In-plane Alignment Research Articles

Rational design of mixed-matrix metal-organic framework membranes for molecular separations.

Conventional separation technologies to separate valuable commodities are energy intensive, consuming 15% of the worldwide energy. Mixed-matrix membranes, combining processable polymers and selective adsorbents, offer the potential to deploy adsorbent distinct separation properties into processable matrix. We report the rational design and construction of a highly efficient, mixed-matrix metal-organic framework membrane based on three interlocked criteria: (i) a fluorinated metal-organic framework, AlFFIVE-1-Ni, as a molecular sieve adsorbent that selectively enhances hydrogen sulfide and carbon dioxide diffusion while excluding methane; (ii) tailoring crystal morphology into nanosheets with maximally exposed (001) facets; and (iii) in-plane alignment of (001) nanosheets in polymer matrix and attainment of [001]-oriented membrane. The membrane demonstrated exceptionally high hydrogen sulfide and carbon dioxide separation from natural gas under practical working conditions. This approach offers great potential to translate other key adsorbents into processable matrix.

Revealing the vertical structure of in-situ fabricated perovskite nanocrystals films toward efficient pure red light-emitting diodes

The development of efficient perovskite light-emitting diodes (PeLEDs) relies strongly on the fabrication of perovskite films with rationally designed structures (grain size, composition, surface, etc.). Therefore, an understanding of structure-performance relationships is of vital importance for developing high-performance perovskite devices, particularly for devices with in-situ fabricated perovskite nanocrystal films. In this study, we reveal the vertical structure of an in-situ fabricated quasi-two-dimensional perovskite film. By combining time-of-flight secondary ion mass spectrometry, energy dispersive spectroscopy, grazing incidence wide-angle X-ray scattering (GIWAXS), and low-temperature photoluminescence spectra, we illustrate that the resulting in-situ fabricated DPPA2Csn-1Pbn(Br0.3I0.7)3n+1 (DPPA+: 3,3-diphenylpropylammonium) film has a gradient structure with a very thin layer of ligands on the surface, predominantly small-n domains at the top, and predominantly large-n domains at the bottom owing to the solubility difference of the precursors. In addition, GIWAXS measurements show that the domain of n = 2 on the top layer has an ordered in-plane alignment. Based on the understanding of the film structure, we developed an in-situ fabrication process with ligand exchange to achieve efficient pure red PeLEDs at 638 nm with an average external quantum efficiency (EQE) of 7.4%. The optimized device had a maximum luminance of 623 cd/m2 with a peak EQE of 9.7%.

High-Strength Liquid Crystal Polymer-Graphene Oxide Nanocomposites from Water.

We report on the morphology and mechanical properties of nanocomposite films derived from aqueous, hybrid liquid crystalline mixtures of rodlike aggregates of a sulfonated, all-aromatic polyamide, poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT), and graphene oxide (GO) platelets. An isothermal step at 200 °C facilitates in situ partial thermal reduction of GO to reduced GO (rGO) in nanocomposite films. X-ray scattering studies reveal that PBDT-rGO nanocomposites exhibit both higher in-plane alignment of PBDT (the order parameter increases from 0.79 to 0.9 at 1.8 vol % rGO) and alignment along the casting direction (from 0.1 to 0.6 at 1.8 vol % rGO). From dynamic mechanical thermal analysis, the interaction between PBDT and rGO causes the β-relaxation activation energy for PBDT to increase with rGO concentration. Modulus mapping of nanocomposites using atomic force microscopy demonstrates enhanced local stiffness, indicating reinforcement. From stress-strain analysis, the average Young's modulus increases from 16 to 37 GPa at 1.8 vol % rGO and the average tensile strength increases from 210 to 640 MPa. Despite polymer alignment along the casting direction, an average transverse tensile strength of 230 MPa is obtained.

Effect of symmetry reduction on the magnetic properties of LnIr[formula omitted]Si[formula omitted] polymorphs

Many tetragonal compounds LnIr2Si2 (Ln = lanthanoid) occur in two polymorphous phases and are therefore well suited to study the relationship between crystal structure and magnetic properties. We have grown GdIr2Si2 single crystals of both polymorphs from a high-temperature indium flux and investigated their anisotropic magnetic properties. The higher symmetric form with the ThCr2Si2 structure (space group I4/mmm) orders antiferromagnetically at TN=87K while for the lower symmetric compound in the CaBe2Ge2 structure (space group P4/nmm) we determined a much lower Néel temperature TN=12K. Our magnetic characterization of the single crystals reveals that for both compounds the magnetic moments are aligned in the a−a plane of the tetragonal lattice, but that the change of the symmetry strongly effects the inplane alignment of the moment orientation. For Ln=Er and Ho, we confirmed the existence of LnIr2Si2 in the space group P4/nmm. The magnetic properties of these lower symmetric compounds are in remarkable difference to their related compounds in the space group I4/mmm.

