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We designed high-volumetric-energy-density supercapacitors from monolithic composites composed of self-standing carbon foam (CF) as the conducting matrix and embedded hierarchically organized porous carbon (PICK) as the active material. Using multiprobe scanning tunneling microscopy at selected areas, we were able to disentangle morphology-dependent contributions of the heterogeneous composite to the overall conductivity. Adding PICK is found to enhance the conductivity of the monoliths by providing additional links for the CF network, enabling high and stable performance. The resulting all-carbon CF-PICK composites were used as self-standing electrodes for symmetric supercapacitors without the need for a binder, additional conducting additive, metals as a current collector, or casting/drying steps. Supercapacitors achieved a capacitance of 181 F g

Application of twin polymerization by a base-catalysed, surface-mediated coating procedure is shown on different templates. Post-polymerization treatment leads to microporous shells on MWCNTs, N-doped carbon particles, and copper particles.

Twin monomers [Mg(2-OCH2-cC6H4O)][L]0.8 (2, L=diglyme) and [Mg(2-OCH2-cC6H4O)][L]0.66 (3, L=tmeda) form by their thermal polymerization interpenetrating organic-inorganic hybrid materials in a straightforward manner. Carbonization (Ar) followed by calcination gave porous MgO (2: surface area 200 m2g-1, 3: 400 m2g-1), which showed in catalytic studies towards Meerwein-Ponndorf-Verley reductions excellent yields and complete conversions for cyclohexanone and benzaldehyde. However, with crotonaldehyde a mixture of C4–C8 compounds was obtained. When MgO was exposed to air then primarily crotyl alcohol was formed. The range of applications could be easily extended by twin polymerization of 3 in presence of [Cu-(O2CCH2O(CH2CH2O)2Me)2] (4) or [Ag(O2CCH2-cC4H3S)(PPh3)] (5), resulting in the formation of nanoparticle-decorated porous CuO@MgO or Ag@MgO materials, which showed high catalytic reactivity towards the reduction of methylene blue.

High mass loading asymmetric micro-supercapacitors (MSCs) are key components for the development of high-performance energy and power supply systems. Here, a concept for achieving high mass loading electrodes is presented and applied to high mass loading micro-supercapacitors with ultrahigh areal energy and power density. The positive electrode is made from porous carbon with birnessite coverage and multiwalled carbon nanotubes (CNTs) as conducting additives (PIC-CNTs-MnO

We study the interplay of chemisorbed hydrogen and physisorbed PbPc molecules on epitaxial graphene by means of surface transport and density functional theory. While the adsorption of atomic hydro...

Besides graphene, further honeycomb 2D structures were successfully synthesized on various surfaces. However, almost flat plumbene hosting topologically protected edge states could not yet be realized. In this Letter, we investigated the intercalation of Pb on buffer layers on SiC(0001). Thereby, suspended and charge neutral graphene emerged, and the intercalated Pb formed plumbene honeycomb lattices, which are rotated by ±7.5° with respect to graphene. Along with this twist, a proximity-induced modulation of the hopping parameter in graphene opens a band gap of around 30 meV at the Fermi energy, giving rise to a metal-insulator transition. Moreover, the edges of the intercalated plumbene layers revealed edge states within the gap of the conduction bands at around 1 eV as expected for charge neutral plumbene.

Protected and spin-polarized transport channels are the hallmark of topological insulators, coming along with an intrinsic strong spin-orbit coupling. Here we identified such corresponding chiral states in epitaxially grown zigzag graphene nanoribbons (zz-GNRs), albeit with an extremely weak spin-orbit interaction. While the bulk of the monolayer zz-GNR is fully suspended across a SiC facet, the lower edge merges into the SiC(0001) substrate and reveals a surface state at the Fermi energy, which is extended along the edge and splits in energy toward the bulk. All of the spectroscopic details are precisely described within a tight binding model incorporating a Haldane term and strain effects. The concomitant breaking of time-reversal symmetry without the application of external magnetic fields is supported by ballistic transport revealing a conduction of G = e2/h.

