High Degree Of Long-range Order Research Articles

Synchrotron Resonant X-Ray Scattering Reveals New Multiscale Ionomer Morphology

Ion-conducting polymer, or ionomer, membranes play a key role as the ion-conducting electrolyte in electrochemical devices, including fuel cells and electrolyzers. The performance of ionomers, for example, its proton conductivity, is defined by its unique molecular structure and multiscale morphology. Perfluorinated sulfonic acid ionomers are the most used ionomers, and they are cast into membranes and thin films from alcohol-rich dispersions. In this work, we examine the connections between the dispersion solvent used for casting and resulting membrane properties. Understanding and controlling the hierarchical phase separated morphology of ionomer membranes and elucidating its relationship to transport properties is crucial for improving device performance. Synchrotron-based x-ray scattering is well-suited to probe the morphology in polymers that lack a high degree of long-range order, including ionomer membranes. However, it is still challenging for conventional high energy hard x-ray scattering to resolve all the morphological details in chemically heterogeneous ionomers. Here, we use emerging synchrotron tender resonant x-ray scattering (TReXS) near the sulfur K-edge to improve scattering contrast and enhance chemical specificity to the sulfonate groups in perfluorinated sulfonic acid ionomers. We find that TReXS reveals unique energy-dependent mesoscale morphological features not apparent in hard x-ray scattering, and these features depend on dispersion composition and ionomer chemistry. These structure-property relationships can be used to guide design of next-generation ionomers for energy applications. Furthermore, this work highlights synchrotron resonant x-ray scattering as an emerging tool for structural characterization of ionomers and electrochemically active polymers in general.

Sub-10 nm Scale Lamellar Structures with a High Degree of Long-Range Order Fabricated by Orthogonal Self-Assembly of Crown Ether/Secondary Dialkylammonium Recognition and Metal···Metal/π-π Interactions.

We here present an orthogonal self-assembly strategy to fabricate a series of metallosupramolecular polymers by coupling planar platinum(II) complexes and starlike poly(ε-caprolactone), through Pt···Pt/π-π interactions and host-guest recognition between secondary dialkylammonium salts and crown ether groups. The solid metallosupramolecular polymers exhibit sub-10 nm scale lamellar structures and one of them occupies an extraordinary degree of long-range order. The platinum(II) complexes can be regarded as an individual supramolecular block to microphase segregate the polymeric segment. Moreover, the metallosupramolecular polymers show intense luminescence and appreciable proton conductivity, originating from these two supramolecular connection modes, respectively. This work paves the way for fabricating metallosupramolecular polymers showing both highly ordered nanostructures and multifunctional properties.

Spectrally Switchable Photodetection with Near-Infrared-Absorbing Covalent Organic Frameworks.

Most covalent organic frameworks (COFs) to date are made from relatively small aromatic subunits, which can only absorb the high-energy part of the visible spectrum. We have developed near-infrared-absorbing low bandgap COFs by incorporating donor–acceptor-type isoindigo- and thienoisoindigo-based building blocks. The new materials are intensely colored solids with a high degree of long-range order and a pseudo-quadratic pore geometry. Growing the COF as a vertically oriented thin film allows for the construction of an ordered interdigitated heterojunction through infiltration with a complementary semiconductor. Applying a thienoisoindigo-COF:fullerene heterojunction as the photoactive component, we realized the first COF-based UV- to NIR-responsive photodetector. We found that the spectral response of the device is reversibly switchable between blue- and red-sensitive, and green- and NIR-responsive. To the best of our knowledge, this is the first time that such nearly complete inversion of spectral sensitivity of a photodetector has been achieved. This effect could lead to potential applications in information technology or spectral imaging.

Morphology control and inducing a curvature on the domain interface by increasing the steric bulk of polymethacrylate in POSS-containing diblock copolymers