Lightweight Polyethylene/Hexagonal Boron Nitride Hybrid Thermal Conductor Fabricated by Melt Compounding Plus Salt Leaching.

Application of porous polymeric materials is severely limited by their ultralow thermal conductivities. Herein, by promoting the formation of thermal conduction pathways, we fabricated open-cellular structured polyethylene/hexagonal boron nitride hybrid thermal conductors via melt compounding plus salt leaching. The structural analyses indicate that the inclusion of hBN can enhance the open-cell level of resultant materials. X-ray diffractions confirm the high in-plane alignments of hBN in each sample. Consequently, the test results evidence the superior thermal conductivities of our samples, and the thermal conductivities of each sample are characterized as functions of hBN loadings. Ultimately, our advanced porous thermal conductor with a low hBN loading of 3.1 vol% exhibits a high specific thermal conductivity of 0.75 (W/mk)/(g/cm3), which is 82.9% higher than virgin PE and far higher than bulk PE/hBN composites. Our work also intends to reveal the architectural advantages of open-cellular, as compared with the close-one, in fabricating porous materials with highly interconnected fillers.

Cationic peptides template the assembly of polyoxometalates into ultrathin nanosheets with in-plane ordered arrangements.

Ultrathin polyoxometalate nanosheets with an in-plane alignment have been constructed in aqueous solution with the assistance of cationic peptides. Different POMs varying in topology, size, and charges could be templated into ordered 2D nanostructures based on this generalized approach, allowing the fabrication of customizable 2D materials.

On the optical anisotropy in 2D metal-halide perovskites.

Two-dimensional metal-halide perovskites (MHPs) are versatile solution-processed organic/inorganic quantum wells where the structural anisotropy creates profound anisotropy in their electronic and excitonic properties and associated optical constants. We here employ a wholistic framework, based on semiempirical modeling (k·p/effective mass theory calculations) informed by hybrid density functional theory (DFT) and multimodal spectroscopic ellipsometry on (C6H5(CH2)2NH3)2PbI4 films and crystals, that allows us to link the observed optical properties and anisotropy precisely to the underlying physical parameters that shape the electronic structure of a layered MHP. We find substantial frequency-dependent anisotropy in the optical constants and close correspondence between experiment and theory, demonstrating a high degree of in-plane alignment of the two-dimensional planes in both spin-coated thin films and cleaved single crystals made in this study. Hybrid DFT results elucidate the degree to which organic and inorganic frontier orbitals contribute to optical transitions polarized along a particular axis. The combined experimental and theoretical approach enables us to estimate the fundamental electronic bandgap of 2.65-2.68 eV in this prototypical 2D perovskite and to determine the spin-orbit coupling (ΔSO = 1.20 eV) and effective crystal field (δ = -1.36 eV) which break the degeneracy of the frontier conduction band states and determine the exciton fine structure. The methods and results described here afford a better understanding of the connection between structure and induced optical anisotropy in quantum-confined MHPs, an important structure-property relationship for optoelectronic applications and devices.

Ion-beam-induced in-plane a-axis oriented (0001) AlN and ScAlN thin film BAW resonators

High-Q RF bulk acoustic wave filters are still required for mobile communication applications. However, the in-plane orientation of commercial AlN films is random, despite their excellent out-of-plane c-axis orientation. We proposed combining two different orientation control techniques: self-texture for out-of-plane alignment and ion beam irradiation for in-plane alignment. To demonstrate the effectiveness of this approach, both in-plane a-axis and out-of-plane c-axis aligned AlN and ScAlN films were grown on Ti/silica glass substrates using 0.3–0.5 keV grazing ion-beam-assisted RF sputtering technique without using epitaxial growth. The clear six symmetry in the pole-figure observed in AlN and ScAlN thin films indicates the single-crystal-like in-plane a-axis orientation. The ion beam direction corresponded to the in-plane 〈101̄0〉 axis. In-plane x-ray diffraction ϕ-scan curve and ω-scan curve FWHM were measured to be 25° and 2.2°.