We report on the fabrication of Polyacrylonitrile (PAN) based electrospun carbon nanofiber (ECNF) reinforced with multi-walled carbon nanotubes (MWCNTs) and characterization of the graphitic structure as well as electrical transport properties for four different ECNF systems. The different systems were obtained by the combination of two different ways of cyclization for pristine PAN and PAN with CNTs addition (PAN/CNT), typically by the application of constant creep stress and a constraint fixing. The addition of CNTs improved the graphitic structure of PAN. For the detailed analysis of different systems, carbonization was performed at 1700 °C and the graphitic structures were characterized. The CNTs improve the alignment of graphitic domains even for non-creep cyclized systems. The application of creep stress during cyclization results in highly aligned graphene planes. However, the creep stress cyclized PAN/CNT system exhibited a reduction in the alignment of graphene planes coming along with the observation of discontinuous, randomly orientated domains and a reduced conductivity. The electrical anisotropy increased for creep cyclized PAN and PAN/CNT compared to non-creep stress cyclized system. Our findings reveal that electrical transport in carbon nanofibers need to be considered as a cumulative effect of hopping and band transport along chemically and structurally inhomogeneous ECNFs.

Topological insulators (TIs) gained high interest due to their protected electronic surface states that allow dissipation‐free electron and information transport. In consequence, TIs are recommended as materials for spintronics and quantum computing. Yet, the number of well‐characterized TIs is rather limited. To contribute to this field of research, we focused on new bismuth‐based subiodides and recently succeeded in synthesizing a new compound Bi12Rh3Sn3I9, which is structurally closely related to Bi14Rh3I9 – a stable, layered material. In fact, Bi14Rh3I9 is the first experimentally supported weak 3D TI. Both structures are composed of well‐defined intermetallic layers of ∞ 2[(Bi4Rh)3I]2+ with topologically protected electronic edge‐states. The fundamental difference between Bi14Rh3I9 and Bi12Rh3Sn3I9 lies in the composition and the arrangement of the anionic spacer. While the intermetallic 2D TI layers in Bi14Rh3I9 are isolated by ∞ 1[Bi2I8]2− chains, the isoelectronic substitution of bismuth(III) with tin(II) leads to ∞ 2[Sn3I8]2− layers as anionic spacers. First transport experiments support the 2D character of this material class and revealed metallic conductivity., Insulating: Bi12Rh3Sn3I9, a weak 3D topological insulator (TI) is derived from Bi14Rh3I9, which was the first weakly coupling (“weak”) 3D TI; a bulk semiconductor that hosts protected electronic surface states that allow dissipation‐free electron and information transport due to the specific symmetries of its electronic band structure. In consequence of their topological properties, TIs are envisioned as promising candidates for high‐performance spin field‐effect transistors and quantum bits.

Graphene was shown to reveal intriguing properties of its relativistic two-dimensional electron gas; however, its implementation to microelectronic applications is missing to date. In this work, we present a comprehensive study of epitaxial graphene on technologically relevant and in a standard CMOS process achievable Ge(100) epilayers grown on Si(100) substrates. Crystalline graphene monolayer structures were grown by means of chemical vapor deposition (CVD). Using angle-resolved photoemission spectroscopy and in situ surface transport measurements, we demonstrate their metallic character both in momentum and real space. Despite numerous crystalline imperfections, e.g., grain boundaries and strong corrugation, as compared to epitaxial graphene on SiC(0001), charge carrier mobilities of 1 × 104 cm2/Vs were obtained at room temperature, which is a result of the quasi-charge neutrality within the graphene monolayers on germanium and not dependent on the presence of an interface oxide. The interface roughness due to the facet structure of the Ge(100) epilayer, formed during the CVD growth of graphene, can be reduced via subsequent in situ annealing up to 850 °C coming along with an increase in the mobility by 30%. The formation of a Ge(100)-(2 × 1) structure demonstrates the weak interaction and effective delamination of graphene from the Ge/Si(100) substrate.

The self-assembly process of racemic mixtures of right(L)- and left(D)-handed α-polyalanine molecules (DL-PA) with a length of 4 nm (27 alanine units) and a helix pitch of λ=0.54 nm on HOPG was inv...