Herein, a novel rod-coil type polyhedral oligomeric silsesquioxane (POSS)-containing diblock copolymer was designed to enable the self-assembly of hexagonally packed cylinders of the POSS-containing domain in a poly(n-butyl methacrylate) (PnBMA) matrix. When POSS-containing diblock copolymers were synthesized with polyisoprene or poly(methyl methacrylate), cylindrical structures could not be obtained as POSS-containing polymers form stretched rigid rods. This makes the formation of cylindrical structures with the POSS-containing domain entropically unfavorable. Therefore, to obtain the cylindrical structures, we constructed a novel diblock copolymer using PnBMA to increase the steric bulk and segment volume of the flexible coil. Steric crowding of the butyl groups reduces the entropic free stretching energy of the PnBMA chains, which in turn encourages the formation of a POSS-containing hexagonally packed cylindrical structure within the PnBMA matrix as the system minimizes the total free energy of the thermodynamically stable nanostructure. Small angle X-ray scattering and transmission electron microscopy analyses indicated that cylinders of the POSS domain had formed. Oxygen plasma etching was then used on the thin film to selectively remove the PnBMA domain to yield line and space structures with a high degree of long-range order and a 14 nm feature size. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2234–2242

On-Surface Synthesis of BN-Substituted Heteroaromatic Networks.

We report on the bottom-up fabrication of BN-substituted heteroaromatic networks achieved by surface-assisted polymerization and subsequent cyclodehydrogenation of specifically designed BN-substituted precursor monomers based on a borazine core structural element. To get insight into the cyclodehydrogenation pathway and the influence of molecular flexibility on network quality, two closely related precursor monomers with different degrees of internal cyclodehydrogenation have been employed. Scanning tunneling microscopy shows that, for both monomers, surface-assisted cyclodehydrogenation allows for complete monomer cyclization and the formation of covalently interlinked BN-substituted polyaromatic hydrocarbon networks on the Ag(111) surface. In agreement with experimental observations, density functional theory calculations reveal a significantly lower energy barrier for the cyclodehydrogenation of the conformationally more rigid precursor monomer, which is also reflected in a higher degree of long-range order of the obtained heteroaromatic network. Our proof-of-concept study will allow for the fabrication of atomically precise substitution patterns within BNC heterostructures.

Molecules-oligomers-nanowires-graphene nanoribbons: a bottom-up stepwise on-surface covalent synthesis preserving long-range order.

We report on a stepwise on-surface polymerization reaction leading to oriented graphene nanoribbons on Au(111) as the final product. Starting from the precursor 4,4″-dibromo-p-terphenyl and using the Ullmann coupling reaction followed by dehydrogenation and C-C coupling, we have developed a fine-tuned, annealing-triggered on-surface polymerization that allows us to obtain an oriented nanomesh of graphene nanoribbons via two well-defined intermediate products, namely, p-phenylene oligomers with reduced length dispersion and ordered submicrometric molecular wires of poly(p-phenylene). A fine balance involving gold catalytic activity in the Ullmann coupling, appropriate on-surface molecular mobility, and favorable topochemical conditions provided by the used precursor leads to a high degree of long-range order that characterizes each step of the synthesis and is rarely observed for surface organic frameworks obtained via Ullmann coupling.

Through‐Hole, Self‐Ordered Nanoporous Oxide Layers on Titanium, Niobium and Titanium–Niobium Alloys in Aqueous and Organic Nitrate Electrolytes

Leaky layers: Several 10 μm-thick, highly aligned, porous structures of titanium dioxide, niobium pentoxide and mixed oxides can be grown anodically in nitrate-containing electrolytes with channel diameters in the range of 10–20 nm. Depending on the substrate, the electrochemical growth parameters need to be optimized to achieve a high degree of long-range order.

Freeze-Fracture TEM Imaging of Robust Order in Swollen Phases of Amphiphilic Diblock Copolymers

We report on the structures exhibited by two different diblock poly(styrene)-b-poly(acrylic acid) (PS-b-PAA) copolymers in water, a selective solvent. Using a combination of X-ray scattering and freeze fracture-transmission electron microscopy (FF-TEM), we show that these structures can be widely swollen while retaining their initial morphology and a high degree of long-range order. The analysis of the FF-TEM pictures also evidences the presence of water crystallites of regular size and shape within the confined water domains. We relate the growth of these crystallites to the high local ionic strength of the water swelling the PAA brushes. Moreover, the confinement of the crystallites growth shows that the swollen phases have a very robust structure, potentially useful for confining colloidal particles.