Fabrication and Mechanical Performance of Graphene Nanoplatelet/Glass Fiber Reinforced Polymer Hybrid Composites

Glass fiber reinforced polymer (GFRP) composites are promising alternatives for the traditional carbon steel pipes used in the oil and gas industry due to their corrosion and chemical resistance. However, the out-of-plane mechanical properties of GFRPs still need further improvement to achieve this goal. Hence, in this work, two methods combining either vacuum mixing or spray coating with vacuum-assisted resin infusion were studied to fabricate graphene nanoplatelet (GNP)/GFRP hybrid composites. The former method resulted in a severe filtering effect, where the GNPs were not evenly distributed throughout the final composite, whereas the latter process resulted in a uniform GNP distribution on the glass fabrics. The addition of GNPs showed no modest contribution to the tensile performance of the GFRP composites due to the relatively high volume and in-plane alignment of the glass fibers. However, the GNPs did improve the flexural properties of GFRP with an optimal loading of 0.15 wt% GNPs, resulting in flexural strength and modulus increases of 6.8 and 1.6%, respectively. This work indicates how GNPs can be advantageous for out-of-plane mechanical reinforcement in fiber-reinforced composites.

Revealing Pt-seed-induced structural effects to tribological/electrical/thermoelectric modulations in two-dimensional PtSe2 using scanning probe microscopy

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) provide an opportunity to investigate diverse scientific phenomena at an atomic level and have effective technological potential. In recent times, unlike conventional TMDCs, platinum diselenide (PtSe2) has garnered considerable attention owing to its i) fascinating electrical and optical features coupled with mechanical strain and ii) scalable synthesis method. However, its local electrical/tribological/mechanical properties are yet to be examined in detail. In this study, we prepared two different types of PtSe2 layers by controlling the thickness of the Pt-seed film: i) one with horizontal alignments, which are made from ultrathin Pt films and ii) one with vertical and horizontal alignments, which are made from a relatively thick Pt film. Then, the local tribological, mechanical, and electrical properties of PtSe2 were evaluated mainly with scanning probe microscopy (SPM). The local friction study unveiled the marked friction variation depending on the layer directions. An additional study on the local mechanical property indicated that the apparent modulus difference between the two growth directions can lead to dissimilar friction behaviors. Furthermore, local current probing using SPM showed that PtSe2 with both layer directions provides ohmic features to both directions, although the magnitude of conductance along the horizontal direction is ~100 times smaller than that along the vertical one. On the contrary, PtSe2 with only in-plane alignments is configured with multiple horizontal PtSe2 layers, densely stitching themselves together one after another with a very narrow trench region at their boundary. Surprisingly, a local current–voltage spectroscopy analysis showed a small current gap on the bridged trench region, in contrast to the ohmic behavior of the grain interior. This indicates that the local metal-to-semiconductor transition is available, owing to thin PtSe2 layers in the trench regions. The following study at macroscale showed how the overall electrical and thermoelectric properties of PtSe2 can be influenced by local structures triggered by the variation in Pt-seed thickness. The results not only provide a new insight on better understanding the intrinsic features of 2D PtSe2, but also offer important characterization guidance on tailoring their functionalities.

Large rewritable liquid crystal pretilt angle by in situ photoalignment of brilliant yellow films

The ability to control the alignment of liquid crystals (LCs) is a challenge that is near-universal in LC research and applications. While several practical solutions exist for controlling the azimuthal (in-plane) alignment of LCs at an interface, control over the polar, or pretilt angle of the LC often requires a combination of materials or expensive and intricate processing. Here, we introduce a method for exerting control over large pretilt angles utilizing a two-step exposure method applied to Brilliant Yellow (BY) photoalignment films. We demonstrate that BY photoalignment films have the unique ability to enforce a large range of pretilt angles spanning homeotropic (90°) and planar (0°) anchoring conditions at the LC-substrate interface. The alignment is stable over time, rewritable, and patternable. Ultimately the control established here provides a powerful and low-cost means to align and take full advantage of the anisotropic and electro-optic properties of LCs for a wide range of applications.

Hydrodynamics of fringing-field induced defects in nematic liquid crystals

Consumer demand for high resolution and high refresh-rate displays has naturally led to the fabrication of liquid crystal displays with ever smaller pixels. As a consequence, fringing fields between adjacent pixels grow in magnitude, leading to abrupt changes in orientation. Electric field strengths above some threshold can lead to order melting and, in turn, disclinations. This paper presents accurate modeling of disclinations induced by fringing fields due to interdigitated electrodes in a nematic liquid crystal calculated by means of the Landau–de Gennes theory. Disclination paths are determined while taking into account the flow of the liquid crystal. Making use of interdigitated electrodes, precise electrical control over the creation and positioning of defects is demonstrated for homeotropic, planar, hybrid, and in-plane surface alignments.

Thickness-Dependent Photo-Aligned Thin-Film Morphologies of a Block Copolymer Containing an Azobenzene-Based Liquid Crystalline Polymer and a Poly(ionic liquid).