The synthesis of [Au{S=C(NH2)2}2][SO3Me] (1) (a) by the anodic oxidation of gold metal in an anolyte of thiourea and methansulfonic acid and (b) by the reaction of Au(OH)3 with an aqueous solution of methanesulfonic acid in the presence of thiourea is reported. The structure of 1 in the solid state has been determined by single-crystal X-ray diffraction showing a linear S–Au–S unit with the thiourea ligands in a leaflet structure folded by 113.2(3)°. The cation of complex 1 is a dimer, based on short S · · · C interactions between two adjacent mononuclear cations. The thermal decomposition behavior of 1 was studied by TG and TG-MS confirming that it decomposes under inert gas or oxygen atmosphere in four steps in the temperature range of 200–650°C. Initial decomposition starts with the release and fragmentation of one of the thiourea ligands, followed by the anion degradation. Powder X-ray diffraction studies specified the formation of gold metal. Based on this observation, complex 1 was used as precursor for the formation of gold nanoparticles (Au NPs) in 1-hexadecylamine (c = 4.0 mol L−1) at T = 330°C without any addition of reducing agents. TEM, electron diffraction, and UV/Vis spectroscopy studies were carried out. Au NPs of size 15 ± 4 nm were formed, showing the characteristic surface plasmon resonance at 528 nm.

The adsorption of chiral molecules was recently shown to trigger a change in the magnetisation of mesoscopic magnetic domains in a ferromagnetic underlayer. In this work, we investigated the macroscopic (magneto-)optical response of chemisorbed α-helical polyalanine self-assembled monolayers (SAMs) on a gold and gold-capped-cobalt thin film on Au substrates using spectroscopic ellipsometry and magneto-optical Kerr effect spectroscopy and microscopy. The optical and magneto-optical spectra reveal selective chemisorption of the α-helical polyalanine molecules depending on the orientation of the substrate remanent magnetisation during the SAMs process. Moreover, a sign change of the magneto-optical response was observed in some of the magnetic substrates after the chiral SAMs formation.

Polyalanine molecules (PA) with an α-helix conformation have recently attracted a great deal of interest, as the propagation of electrons through the chiral backbone structure comes along with spin polarization of the transmitted electrons. By means of scanning tunneling microscopy and spectroscopy under ambient conditions, PA molecules adsorbed on surfaces of epitaxial magnetic Al2O3/Pt/Au/Co/Au nanostructures with perpendicular anisotropy were studied. Thereby, a correlation between the PA molecules ordering at the surface with the electron tunneling across this hybrid system as a function of the substrate magnetization orientation as well as the coverage density and helicity of the PA molecules was observed. The highest spin polarization values, P, were found for well-ordered self-assembled monolayers and with a defined chemical coupling of the molecules to the magnetic substrate surface, showing that the current-induced spin selectivity is a cooperative effect. Thereby, P deduced from the electron transmission along unoccupied molecular orbitals of the chiral molecules is larger as compared to values derived from the occupied molecular orbitals. Apparently, the larger orbital overlap results in a higher electron mobility, yielding a higher P value. By switching the magnetization direction of the Co layer, it was demonstrated that the non-spin-polarized STM can be used to study chiral molecules with a submolecular resolution, to detect properties of buried magnetic layers and to detect the spin polarization of the molecules from the change in the magnetoresistance of such hybrid structures.

