordered crystal plane (110) orientation and then rearrange and attach to the quasi-2D nanofilm. This quasi-2D nanofilm shows enhanced electric conductivity and unique optical properties compared with its corresponding 1D geometry materials. Uncovering these growth pathways of the 1D-to-2D transition provides opportunities for future material design and synthesis at the interface.

Polymer-dispersed liquid-crystal coatings for ultrasound visualization: Experiment and theory.

Polymer dispersed liquid crystal (PDLC) films are formed of droplets of liquid crystal (LC) held in a polymer matrix. Similar to aligned LC films, PDLCs exhibit the acousto-optic (AO) effect when excited by acoustic waves of sufficient amplitude, whereby the PDLC film becomes transparent in the excited regions (acoustic clearing). Despite decades of research there is still debate over the mechanisms of the AO effect for the case of LC films, with several competing theories, and AO effects in PDLC have not been studied theoretically. This paper explores the AO effect in PDLC both experimentally and theoretically, and attempts a theoretical description of the observed phenomena based on the theoretical approach by Selinger etal. for aligned LC films. The acousto-optic effect in PDLC is shown to be due to direct interaction of acoustic waves with LC droplets, rather than due to compression of the droplet itself. Polarizing microscopy revealed changes in droplet shape at excited points. This is consistent with reorientation as a contributing factor, possibly coexisting with flows at higher excitation powers. In previous experimental studies PDLC films were prepared with cover slides, in the same way as LC AO cells, significantly limiting applications by adding complexity to the design. Also, to exhibit AO clearing it was considered that the PDLC needed to be prepared with high LC concentrations (over 75% by weight). We demonstrate that no cover slide is necessary, and that PDLC coatings without a cover have improved sensitivity to acoustic waves. We demonstrate the AO effect for LC concentrations as low as 40% by weight. The ability to use standard composition PDLC, with no top cover, is paving the way to paint-on visual ultrasound sensors.

Efficient Emission of Highly Polarized Thermal Radiation from a Suspended Aligned Carbon Nanotube Film.

A polarized light source covering a wide wavelength range is required in applications across diverse fields, including optical communication, photonics, spectroscopy, and imaging. For practical applications, high degrees of polarization and thermal performance are needed to ensure the stability of the radiation intensity and low energy consumption. Here, we achieved efficient emission of highly polarized and broadband thermal radiation from a suspended aligned carbon nanotube film. The anisotropic nature of the film, combined with the suspension, led to a high degree of linear polarization (∼0.9) and great thermal performance. Furthermore, we performed time-resolved measurements of thermal emission from the film, revealing a fast time response of approximately a few microseconds. We also obtained visible light emission from the device and analyzed the film's mechanical breakdown behavior to improve the emission intensity. Finally, we demonstrated that suspended devices with a constriction geometry can enhance the heating performance. These results show that carbon nanotube film-based devices, as electrically driven thermal emitters of polarized radiation, can play an important role for future development in optoelectronics and spectroscopy.

Synthesis of liquid crystalline compounds containing thiol groups at both ends as reactive substituents and their immobilization on a gold substrate

In this study, we synthesized four bifunctional compounds containing two alkoxy groups, at which reactive thiol groups were introduced. Among these compounds, a compound with four and five methylene units in each alkyl chain did not exhibit a liquid crystalline phase. The other three compounds exhibit one or two liquid crystalline phases, and the number of liquid crystalline phases depends on the number of methylene units in their alkyl chains. These liquid crystalline compounds were oriented in one direction using a rubbed alignment film, and the oriented compounds were transferred onto a gold substrate. Using these gold substrates as working electrodes, cyclic voltammetry (CV) was performed with potassium ferricyanide as the redox probe. As the deposition time increased, the current intensities of a pair of redox waves gradually decreased. This trend suggests that with longer deposition times, a larger amount of the liquid crystalline compound was transferred to the gold substrate surface. These findings shed light on the relationship among the structures of bifunctional compounds, their liquid crystalline behavior, and their alignment properties on gold substrates, thereby offering valuable insights for potential applications in nanotechnology and materials science.

Unraveling the Molecular Weight Dependence of High Magnetic Field to Manipulate the Semiconducting Polymer Molecular Orientation.

The magnetic alignment of molecules, which exploits the anisotropy of diamagnetic susceptibility, provides a clean and versatile approach to the structural manipulation of semiconducting polymers. Here, the magnetic-alignment dynamics of two molecular-weight (MW) batches of a diketopyrrolopyrrole (DPP)-based copolymer (PDVT-8) were investigated. Microstructural characterizations revealed that the magnetically aligned, high-MW (Mn = 53.7 kDa) PDVT-8 film exhibited a higher degree of backbone chain alignment and film crystallinity compared with the low-MW (Mn = 17.6 kDa) PDVT-8 film grown via the same magnetic alignment method. We found that as the MW increases, the degree of preaggregation of the polymer molecules in solution significantly increases and the aggregation mode changes from H-aggregation to J-aggregation through a cooperative assembly mechanism. These events improved the responsiveness of high-MW polymer molecules to magnetic fields. Field-effect transistors based on the magnetic aligned high-MW PDVT-8 films exhibited a 6.8-fold increase in hole mobility compared to the spin-coated films, along with a mobility anisotropy ratio of 12.6. This work establishes a significant correlation among chain aggregation behavior in solution, polymer film microstructures, magnetic responsiveness, and carrier transport performance in donor-acceptor polymer systems.