Photo-induced alignment of the thin-film morphologies of azobenzene-containing block copolymers (BCPs) is an effective method to obtain a uniaxial pattern of nanocylinders. Although film thickness is an important factor affecting the self-assembly of BCP thin films, the influence of film thickness on the photo-induced alignment of BCP thin-film morphology has never been systematically studied. Herein, we report the thickness-dependent photo-aligned film morphologies of the BCP containing an azobenzene-based liquid crystalline polymer and a poly(ionic liquid) (PIL), with a perfect uniaxial pattern of PIL nanocylinders. For films aligned with the unpolarized light (UPL), the out-of-plane PIL nanocylinders can be obtained in the film with a thickness of only 1L0 (∼30 nm, where L0 is the layer spacing of the hexagonally packed cylinder array), which is far lower than the thickness (more than 4L0) of the thermally annealed film needed to obtain the same morphology. This change is attributed to the orientation effect of UPL on azobenzene mesogens that suppresses the excluded volume effect. For the films aligned with linearly polarized light (LPL), to take advantage of the excluded volume effect to obtain the planar orientation of azobenzene mesogens, the thickness should be controlled to be no more than 3L0 to achieve an in-plane uniaxial alignment of PIL nanocylinders. The above relationship between the morphology and thickness of photo-aligned film eliminates the obstacles encountered in preparing films with well-ordered photo-aligned morphologies.

Formation mechanism of ferroelectric poly (vinylidene fluoride-trifluoroethylene) copolymers with in-plane dipole alignment under low electric field from melt and its SPR based pyroelectric sensor

P(VDF/TrFE) thin films were annealed under a low electric field using microgapped comb-like electrodes (IDT structure), and their structures and pyroelectric properties were investigated. In-plane dipole alignment of P(VDF/TrFE) was achieved by applying a low electric field (7.7 MV m−1), and the I phase crystal structure with in-plane dipole alignment was transformed following nucleation of the III phase structure. Despite the absence of a Fabry–Perot-type infrared absorption structure, the P(VDF/TrFE) thin films, which were continuously subjected to a low electric field from the melting point to para-ferroelectric phase transition temperature, exhibited a large pyroelectric signal. The voltage sensitivity was 242 V W−1, which is much higher than that of the sandwich type sensor equipped with a Fabry–Perot-type infrared absorption structure on Si substrates (72 V W−1). The improved sensitivity could be attributed to the suppression of the injected charges under the application of a low electric field and the enhancement of the infrared absorption and infrared-to-thermal conversion owing to the surface plasmon resonance on the microgapped IDT structure.

Towards high-performance linear piezoelectrics: Enhancing the piezoelectric response of zinc oxide thin films through epitaxial growth on flexible substrates

Ferroelectrics are popular for sensors, actuators and transducers. However, the energy barrier for reversing the polarization leads to extra energy losses, while the hysteresis causes phase-lags and non-linearities between input and output signals. The high piezoelectric constants of ferroelectrics dictate the figure-of-merit of piezoelectric devices. Enhancing the piezoelectric constant of linear-piezoelectrics potentially leads to next-generation piezoelectric devices free from issues associated with ferroelectrics. By epitaxial growth of undoped ZnO films on flexible Hastelloy substrates, we demonstrated an ~85% improvement in the piezoelectric constant, and more importantly maintained the linearity of the piezoelectric response. Strong out-of-plane and in-plane crystallographic alignments are detected in the epitaxial sample, yet modeling of the effective thin-film piezoelectric constant shows only a limited contribution of the optimized textures. The improvement in the piezoelectric response is ascribed mostly to the in-plane epitaxial strain resulted from the lattice mismatch of ZnO to the substrate. The epitaxial ZnO film on Hastelloy promisingly offer high-precision positioners with nano-/pico-meter resolutions. Enhancing the piezoelectric constant by strain engineering potentially removes the barrier for applications of linear-piezoelectrics and enriches the piezoelectric research community.