The complex behavior of magnetoconductance of Bi films grown epitaxially on Si(111) with a thickness of 20--100 bilayers (BL) was measured at $T$= 9 K in magnetic fields up to $B=4\phantom{\rule{0.16em}{0ex}}\mathrm{T}$, oriented in-plane parallel and perpendicular to the electric dc current $I$. Contributions to magnetoconductance (MC) by diffuse scattering, by weak localization (WL) as well as by weak antilocalization (WAL) were identified. All these components to MC turned out to be isotropic in two dimensions, i.e., no dependence on angle between $B$ and $I$ within the surface plane was found. Only for $B\phantom{\rule{0.16em}{0ex}}\ensuremath{\perp}\phantom{\rule{0.16em}{0ex}}I$ an increase of MC was detected that is, to first approximation, $\ensuremath{\propto}{B}^{2}$. It is ascribed to ballistic scattering between the Rashba-split interfaces that allow Umklapp scattering without spin flip. While MC within the surface states, dominant at small thicknesses, $d$, shows negligible diffuse scattering under the chosen geometry, their quantum corrections are characterized by WAL with $\ensuremath{\alpha}=\ensuremath{-}0.3$ and a coupling strength that decays $\ensuremath{\propto}1/d$ with layer thickness. The admixing of quantized bulk states, which dominates MC above 50 BL, not only increases diffuse scattering, it introduces WL in combination with WAL. Presumably due to hybridization with the surface states, it also modifies strongly the WAL component for $dg60$ BL. Thus our findings suggest an intriguing interplay in magnetotransport between 2D and quantized 3D states at the Fermi surface of ultrathin bismuth quantum films and provide further deep insight into the electronic transport in quantized and partly spin split bands.

The strong sensitivity of plasmonic excitations on nanostructures to their environment is studied, going to the ultimate limit of single atomic chains. As a first step, we investigated how metallic...

Proximity coupling is discussed as a promising approach to tune further graphene’s properties. Organic π-conjugated molecules couple per se weakly to surfaces and the class of phthalocyanines provides manifold possibilities for molecular functionalization. We have investigated the adsorption of lead phthalocyanine (PbPc) on epitaxial graphene by means of scanning tunneling microscopy and in-situ electronic transport measurements in order to quantify both a molecular charge transfer and modifications of the carrier mobility in graphene. Compared to other metallic surfaces, monolayer structures of PbPc adsorbed on graphene solely pointing upwards, apparently, due to the antibonding character of the Pb-states with the pz-orbitals of graphene. The squared lattice of the molecular layer is not commensurate with the honeycomb lattice of graphene and the PbPc molecules are slightly tilted, thus forming a chiral monolayer structure. Despite this interaction with graphene, the charge state of the molecule as well as the mobility of the charge carriers in graphene are not altered. Therefore, monolayer structures of Pb molecules are promising candidates for proximity studies in graphene.

Graphene nanoribbons (GNRs) are considered as major building blocks in future carbon-based electronics. The electronic performance of graphene nanostructures is essentially influenced and determined by their edge termination and their supporting substrate. In particular, semi-conducting, as well as metallic GNRs, can be fabricated by choosing the proper template which is favorable for device architecture designs. This study highlights the impact of microscopic details of the environment of the GNRs on the charge transport in GNRs. By means of lateral force, conductive atomic force and nanoprobe measurements, we explore the charge propagation in both zig-zag and armchair GNRs epitaxially grown on SiC templates. We directly image transport channels on the nanoscale and identify SiC substrate steps and nano-instabilities of SiC facets as dominant charge scattering centers. [Figure not available: see fulltext.].

BiFeO3 nanoparticles were synthesized using a sol gel method and its photocatalytic ability for formic acid reformation is reported, for the first time, focusing on the BiFeO3 stability after photocatalytic reaction at ∼ pH 3. Reformation of formic acid in O2-free aqueous suspensions was found to result in the evolution of CO2 and H2 gases. However, the expected molar ratio of 1:1 was not evolved. Significantly lower amounts of H2 than expected were detected. The position of the conduction band of BiFeO3 resides well below the reduction potential of the protons to form molecular H2, hence it is anticipated that the photoexcited electrons react mainly with other species being present in the reactor, probably the photocatalyst itself. To assess the changes occurring in the photocatalyst, bulk and surface analysis before and after the photocatalytic reaction were performed using different techniques. XRD revealed changes occurring in the bulk of the photocatalyst such as leaching of most of the impurity phases accompanied by the relaxation of the strained lattice to its ideal position. From XPS, the ratio between Fe3+: Fe2+ before and after photocatalytic reaction with formic acid was found to be 86:14 and 64:36, respectively, thus evincing a reduction process of Fe3+ by the photo generated electrons in the conduction band that were unable to reduce H+ into H2. Leaching of Fe and, to less extent, Bi ions into the solution after reaction was recorded. From the fitted XPS, the nominal composition of BFO was calculated to be Bi1Fe0.9O2.9 and Bi1Fe0.71O2.7 before and after the photocatalytic reaction. The results presented in this work signify the importance of addressing bulk and surface stability of iron-based photocatalysts to ensure long-term usability.

