Modification of the electronic structure of graphene by intercalation of iron and silicon atoms

The ab initio calculations of the electronic structure of low-dimensional graphene–iron–nickel and graphene–silicon–iron systems were carried out using the density functional theory. For the graphene–Fe–Ni(111) system, band structures for different spin projections and total densities of valence electrons are determined. The energy position of the Dirac cone caused by the p _z states of graphene depends weakly on the number of iron layers intercalated into the interlayer gap between nickel and graphene. For the graphene–Si–Fe(111) system, the most advantageous positions of silicon atoms on iron are determined. The intercalation of silicon under graphene leads to a sharp decrease in the interaction of carbon atoms with the substrate and largely restores the electronic properties of free graphene.

     

Intercalation synthesis of cobalt silicide under a graphene layer

The silicon intercalation under single-layer graphene formed on the surface of an epitaxial Co(0001) film was investigated. The experiments were performed under conditions of ultra-high vacuum. The thickness of silicon films was varied within the range of up to 1 nm, and the temperature of their annealing was 500°C. The characterization of the samples was carried out in situ by the methods of low-energy electron diffraction, high-energy-resolution photoelectron spectroscopy using synchrotron radiation, and magnetic linear dichroism in photoemission of Co 3p electrons. New data were obtained on the evolution of the atomic and electronic structure, as well as on the magnetic properties of the system with an increase in the amount of intercalated silicon. It was shown that the intercalation under a graphene layer is accompanied by the synthesis of surface silicide Co₂Si and a solid solution of silicon in cobalt.     

Sodium Intercalation of Graphene Films on Re( $$10\bar 10$$ 10 1 ¯ 0 )

It is shown that during low-temperature (300–500 K) intercalation of sodium atoms into thin multilayer graphene and graphite films on rhenium the first graphene layer plays the role of a trap to which atoms coming on the surface diffuse through a graphite film. The intercalation phase of the interlayer space in the graphite bulk is actively filled at a sodium atoms concentration under the first graphene layer close to the maximum possible (2 ± 0.5) × 10¹⁴ cm^–2. This phase capacity is proportional to the graphite film thickness that can be varied in this work from one graphene layer to ~50 atomic layers. The diffusion energy E _d of Na atoms through the graphite film was estimated to be E _d ≈ 1.4 eV.

     

Quasi‐Freestanding Graphene on SiC(0001) by Ar‐Mediated Intercalation of Antimony: A Route Toward Intercalation of High‐Vapor‐Pressure Elements

A novel strategy for the intercalation of antimony (Sb) under the $\text{(6}\sqrt{\mathrm{3}}\times \mathrm{6}\sqrt{\mathrm{3}})R\text{30}$° reconstruction, also known as buffer layer, on SiC(0001) is reported. Using X‐ray photoelectron spectroscopy, low‐energy electron diffraction, and angle‐resolved photoelectron spectroscopy, it is demonstrated that, while the intercalation of the volatile Sb is not possible by annealing the Sb‐coated buffer layer in ultrahigh vacuum, it can be achieved by annealing the sample in an atmosphere of Ar, which suppresses Sb desorption. The intercalation leads to a decoupling of the buffer layer from the SiC(0001) surface and the formation of quasi‐freestanding graphene. The intercalation process paves the way for future studies of the formation of quasi‐freestanding graphene by intercalation of high‐vapor‐pressure elements, which are not accessible by previously known intercalation techniques, and thus provides new avenues for the manipulation of epitaxial graphene on SiC.     

”Eau de graphene” from a KC8 graphite intercalation compound prepared by a simple mixing of graphite and molten potassium

We synthesized KC₈ by simply mixing molten potassium and graphite at 180 °C under inert atmosphere. The KC₈ shows typical shiny bronze color, Raman characteristics and XRD pattern of an efficiently intercalated stage 1 GIC, and is of sufficient quality to produce fully exfoliated graphenide solutions in tetrahydrofuran (THF) and subsequently single layer graphene in water as ”eau de graphene” (EdG). The evolution of absorption and Raman spectroscopic signatures of the EdG as a function of processing conditions give key indications on the number of layers of the graphene flakes dispersed in EdG. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Synthesis of Amide Compounds of Ferulic Acid and Their Association with Bovine Serum Albumin