Ultrathin Co films with Pt and Au covers—magnetic and structural properties driven by Ga+ ion irradiation

The X/Co 3 nm/Y (where X, Y = Au, Pt) trilayers with as deposited in-plane magnetization alignment were irradiated with 30 keV Ga+ ions in the wide range of ion fluence. The samples were investigated by means of complementary techniques: magneto-optical magnetometry and spectroscopy (in the photon energy range from 1.2 eV to 4.5 eV), magnetic force microscopy, positron annihilation spectroscopy, x-ray diffraction and reflectivity. Difference in miscibility of interface atoms is clearly manifested in various intermixing extent at Co/Pt and Co/Au interfaces and consequently in magnetic properties of the irradiated trilayers. Low irradiation fluence (∼1014 ions cm−2) leads to ∼1 nm interfaces broadening without visible surface etching for all samples, which is related with a distinct drop of magnetic anisotropy. However, the high irradiation fluence (∼5 × 1015 ions cm−2) results in enhanced interface broadening and significant surface etching (∼5 nm) partially removing also Co atoms. Tensile strains (up to 0.5%) were developed in the cover layers. The tensile strain, layers intermixing and the creation of Co–Pt(Au) alloys with different composition formed by irradiation are correlated with the increase of magnetic anisotropy. Moreover it was observed that substitution of Au instead of Pt (as a cap or buffer layer) results in substantial increase of perpendicular magnetic anisotropy. Maximal increase of magnetooptical parameters was observed for Pt/Co/Pt layer. Irradiation induced changes of concentration profiles are revealed using magnetooptical spectra, x-ray reflectivity spectra and simulations with use of binary collision approximation.

Polarization resolved radiation angular patterns of orientationally ordered nanorods

We combine the transfer matrix based algebraic approach with the Green’s function method to theoretically study polarization resolved far-field angular distributions of photoluminescence from quantum nanorods (NRs) embedded in an optically anisotropic film. The emission and excitation properties of NRs are described by the emission and excitation anisotropy tensors. These tensors and the solution of the emission problem expressed in terms of the evolution operators are used to derive the orientationally averaged coherency matrix of the emitted wavefield. For the case of in-plane alignment and unpolarized excitation, we estimate the emission anisotropy parameter and compute the angular profiles for the photoluminescence polarization parameters such as the degree of linear polarization, the Stokes parameter s1, the ellipticity and the polarization azimuth. We show that the alignment order parameter has a profound effect on the angular profiles.

Directional crystallization of C8-BTBT-C8 thin films in a temperature gradient

A directional crystallization of C8-BTBT-C8 in a temperature gradient reduces film roughness and improves in-plane alignment.

Effects of filling, strain, and electric field on the Néel vector in antiferromagnetic CrSb

CrSb is a layered antiferromagnet (AFM) with perpendicular magnetic anisotropy, a high N\'{e}el temperature, and large spin-orbit coupling (SOC), which makes it interesting for AFM spintronic applications. To elucidate the various mechanisms of N\'{e}el vector control, the effects of strain, band filling, and electric field on the magnetic anisotropy energy (MAE) of bulk and thin-film CrSb are determined and analysed using density functional theory. The MAE of the bulk crystal is large (1.2 meV per unit cell). Due to the significant ionic nature of the Cr-Sb bond, finite slabs are strongly affected by end termination. Truncation of the bulk crystal to a thin film with one surface terminated with Cr and the other surface terminated with Sb breaks inversion symmetry, creates a large charge dipole and average electric field across the film, and breaks spin degeneracy, such that the thin film becomes a ferrimagnet. The MAE is reduced such that its sign can be switched with realistic strain, and the large SOC gives rise to an intrinsic voltage controlled magnetic anisotropy (VCMA). A slab terminated on both faces with Cr remains a compensated AFM, but with the compensation occurring nonlocally between mirror symmetric Cr pairs. In-plane alignment of the moments is preferred, the magnitude of the MAE remains large, similar to that of the bulk, and it is relatively insensitive to filling.

High-performance fluoroelastomer-graphene nanocomposites for advanced sealing applications

High-performance sealing materials that can guard key components against high pressure gases and liquid chemicals while withstanding mechanical deformation are of utmost importance in a number of industries. In this present work, graphene nanoplatelets (GNPs) were introduced into a fluoroelastomer (FKM) matrix to improve its mechanical and barrier properties and test its suitability for sealing applications. Nanocomposites filled with different loadings of GNPs were prepared and compared with their counterparts loaded with carbon black (CB). GNPs were dispersed homogeneously with a high degree of in-plane alignment. The tensile and barrier properties of the FKM were improved significantly by the addition of GNPs. Micromechanical modelling based on the shear-lag/rule-of-mixtures theory was used to analyse the reinforcing efficiency of the GNPs. Upon the addition of the GNPs, the elastomer was able to swell anisotropically in liquids, a fact that can be used to tune the swelling properties for sealing applications. In terms of gas permeability, a modification of the well-established Nielsen's theory was introduced to analyse the CO2 permeability for the bulk composite samples. The significantly improved mechanical, thermal and barrier properties at relatively low filler loadings, reveal that the FKM/GNP nanocomposites produced are very promising for use in advanced sealing applications.