In this study, we first show that the argon flow during epitaxial graphene growth is an important parameter to control the quality of the buffer and the graphene layer. Atomic force microscopy (AFM) and low-energy electron diffraction (LEED) measurements reveal that the decomposition of the SiC substrate strongly depends on the Ar mass flow rate while pressure and temperature are kept constant. Our data are interpreted by a model based on the competition of the SiC decomposition rate, controlled by the Ar flow, with a uniform graphene buffer layer formation under the equilibrium process at the SiC surface. The proper choice of a set of growth parameters allows the growth of defect-free, ultra-smooth and coherent graphene-free buffer layer and bilayer-free monolayer graphene sheets which can be transformed into large-area high-quality quasi-freestanding monolayer and bilayer graphene (QFMLG and QFBLG) by hydrogen intercalation. AFM, scanning tunneling microscopy (STM), Raman spectroscopy and electronic transport measurements underline the excellent homogeneity of the resulting quasi-freestanding layers. Electronic transport measurements in four-point probe configuration reveal a homogeneous low resistance anisotropy on both {\mu}m- and mm scales., Comment: Supplementary data is included

The stacking of different two-dimensional (2D) materials provides a promising approach to realize new states of quantum matter. In this combined scanning tunneling microscopy (STM) and density functional theory (DFT) study we show that the structure in weakly bound, purely van der Waals (vdW) interacting systems is strongly influenced by screening and relaxation. We studied in detail the physisorption of lead phthalocyanine (PbPc) molecules on epitaxial monolayer graphene on SiC(0001) as well as on highly ordered pyrolytic graphite (HOPG), resembling truly 2D and anisotropic, semi-infinite three-dimensional (3D) supports. Our analysis demonstrates that the different deformation ability of the vdW coupled systems, i.e., their actual thickness and buckling, triggers the molecular morphology and exhibits a proximity coupled band structure. It thus provides important implications for future 2D design concepts.

This article shows a new way to produce hierarchical microsieves by layering three types of float-cast microsieves, differing from each other in their pore diameters (approximately 68 μm, 7 μm, and 0.24 μm) on top of each other. The unsupported microsieves with 7 and 0.24 μm pore sizes are mechanically fragile. The complete hierarchical sieve composed of all three layers, however, can be handled manually without special precaution. This article further investigates the flow through the hierarchical sieve and filtration via experiment, theory (Hagen-Poiseuille's and Sampson-Roscoe's law), and simulation (numerically solving the Navier-Stokes equations for a predefined set of discrete volumetric elements). The experimental, theoretical, and simulated permeances of the microsieves and the hierarchical sieves are in reasonable agreement with each other and are significantly higher than the permeances of conventional filtration media. In filtration experiments, the hierarchical sieves show the expected sharp size cut-off, retaining particles of diameters exceeding the pore diameter.

Self-organized gold chains on vicinal Si(111) surfaces represent prototype examples of quasi-one-dimensional objects that are stabilized by hybridization with Si surface states. Their plasmons contain important information about the unoccupied bandstructure close to the Fermi level. Using Si(775)–Au as an example, we report here the modifications of the plasmon dispersion by the simple atomic adatom species H and O. Using a combination of low energy electron diffraction and high-resolution electron energy loss spectroscopy, we study the interconnection between plasmonic excitation and the corresponding local surface structure. Both adsorbates do not destroy metallicity, but, similar to Si(553)–Au, atomic hydrogen enhances dimerization of the Au chains, which at small concentrations counteracts the disorder introduced by random adsorption. This effect, most likely caused by electron donation of H to the surface states, is missing in case of adsorbed oxygen, so that only the effect of disorder is observed. For both adsorbates increasing disorder as a function of adsorbate concentration finally results in plasmon localization and opening of a band gap.