Anisotropic adhesive interface formed by the spontaneous orientation behavior of liquid crystal polymers

Abstract Adhesive layers were prepared using photoreactive polymer liquid crystals and their application as dismantled adhesives, based on the change in thermal properties associated with photoisomerization, was investigated. Anisotropy in adhesive strength was successfully achieved by controlling the alignment of the liquid crystal using a polyimide alignment film. Furthermore, anisotropy in the adhesive strength due to photoalignment was investigated using the axis-selective photoreactivity of polymer liquid crystals to linearly polarized light.

Removal of conjugated polymer on carbon nanotube array by dry process

With the progress in the purity and alignment of semiconductor carbon nanotubes (CNTs), how to efficiently remove the conjugated polymers twining round CNTs has become an important and urgent matter for the further development of CNT electronics. The removal of conjugated polymers (CPs) by wet cleaning will inevitably lead to the destruction of the morphology of aligned CNT array films, which will cause the monolayered CNTs to form agglomeration or stacking. Therefore, it is necessary to develop a dry method to remove CPs on the aligned CNT films. In this work, we studied the thermal decomposition characteristics of CNTs and CPs in detail, and found that the ratio of the oxidative decomposition rate of CNTs and CPs could reach up to 35.7 in the oxygen environment at 450 °C. The transmission electron microscopes (TEMs) show that such a dry treatment process can effectively remove the polymer on CNTs without affecting the morphology of CNT arrays. The Raman spectrum show that ratio of G/D of the annealed sample is as high as 41.8, which indicates that the CNTs are not detectable damaged during the annealed process. The fabricated field-effect transistors (FETs) with a length of 2 μm exhibit a current on/off ratio higher than 104 and a current density higher than 660 μA/μm, which further justifies that the CNT arrays treated by the dry method exhibit high quality.

Structure-Piezoelectric Property Relationships of Thin Films Composed of Electrospun Aligned Poly(vinylidene fluoride) Nanofibers.

In the past two decades, many studies on piezoelectric nanofibers (NFs) prepared from poly(vinylidene fluoride) (PVDF) and its copolymers, including single NFs, randomly oriented nonwoven mats, and aligned NFs, have been reported. However, studies on the relationships between the PVDF NF diameter, the orientation of the β-phase crystals inside NFs, and the piezoelectric properties of the NFs are still limited. In this study, the effect of the fiber diameter on the internal molecular packing/orientation and piezoelectric properties of aligned PVDF NF thin films was investigated. Herein, piezoelectric thin films composed of densely packed, uniaxially aligned, PVDF NFs with diameters ranging from 228 to 1315 nm were prepared by means of electrospinning with a rotating collector and successive hot-pressing and poling. The effect of the diameters of PVDF NFs on their internal structures, as well as the piezoelectric properties of the thin films, was investigated. All prepared NFs mainly contained β-phase crystals with a similar total crystallinity. The orientation of the β-phase crystals inside the NFs increased with an increase in the fiber diameter, resulting in an improved transverse piezoelectric coefficient (d31) for the thin films. The output voltage of the prepared thin films reached a maximum of 2.7 V at 104 Hz.

Aligned and unaligned single-walled carbon nanotube bilayer films for uncooled infrared sensors

Semiconducting single-walled carbon nanotube (SWCNT) film fabrication using the dip-coating method has successfully produced a unique film with two layers of different morphologies, an upper layer of aligned SWCNT film and a lower layer of non-aligned SWCNT network film. In the upper layer, SWCNTs form SWCNT bundles of several SWCNT thicknesses, and the bundles form thin aligned SWCNT films of 2–7 nm in thickness with parallel and equally spaced bundles of SWCNTs. When a bolometer device with this bilayer film was fabricated on electrodes, the upper aligned SWCNT film was the main conductive path with a low resistivity of about 0.2 Ωcm around room temperature. The alignment film also achieved a high temperature coefficient of resistance (TCR) of more than −5%/K due to its thin thickness, which is hardly affected by the slight metallic SWCNT presence. These excellent properties of a high TCR and low resistance are advantageous for the development of innovative sensor elements.