Influence of current density on the distribution of tungsten tracer in porous anodic alumina films

AbstractPorous anodic alumina films have been much studied recently due to interest in the application of the self‐ordered porosity in nanotechnological systems. Experimental investigations have identified anodising regimes that generate pores with a relatively high degree of long‐range order. However, the growth mechanism of the films, and its relation to the ordering of pores, is only partially understood. In the present work, the growth processes are studied over a range of current densities for films formed in oxalic acid. The films are formed on sputtering‐deposited substrates containing tungsten nanolayers that provide W6+ tracer species in the films. The distributions of tracer species are observed by scanning and transmission electron microscopes and the amounts of tracer species quantified by Rutherford backscattering spectroscopy. It is shown that the tungsten tracer remains within an inner region of the cells, with a tungsten‐free region being present next to the pore walls during the growth of the anodic films. Further, the thickness of the anodic film relative to that of oxidised metal increases with increasing current density, which is associated with an increase in the efficiency of film formation. This behaviour is consistent with the formation of pores by flow of film material in the barrier layer to the pore wall regions. Copyright © 2010 John Wiley & Sons, Ltd.

Periodic Arrays of Cu-Phthalocyanine Chains on Au(110)

The structure of ultrathin Cu-phthalocyanine (Cu-Pc) films on the (1 × 2)-Au(110) surface has been studied. The overlayer deposition has been monitored in real time by helium atom scattering (HAS) and low energy electron diffraction (LEED). Throughout the monolayer regime the Cu-Pc molecules are systematically observed to line-up edge-to-edge along the [11̅0] direction of the Au substrate, yielding a commensurate 5-fold periodicity (14.4 Å). Cu-Pc chains deconstruct the 2-fold Au missing row order in the early stage of deposition. A set of higher order periodicities (5-, 7-, and 3-fold) are progressively observed along [001] with increasing Cu-Pc deposition, the 3-fold phase appearing at the monolayer saturation coverage. The corresponding molecular orientation has been studied by variable polarization absorption spectroscopy (XAS), whereas the Au substrate structure has been determined by out-of-plane surface X-ray diffraction. The (5 × 5) phase is found to be rather corrugated, and it exhibits a high degree of long-range order yielding the most prominent diffraction pattern. In the (5 × 5) phase, the Cu-Pc chains are found to lift the underneath missing row reconstruction, being separated by residual Au rows. Similarly, in the more compressed 3-fold monolayer phase, the Cu-Pc molecules were formerly found to lie within a shallow (1 × 3) Au reconstruction [Cossaro, A.; et al. J. Phys. Chem. B 2004, 108, 14671]. From comparison of the different deposition stages, as measured in real time by HAS, we can draw a comprehensive picture of the system evolution. In fact, the observed periodicities at different coverage are always formed by an array of Cu-Pc chains in shallow troughs that are equally spaced by a number of uncovered Au rows, as dictated by the Cu-Pc coverage. The growth of Cu-Pc arrays in the submonolayer range is thus driven by an interchain repulsion mechanism.

Fabrication of 2D Ordered Films of Tobacco Mosaic Virus (TMV): Processing Morphology Correlations for Convective Assembly

Biological colloids, and in particular viruses, have demonstrated substantial potential as scaffolds for nanoparticle arrays. However, the large-area, low-cost, and rapid assembly of viruses, such as by traditional colloidal processing techniques, is not well-established. Systematic exploration of processing space (virus concentration, assembly speed, and substrate surface energy) for the convective assembly method enables the fabrication of films of rod-shaped viruses (tobacco mosaic virus, TMV) with a high degree of long-range order. Monolayer assemblies several centimeters in length are comprised of TMV aligned parallel to the direction of assembly. Increasing TMV concentration and reducing assembly speed resulted in well-ordered viral layering ( N = 2 to N = 12); however, the top virus layer exhibits varying degrees of in-plane disorder.

Odd−Even Effects in Self-Assembled Monolayers of ω-(Biphenyl-4-yl)alkanethiols: A First-Principles Study

Conjugated molecules with a saturated alkyl linker between a thiol docking group and the pi-conjugated core have been shown to form self-assembled monolayers (SAMs) with a high degree of long-range order and uniformity. Additionally, pronounced odd-even effects have been observed in a number of properties characterizing these SAMs. We focus on omega-(biphenyl-4-yl)alkanethiols with n = 0-6 -(CH2)n- units deposited on Au(111) and investigate the microscopic origin of these odd-even effects in terms of the local sulfur-gold bonding geometry by employing first-principles calculations. An additional structural parameter, the torsion angle between the two phenyl rings in the biphenyl moiety, is identified and its relation to the experimentally observed odd-even effects is discussed. More importantly, we address relevant quantities for the application of these SAMs in molecular electronic devices, in particular, the modification of the work function of the underlying metal substrate and the energetic alignment of the molecular orbitals in the SAM with the Fermi level. While no clear trend emerges for the former, we find pronounced odd-even effects for the latter. Furthermore, the insertion of a single methylene unit between the biphenyl core and the thiol appears to largely decouple the valence electronic systems of the pi-conjugated segment and the gold substrate. Our results thus provide a solid theoretical basis for the interface energetics in this important class of systems.