Helical molecules have recently attracted interest due to their capability for robust spin polarization of transmitted electrons. By means of mechanically controlled break Au junctions, we analyze the transport properties of single lysine-doped and cysteine-terminated polyalanine (PA) molecules of various lengths (2.4--5.4 nm). The conductance varies exponentially with the (effective) length of the molecules and does not depend on the temperature (90--300 K), thus electron tunneling is the dominant transport mechanism. The decay constant for the PA molecule is found to be $3.5\phantom{\rule{0.28em}{0ex}}{\mathrm{nm}}^{\ensuremath{-}1}$, significantly smaller compared to those of other organic molecules, emphasizing the high conductivity along the helical polypeptides and reflecting a low tunneling barrier, which decreases further for fields exceeding $5\ifmmode\times\else\texttimes\fi{}{10}^{5}\phantom{\rule{0.28em}{0ex}}\mathrm{V}/\mathrm{cm}$. The conductance histograms of all PA molecules investigated reveal characteristic satellite peaks, which correlate with the apparent molecule length in multiples of characteristic peptide sequences. We attribute this effect to a racheting of interdigitated molecules adsorbed on each side of the electrodes during the opening/closing cycles.

In bismuth quantum films, a fascinating interplay between (bulk) quantum well and interface (edge) states is observed in this comprehensive study of DC magnetoconductance and Hall resistivity as a function of film thickness. While for thin layers (up to 40 bilayers, BL) conductance is governed by the surface states, strong contributions of a quantum well state dominate above 70 BL. Quantum corrections in a magnetic field normal to the surface, however, are dominated by the interface states for all thicknesses investigated for reasons discussed in the paper.

The low-temperature spin-orbit density phase of Pb quantum wires on Si(557) was investigated by scanning tunneling microscopy. High resolution images of this phase allow the proposal of an atomistic model for the densely-packed Pb coverages on the (223) facets. A metal-insulator phase transition was confirmed by local spectroscopy and the BCS-like gap feature of $2\mathrm{\ensuremath{\Delta}}\ensuremath{\approx}30\phantom{\rule{0.28em}{0ex}}\text{meV}$ at 10 K correlates with the transition temperature of ${T}_{c}=78\phantom{\rule{0.28em}{0ex}}\text{K}$ seen in surface transport experiments. Moreover, Pb excess coverage adds an extra row of Pb atoms on the mini-(111) terraces. These atoms induce a metallic state located at the step edge at low temperature and quench the charge and spin correlations of the spin-orbit density phase.

Improving the graphitic structure in carbon nanofibers (CNFs) is important for exploiting their potential in mechanical, electrical and electrochemical applications. Typically, the synthesis of carbon fibers with a highly graphitized structure demands a high temperature of almost 2500 &deg, C. Furthermore, to achieve an improved graphitic structure, the stabilization of a precursor fiber has to be assisted by the presence of tension in order to enhance the molecular orientation. Keeping this in view, herein we report on the fabrication of graphene nanoplatelets (GNPs) doped carbon nanofibers using electrospinning followed by oxidative stabilization and carbonization. The effect of doping GNPs on the graphitic structure was investigated by carbonizing them at various temperatures (1000 &deg, C, 1200 &deg, C, 1500 &deg, C and 1700 &deg, C). Additionally, a stabilization was achieved with and without constant creep stress (only shrinkage stress) for both pristine and doped precursor nanofibers, which were eventually carbonized at 1700 &deg, C. Our findings reveal that the GNPs doping results in improving the graphitic structure of polyacrylonitrile (PAN). Further, in addition to the templating effect during the nucleation and growth of graphitic crystals, the GNPs encapsulated in the PAN nanofiber matrix act in-situ as micro clamp units performing the anchoring function by preventing the loss of molecular orientation during the stabilization stage, when no external tension is applied to nanofiber mats. The templating effect of the entire graphitization process is reflected by an increased electrical conductivity along the fibers. Simultaneously, the electrical anisotropy is reduced, i.e., the GNPs provide effective pathways with improved conductivity acting like bridges between the nanofibers resulting in an improved conductivity across the fiber direction compared to the pristine PAN system.