ABSTRACT

In this work, three new amide compounds of ferulic acid (FA) were synthesized. The fluorescence and ultraviolet spectroscopy were explored to study the interactions between three amide compounds of FA and bovine serum albumin (BSA) under imitated physiological conditions. The experimental results showed that the fluorescence quenching mechanism between BSA and three amide compounds of FA were mainly static quenching and nonradiation energy transfer at 25°C, 30°C, and 37°C. The Stern–Volmer quenching constants, the binding constants, and the number of binding sites and corresponding thermodynamic parameters ΔH, ΔG, and ΔS were calculated at different temperatures. From the thermodynamic parameters, we concluded that the action force was mainly a hydrophobic interaction. According to the F?rster theory of nonradiation energy transfer, the binding distances (r) between BSA and amide compounds are less than 7 nm. Furthermore, the effects of amide compounds on the conformation of BSA were analyzed using synchronous fluorescence spectroscopy.     

Graphene on ordered Ni-alloy surfaces formed by metal (Sn,Al) intercalation between graphene/Ni(111)

Deposition and intercalation of Al and Sn on Ni(111) supported graphene is investigated by Auger electron spectroscopy, low energy electron diffraction, and scanning tunneling microscopy. Al intercalates at ~ 200 °C while Sn intercalates at ~ 350 °C, indicating that the intercalation process is element specific. Both Al and Sn alloy with the Ni-substrate at higher annealing temperatures and form ordered alloy surfaces and surface alloys, respectively. Sn forms a (√3 × √3) R30° surface alloy by substituting surface Ni-atoms with Sn and thus the alloy maintains the same good lattice match with graphene as for Ni(111). Both Sn and Al are interacting weakly with graphene and can therefore be used to decouple graphene from the strongly interacting Ni substrate.     

Formation of a quasi-free-standing graphene with a band gap at the dirac point by Pb atoms intercalation under graphene on Re(0001)

The control of the graphene electronic structure is one of the most important problems in modern condensed matter physics. The graphene monolayer synthesized on the Re(0001) surface and then subjected to the intercalation of Pb atoms is studied by angle-resolved photoelectron spectroscopy and low-energy electron diffraction. The intercalation of Pb atoms under graphene takes place when the substrate is annealed above 500°C. As a result of the intercalation of Pb atoms, graphene becomes quasi-free-standing and a local band gap appears at the Dirac point. The band gap changes with the substrate temperature during the formation of the graphene/Pb/Re(0001) system. The band gap is 0.3 eV at an annealing temperature of 620°C and it increases up to 0.4 eV upon annealing at 830°C. Based on our data, we conclude that the band gap is mainly caused by the hybridization of the graphene π state with the rhenium 5d states located near the Dirac point of the graphene π state.     

Intercalation of germanium oxide beneath large-area and high-quality epitaxial graphene on Ir(111) substrate

Epitaxial growth on transition metal surfaces is an effective way to prepare large-area and high-quality graphene.However,the strong interaction between graphene and metal substrates suppresses the intrinsic excellent properties of graphene and the conductive metal substrates also hinder its applications in electronics.Here we demonstrate the decoupling of graphene from metal substrates by germanium oxide intercalation.Germanium is firstly intercalated into the interface between graphene and Ir(111) substrate.Then oxygen is subsequently intercalated,leading to the formation of a GeO_x layer,which is confirmed by x-ray photoelectron spectroscopy.Low-energy electron diffraction and scanning tunneling microscopy studies show intact carbon lattice of graphene after the GeO_x intercalation.Raman characterizations reveal that the intercalated layer effectively decouples graphene from the Ir substrate.The transport measurements demonstrate that the GeO_x layer can act as a tunneling barrier in the fabricated large-area high-quality vertical graphene/GeO_x/Ir heterostructure.     