Enantiospecific Adsorption of Alanine on the Chiral Cu{531} Surface

We have studied enantiospecific differences in the adsorption of (S)- and (R)-alanine on Cu{531}R using low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy, and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. At saturation coverage, alanine adsorbs as alaninate forming a p(1 × 4) superstructure. LEED shows a significantly higher degree of long-range order for the S than for the R enantiomer. Also carbon K-edge NEXAFS spectra show differences between (S)- and (R)-alanine in the variations of the π resonance when the linear polarization vector is rotated within the surface plane. This indicates differences in the local adsorption geometries of the molecules, most likely caused by the interaction between the methyl group and the metal surface and/or intermolecular hydrogen bonds. Comparison with model calculations and additional information from LEED and photoelectron spectroscopy suggest that both enantiomers of alaninate adsorb in two different orientations associated ...

Influence of long-range structural order on electrostriction in the as-sintered and annealed (0.4)Pb(In1/2Nb1/2)O3 : (0.6) Pb(Mg1/3Nb2/3)O3 relaxor ceramics

Longitudinal electrostrictive strains in an as-sintered and two annealed (0.4)Pb(In1/2Nb1/2)O3 : (0.6)Pb(Mg1/3Nb2/3)O3 relaxor ceramics were measured by laser-interferometry. The field-related electrostriction coefficients (M33) of the ceramics were then determined. The electrostrictive coefficients progressively decreased with annealing and the strain responses became nonlinear. The ferroelectric hysteresis loops of the as-sintered and annealed ceramics showed progressive decrease in coercive fields and maximum polarizations with increasing annealing time. Transmission electron microscopy studies revealed enlargement of 1 : 1 B-site ordered domains with annealing. The changes in the high-field responses of the annealed ceramics are interpreted as arising from a higher degree of long-range order caused by annealing. A field-induced mechanism is proposed to explain the correlation between the B-site cation long-range order and the electrostrictive behaviour in this relaxor.

Ordered Assembly of α‐Quinquethiophene on a Copper Oxide Nanotemplate

The organic semiconductor alpha-quinquethiophene (T5) is used as the active layer in organic field-effect transistors. We have investigated the adsorption of T5 on the (110) surface of copper and on the CuO nanotemplate formed by the high-temperature exposure of Cu(110) to molecular oxygen. The results were obtained with high-resolution scanning tunneling microscopy (STM) under ultra-high-vacuum (UHV) conditions. The adsorption of T5 on copper is an important model system because it mimics the active-layer-electrode interface in organic devices. The molecules were observed to adsorb onto both the pristine Cu(110) surface and the CuO nanotemplate, showing a greater affinity for the pristine copper surface. Surprisingly, however, the T5 molecules assembled with a much higher degree of long-range order on the oxygen-passivated portion of the surface.

Fabrication of three-dimensional periodic microstructures in photoresist SU-8 by phase-controlled holographic lithography

Three-dimensional (3D) periodic dielectric structures were recorded in a commercial photoresist SU-8 by exposure to intensity patterns created by five interfering coherent femtosecond Ti : sapphire laser pulses. Periodic symmetry of these patterns was controlled by the choice of mutual convergence angles of the beams as well as their phases. The fabricated structures are mechanically and chemically stable, well-connected frameworks of SU-8 regions in air; the smallest dimensions of SU-8 features are in the sub-micrometre range. The structures exhibit a high degree of long-range order across areas as large as 1 mm in cross-section.