Controlled doping rates of graphene oxide in aluminum for high electrical performance and oxygen reduction reaction

The brush coating method allows the advantage of being able to produce thin films simply and quickly. This study introduces a method for thin-film production by brushing a solution containing graphene doped in Al2O3 using the sol–gel method. Graphene oxide (GO) is suitable for semiconductors with bandgap values of about 1.7 eV at room temperature, and the characteristics of the thin films were analyzed according to the doping ratio. First, X-ray photoelectron spectroscopy measurements were obtained to analyze the chemical composition of the thin-film surface. Since graphene is a carbon isomer, the characteristic of oxygen vacancies was confirmed by the increasing C–C bond intensity with increasing GO doping concentration. In addition, Raman analysis was performed to analyze the concentration of molecular groups of compounds for defects in graphene. Thereafter, through atomic force microscopy measurements, as the graphene doping ratio increased, the average roughness increased from 1.785 to 33.67, the residual DC voltage also increased by about 48.42 %, and the polar anchoring energy also increased by about 16.33 %. In addition, response-time–transmittance measurements were performed to measure the electro-optical properties of the thin film, and excellent Vth and stable response speed were obtained. Additionally, the validity of the results was supported through bandgap analysis. Finally, the degree of alignment of liquid–crystal molecules on the film surface was confirmed by polarized optical microscopy and pretilt angle measurements, and the suitability of the thin film for display devices was shown via transmittance measurements. As a result, GO:Al2O3 hybrid thin film is an excellent candidate for use as an alignment film for solar energy, secondary batteries, and next-generation liquid crystal displays.

Preparing a liquid crystalline dispersion of carbon nanotubes with high aspect ratio.

We successfully prepared a surfactant-assisted carbon nanotube (CNT) liquid crystal (LC) dispersion with double-walled CNTs (DWCNTs) having a high aspect ratio (≈1378). Compared to dispersions of single-walled CNTs (SWCNTs) with lower aspect ratio, the transition concentrations from isotropic phase to biphasic state, and from biphasic state to nematic phase are lowered, which is consistent with the predictions of the Onsager theory. An aligned DWCNT film was prepared from the DWCNT dispersion by a simple bar-coating method. Regardless of the higher aspect ratio, the order parameter obtained from the film is comparable to that from SWCNTs with lower aspect ratios. This finding implies that precise control of the film formation process, including a proper selection of substrate and deposition/drying steps, is crucial to maximize the CNT-LC utilization.

Interplay between Side Chain Density and Polymer Alignment: Two Competing Strategies for Enhancing the Thermoelectric Performance of P3HT Analogues.

A series of polythiophenes with varying side chain density was synthesized, and their electrical and thermoelectric properties were investigated. Aligned and non-aligned thin films of the polymers were characterized in the neutral and chemically doped states. Optical and diffraction measurements revealed an overall lower order in the thin films with lower side chain density, also confirmed using polarized optical experiments on aligned thin films. However, upon doping the non-aligned films, a sixfold increase in electrical conductivity was observed for the polythiophene with the lowest side chain density compared to poly(3-hexylthiophene) (P3HT). We found that the improvement in conductivity was not due to a larger charge carrier density but an increase in charge carrier mobility after doping with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). On the other hand, doped aligned films did not show the same trend; lower side chain density instead led to a lower conductivity and Seebeck coefficient compared to those for P3HT. This was attributed to the poorer alignment of the polymer thin films with lower side chain density. The study demonstrates that optimizing side chain density is a synthetically simple and effective way to improve electrical conductivity in polythiophene films relevant to thermoelectric applications.

Waveguide Properties of Homogeneously Aligned Liquid Crystal Layers between ITO Electrodes and Thin Alignment Films

Numerical studies of the waveguide properties of liquid crystal layers bounded by substrates with indium tin oxide (ITO) electrodes using the finite difference time-domain (FDTD) method are carried out. On the basis of the experimental transmittance spectra of ITO-coated glass substrates in the visible and near-infrared ranges, a Lorentz model describing the dielectric properties of the ITO electrodes is created. Then, by numerical modeling, optical systems including a homogeneously aligned LC layer between the thin alignment films and the ITO electrodes on the quartz substrates are studied. It is shown that, in the case of the use of traditional alignment films or their absence, the ITO electrodes lead to significant resonant losses in the waveguide mode for both TE- and TM-polarized light. The losses mechanism based on a phase-synchronized mode coupling occurring in relatively narrow spectral ranges is discussed. We also propose a method to control and exclude the losses using thin alignment films with a proper thickness and low refractive index.

Rigid-flex stamped indium tin oxide film for convertible self-alignment

The alignment layer process, which is a key element for liquid crystal (LC) displays, was investigated for efficiency improvement and for suggesting a new mode. To produce alignment films that can be used in both twisted-nematic (TN) and vertical alignment (VA) configurations, InO solution is doped with SnO. Then, the pattern was transferred by attaching a one-dimensional soft-imprint mold, and pattern and orientation analyses were performed in accordance with the SnO ratio. The horizontal orientation performance improved as the SnO ratio increased, and the best orientation performance was observed for a film doped with 70% SnO. Further, the thermal stability improved and anchoring energy increased, which was measured to be very close to that of the rubbed polyimide film. The low transmittance of InO was overcome by doping with SnO, which has high transmittance. In the film doped with 80% SnO, the LC molecules were aligned in a vertical direction and were suitable for VA mode operation. By simple adjustment of the doping ratio, differences are observed with respect to the existing films in that the performance of the alignment layer is improved and the pretilt angles of the LC molecules can be changed. These convertible characteristics are expected to play a revolutionary role in the development of new LC driving modes.