Fabrication of coaxial nanowire heterostructures: SiO x nanowires with conformal TiO2 coatings

Silica nanowires, grown via the active oxidation of a silicon substrate, have been coated with TiO₂ using two coating methods: solution-based deposition of Ti-alkoxides and atomic layer deposition. Analysis of as-deposited and annealed films shows that it is possible to produce stable conformal coatings of either the anatase or rutile phases of TiO₂ on nanowires with diameters greater than 100 nm when annealed between 500–600°C and 800–900°C, respectively, with annealing at higher temperatures (1050°C) producing coatings with a highly facetted rutile morphology. The efficacy of the process is shown to depend on nanowire diameter, with nanowires having diameters less than about 100 nm fusing together during solution-based coating and decomposing during TiO₂ atomic layer deposition. The use of a suitable buffer layer is shown to be an effective means of minimizing nanowire decomposition. Finally, annealing coated nanowires under active oxidation conditions (1100°C) is shown to be an effective technique for depositing additional conformal SiO _x coatings, thereby providing a means of fabricating multi-layered coaxial nanostructures.     

Studies of Li intercalation of hydrogenated graphene on SiC(0001)

The effects of Li deposition on hydrogenated bilayer graphene on SiC(0001) samples, i.e. on quasi-freestanding bilayer graphene samples, are studied using low energy electron microscopy, micro-low-energy electron diffraction and photoelectron spectroscopy. After deposition, some Li atoms form islands on the surface creating defects that are observed to disappear after annealing. Some other Li atoms are found to penetrate through the bilayer graphene sample and into the interface where H already resides. This is revealed by the existence of shifted components, related to H–SiC and Li–SiC bonding, in recorded core level spectra. The Dirac point is found to exhibit a rigid shift to about 1.25 eV below the Fermi level, indicating strong electron doping of the graphene by the deposited Li. After annealing the sample at 300–400 °C formation of LiH at the interface is suggested from the observed change of the dipole layer at the interface. Annealing at 600 °C or higher removes both Li and H from the sample and a monolayer graphene sample is re-established. The Li thus promotes the removal of H from the interface at a considerably lower temperature than after pure H intercalation.     

Defect-dependent nitride surface layer development upon nitriding of Fe–1 at.% Mo alloy

Upon nitriding of binary Fe–1 at.% Mo alloy in a NH₃/H₂ gas mixture under conditions (thermodynamically) allowing γ′-Fe₄N_{1– x} compound layer growth (nitriding potential: 0.7?atm^?1/2 at 753?K (480?°C) – 823?K (550?°C)), a strong dependency of the morphology of the formed compound layer on the defect density of the specimen was observed. Nitriding of cold-rolled Fe–1 at.% Mo specimens leads to the formation of a closed compound layer of approximately constant thickness, comparable to nitriding of pure iron. Within the compound layer, that is, in the near-surface region, Mo nitrides are present. The growth of the compound layer could be described by a modified parabolic growth law leading to an activation energy comparable to literature data for the activation energy of growth of a γ′-Fe₄N_{1? x} layer on pure iron. Upon low temperature nitriding (i.e. ?793?K (520?°C)) of recrystallized Fe–1 at.% Mo specimens, an irregular, ‘needle-like’ morphology of γ′-Fe₄N_{1? x} nucleated at the surface occurs. This γ′ iron nitride has an orientation relationship (OR) with the matrix close to the Nishiyama–Wassermann OR. The different morphologies of the formed compound layer can be interpreted as consequences of the ease or difficulty of precipitation of Mo as nitride as function of the defect density.     

Positron annihilation study of the vacancy clusters in ODS Fe–14Cr alloys

Abstract

Oxide dispersion strengthened Fe14Cr and Fe14CrWTi alloys produced by mechanical alloying and hot isostatic pressing were subjected to isochronal annealing up to 1400 °C, and the evolution and thermal stability of the vacancy-type defects were investigated by positron annihilation spectroscopy (PAS). The results were compared to those from a non-oxide dispersion strengthened Fe14Cr alloy produced by following the same powder metallurgy route. The long lifetime component of the PAS revealed the existence of tridimensional vacancy clusters, or nanovoids, in all these alloys. Two recovery stages are found in the oxide dispersion strengthened alloys irrespective of the starting conditions of the samples. The first one starting at T > 750 °C is attributed to thermal shrinkage of large vacancy clusters, or voids. A strong increase in the intensity of the long lifetime after annealing at temperatures in the 800–1050 °C range indicates the development of new vacancy clusters. These defects appear to be unstable above 1050 °C, but some of them remain at temperatures as high as 1400 °C, at least for 90 min.     