Effects of sediment iron mineral composition on microbially mediated changes in divalent metal speciation: Importance of ferrihydrite

Dissimilatory metal reducing bacteria (DMRB) can influence geochemical processes that affect the speciation and mobility of metallic contaminants within natural environments. Most investigations into the effect of DMRB on sediment geochemistry utilize various synthetic oxides as the Fe III source (e.g., ferrihydrite, goethite, hematite). These synthetic materials do not represent the mineralogical composition of natural systems, and do not account for the effect of sediment mineral composition on microbially mediated processes. Our experiments with a DMRB ( Shewanella putrefaciens 200) and a divalent metal (Zn II) indicate that, while complexity in sediment mineral composition may not strongly impact the degree of “microbial iron reducibility,” it does alter the geochemical consequences of such microbial activity. The ferrihydrite and clay mineral content are key factors. Microbial reduction of a synthetic blend of goethite and ferrihydrite (VHSA-G) carrying previously adsorbed Zn II increased both [Zn II-aq] and the proportion of adsorbed Zn II that is insoluble in 0.5 M HCl. Microbial reduction of Fe III in similarly treated iron-bearing clayey sediment (Fe-K-Q) and hematite sand, which contained minimal amounts of ferrihydrite, had no similar effect. Addition of ferrihydrite increased the effect of microbial Fe III reduction on Zn II association with a 0.5 M HCl insoluble phase in all sediment treatments, but the effect was inconsequential in the Fe-K-Q. Zinc k-edge X-ray absorption spectroscopy (XAS) data indicate that microbial Fe III reduction altered Zn II bonding in fundamentally different ways for VHSA-G and Fe-K-Q. In VHSA-G, ZnO 6 octahedra were present in both sterile and reduced samples; with a slightly increased average Zn-O coordination number and a slightly higher degree of long-range order in the reduced sample. This result may be consistent with enhanced Zn II substitution within goethite in the microbially reduced sample, though these data do not show the large increase in the degree of Zn-O-metal interactions expected to accompany this change. In Fe-K-Q, microbial Fe III reduction transforms Zn-O polyhedra from octahedral to tetrahedral coordination and leads to the formation of a ZnCl 2 moiety and an increased degree of multiple scattering. This study indicates that, while many sedimentary iron minerals are easily reduced by DMRB, the effects of microbial Fe III reduction on trace metal geochemistry are dependent on sediment mineral composition.

Optical and magneto-optical properties of MnPt3 films (abstract)

Optically thick films of MnPt3 were prepared by magnetron sputtering onto quartz substrates. Postdeposition annealing at 850 °C resulted in highly textured (111) films with the L12 (Cu3Au) structure. MnPt3 films are ferromagnetic with a Curie temperature of 380 °C, and they show large magneto-optical effects in the visible.12 These films also show a high degree of long-range order. The diagonal components of the dielectric tensor were determined using variable angle spectroscopic ellipsometry measurements over the spectral range 1.2–2.4 eV. Magneto-optic Kerr rotation and ellipticity measurements were made at near normal incidence over the spectral range 1.4–3.6 eV to determine the off-diagonal components of the MnPt3 dielectric tensor. First-principles electronic structure calculations were carried out for the ordered MnPt3 structure, and from these the components of the dielectric tensor were calculated. We find excellent agreement between the measured and calculated diagonal components, but only fair agreement for the off-diagonal components.

Sb-induced GaAs(111)B surface reconstructions: success and failure of the electron-counting rule

Deposition of antimony on the GaAs(111)B-(2 × 2) surface, followed by annealing in the 300–525°C range, results in reconstructions having Sb trimers and Sb chains as their basic structural units. Scanning tunnelling microscopy data illustrates that a transition from a complex surface terminated by a number of local arrangements of Sb chain pairs and trimers to a (1 × 3) reconstruction having a high degree of long-range order occurs as the annealing temperature is increased. While the various unit cells formed by the combination of chain pairs and trimers satisfy the electron-counting rule, the unit cell of the (1 × 3) structure formed at higher annealing temperatures has partially filled dangling bonds. Some possible reasons for this observed breakdown of the electron-counting model are discussed.

Long-range order and magnetic properties of Mn xPt 1− x thin films

Thin films of Mn x Pt 1− x ( x = 0.18, 0.22, 0.25, 0.30, 0.34) were prepared by magnetron sputtering onto quartz substrates. After annealing in vacuum for 1 h at 850°C, X-ray diffraction indicates that the films have the Cu 3Au cubic structure ( a = 3.87 A ̊ ) and are highly textured with the (111) axis along the film normal. These samples have a high degree of long-range order, as indicated by the ratio of the intensities of the superlattice (100) and fundamental (200) X-ray diffraction reflections. We report here the results of magnetic and magneto-optical measurements on these samples over a wide range of temperatures.