The ability to define an off state in logic electronics is the key ingredient that is impossible to fulfill using a conventional pristine graphene layer, due to the absence of an electronic bandgap. For years, this property has been the missing element for incorporating graphene into next-generation field effect transistors. In this work, we grow high-quality armchair graphene nanoribbons on the sidewalls of 6H-SiC mesa structures. Angle-resolved photoelectron spectroscopy (ARPES) and scanning tunneling spectroscopy measurements reveal the development of a width-dependent semiconducting gap driven by quantum confinement effects. Furthermore, ARPES demonstrates an ideal one-dimensional electronic behavior that is realized in a graphene-based environment, consisting of well-resolved subbands, dispersing and non-dispersing along and across the ribbons respectively. Our experimental findings, coupled with theoretical tight-binding calculations, set the grounds for a deeper exploration of quantum confinement phenomena and may open intriguing avenues for new low-power electronics., Here, the authors investigate armchair graphene nanoribbons by angle-resolved photoelectron spectroscopy, and show the development of a width-dependent semiconducting gap driven by quantum confinement effects, and an ideal one-dimensional electronic behaviour.

A thermal atomic layer deposition process with precursors tris(trimethylsilyl) phosphate (TTMSP), titanium tetrachloride (TiCl4), and water was used with various pulse sequences in order to deposit titanium phosphate onto bundles of carbon fibers (diameter of one filament = 7 μm, 6000 filaments per bundle) and flat silicon substrates. Pulse sequence 1, TTMSP/N2/TiCl4/N2, which comprises no water, yields no significant deposition. Pulse sequence 2, TTMSP/N2/H2O/N2/TiCl4/N2, which comprises a water pulse, yields a mixed phosphate/oxide coating and shows a self-limiting character at 200 °C with a growth per cycle of 0.22 nm cycle-1. Wet chemical analysis of the coating revealed a ratio of Ti:P between 3:1 and 2:1 in reasonable agreement with the composition Ti2.4P1O7 obtained from X-ray photoelectron spectroscopy. Thus, the deposited material can approximately be described as a mixture of Ti¾PO4 and TiO2 in a molar ratio of 1:1.5. The coating shifts the temperature of the onset of oxidation - 3% weight loss in thermogravimetry - of the carbon fibers from 630 °C (uncoated C-fiber) to 750 °C (with the titanium phosphate coating).

This article describes the preparation of hierarchical microsieves via float-casting using raspberry particles. The raspberry particles consist of a larger spherical particle (the core) and smaller particles (satellites) that are attached on the surface of the core and were connected to the core via a surface reaction of isocyanate and amino groups. The raspberry particles were spread onto a water surface as a monolayer and a mixture of polymethylmethacrylate (PMMA) and toluene was poured over this monolayer. After evaporating the solvent, a composite membrane composed of a continuous polymer film with particles protruding out of at least one of its interfaces is obtained. The raspberry particles were etched away, and the membrane thus converted into a hierarchical microsieve comprising larger and smaller pores caused by the core and satellite particles, respectively. The most promising raspberry particles for this purpose consisted of glass beads of 75 μm diameter as core and Stober-particles of 316 nm respectively 275 nm diameter. The resulting microsieves were suitable for filtration and permeance tests. The permeance at low Reynold numbers (liquid flow velocity through the pores) is in accordance with established values for microsieves. The membranes were able to retain particles exceeding the pore size.

Graphene pn-junctions offer a rich portfolio of intriguing physical phenomena. They stand as the potential building blocks for a broad spectrum of future technologies, ranging from electronic lenses analogous to metamaterials in optics, to high-performance photodetectors important for a variety of optoelectronic applications. The production of graphene pn-junctions and their precise structuring at the nanoscale remains to be a challenge. In this work, a scalable method for fabricating periodic nanoarrays of graphene pn-junctions on a technologically viable semiconducting SiC substrate is introduced. Via H-intercalation, 1D confined armchair graphene nanoribbons are transformed into a single 2D graphene sheet rolling over 6H-SiC mesa structures. Due to the different surface terminations of the basal and vicinal SiC planes constituting the mesa structures, different types of charge carriers are locally induced into the graphene layer. Using angle-resolved photoelectron spectroscopy, the electronic band structure of the two graphene regions are selectively measured, finding two symmetrically doped phases with p-type being located on the basal planes and n-type on the facets. The results demonstrate that through a careful structuring of the substrate, combined with H-intercalation, integrated networks of graphene pn-junctions could be engineered at the nanoscale, paving the way for the realization of novel optoelectronic device concepts. Funding Agencies|Deutsche Forschungsgemeinschaft (DFG)German Research Foundation (DFG) [Sta315/9-1, Te386/13-1, Te386/12-1]; Projekt DEAL

Highly efficient magnetic spin memory devices operating at ambient temperatures were recently realized via self-assembled molecular layers of an enantiomeric phase of polyalanine (PA). However, the repeatability and yield of such molecular devices rely sensitively on the layer quality. In this work, we grew molecular layers of α-l-PA (36 monomers of α-amino acid, 5.4 nm) on highly oriented pyrolytic graphite surfaces and investigated the structure by scanning tunneling microscopy under ambient conditions at the liquid–solid interface, complemented by X-ray photoelectron and Raman spectroscopies. Our results suggest that interdigitation of adjacent molecules takes place, which leads to a packing density of 0.8 PA/nm2, which is more than a factor of 2 higher than that of the closed-packed structure. The interdigitation not only stabilizes the PA film by additional H bonds but also ensures chiral alignment between adjacent molecules, which may be a prerequisite for a coherent electron transmission.

The photocatalytic performance of MoO3 is limited due to its weak visible light absorption ability and quick recombination of charge carriers. In the present work, we report the facile synthesis of Fe(iii)-grafted MoO3 nanorods using a hydrothermal method followed by an impregnation technique with the aim of enhancing the light harvesting ability and photocatalytic efficiency of MoO3. The prepared samples were characterized through the standard analytical techniques of XRD, SEM-EDS, TEM, XPS, UV-Vis-DRS, FT-IR, TG-DTA and PL spectrophotometry. XPS and TEM analyses reveal that Fe(iii) ions are successfully grafted onto the surface of the MoO3 nanorod with intimate interfacial contact. The photocatalytic performances of the prepared samples were investigated by studying the degradation of methylene blue (MB), rhodamine B (RhB) and 4-nitrophenol (4-NP) under visible light irradiation. The surface-modified MoO3 with Fe(iii) ions showed excellent photocatalytic activity towards the degradation of the above-mentioned pollutants, where Fe(iii) ions act as effective cocatalytic sites to produce hydroxyl radicals through multi-electron reduction of oxygen molecules. The improved photocatalytic activity could be ascribed to the effective separation of charge carriers and efficient production of hydroxyl radicals via the rapid capture of electrons by Fe(iii) through a well-known photoinduced interfacial charge transfer mechanism. Based on scavenger analysis study, a mechanism for the enhanced photocatalytic activity has been discussed and proposed. The concept of surface grafting onto large bandgap semiconductors with ubiquitous elements opens up a new avenue for the development of visible-light-responsive photocatalysts with excellent photocatalytic activity.

Intercalation experiments on epitaxial graphene are attracting a lot of attention at present as a tool to further boost the electronic properties of 2D graphene. In this work, we studied the intercalation of Pb using buffer layers on 6H-SiC(0001) by means of electron diffraction, scanning tunneling microscopy, photoelectron spectroscopy and in situ surface transport. Large-area intercalation of a few Pb monolayers succeeded via surface defects. The intercalated Pb forms a characteristic striped phase and leads to formation of almost charge neutral graphene in proximity to a Pb layer. The Pb intercalated layer consists of 2 ML and shows a strong structural corrugation. The epitaxial heterostructure provides an extremely high conductivity of σ=100 mS/□. However, at low temperatures (70 K), we found a metal-insulator transition that we assign to the formation of minigaps in epitaxial graphene, possibly induced by a static distortion of graphene following the corrugation of the interface layer.