Atomic layer deposition of HfO2 on graphene from HfCl4 and H2O

Atomic layer deposition of HfO₂ on unmodified graphene from HfCl₄ and H₂O was investigated. Surface RMS roughness down to 0.5 nm was obtained for amorphous, 30 nm thick hafnia film grown at 180°C. HfO₂ was also deposited in a two-step temperature process where the initial growth of about 1 nm at 170°C was continued up to 10–30 nm at 300°C. This process yielded uniform, monoclinic HfO₂ films with RMS roughness of 1.7 nm for 10–12 nm thick films and 2.5 nm for 30 nm thick films. Raman spectroscopy studies revealed that the deposition process caused compressive biaxial strain in graphene, whereas no extra defects were generated. An 11 nm thick HfO₂ film deposited onto bilayer graphene reduced the electron mobility by less than 10% at the Dirac point and by 30–40% far away from it.     

Thermally stable hydrogen compounds obtained under high pressure on the basis of carbon nanotubes and nanofibers

Compounds containing 6.3–6.5 wt % H and thermally stable in vacuum up to 500°C were obtained by annealing graphite nanofibers and single-walled carbon nanotubes in hydrogen atmosphere under a pressure of 9 GPa at temperatures up to 45°C. A change in the X-ray diffraction patterns indicates that the crystal lattice of graphite nanofibers swells upon hydrogenation and that the structure is recovered after the removal of hydrogen. It was established by IR spectroscopy that hydrogenation enhances light transmission by nanomaterials in the energy range studied (400–5000 cm^?1) and results in the appearance of absorption bands at 2860–2920 cm^?1 that are characteristic of the C–H stretching vibrations. The removal of about 40% of hydrogen absorbed under pressure fully suppresses the C–H vibrational peaks. The experimental results are evidence of two hydrogen states in the materials at room temperature; a noticeable portion of hydrogen forms C–H bonds, but the most of the hydrogen is situated between the graphene layers or inside the nanotubes.     

An iron-57 Mössbauer spectroscopic study of titania-supported iron- and iron-iridium catalysts

⁵⁷Fe Mössbauer spectroscopy shows that titania-supported iron is reduced by treatment in hydrogen at significantly lower temperatures than corresponding silica- and alumina-supported catalysts. The metallic iron formed under hydrogen at 600°C is partially converted to carbide by treatment in carbon monoxide and hydrogen. In contrast to its alumina- and silica-supported counterparts, the remainder of the titania-supported iron is unchanged by this gaseous mixture. The⁵⁷Fe Mössbauer spectra and EXAFS show that iron and iridium in the titania-supported iron-iridium catalysts are reduced in hydrogen at even lower temperatures and, after treatment at 600°C, are predominantly present as the iron-iridium alloy. The treatment of these reduced catalysts in carbon monoxide and hydrogen is shown by Mössbauer spectroscopy and EXAFS to induce the segregation of iron from the iron-iridium alloy and its conversion to iron oxide.     

Adsorption and desorption of fullerene on graphene/SiC(0001)

Adsorption and desorption of fullerene on a single layer of graphene grown on SiC(0001) were investigated by photoemission spectroscopy (PES). No significant change in the band structure of graphene was observed after fullerene deposition on the graphene layer under vacuum conditions, and subsequent exposure to the air. After annealing the fullerene layer at 275 °C in a vacuum, complete desorption of fullerene was observed without any resulting damage to the graphene structure. The desorption temperature of fullerene was significantly higher than that of pentacene, indicating that fullerene layers show higher stability than pentacene as protection layers of graphene-based devices.     

Buffer layer free large area bi-layer graphene on SiC(0 0 0 1)

The influence of hydrogen exposures on monolayer graphene grown on the silicon terminated SiC(0 0 0 1) surface is investigated using photoelectron spectroscopy (PES), low-energy electron microscopy (LEEM) and micro low-energy electron diffraction (μ-LEED). Exposures to ionized hydrogen are shown to have a pronounced effect on the carbon buffer (interface) layer. Exposures to atomic hydrogen are shown to actually convert/transform the monolayer graphene plus carbon buffer layer to bi-layer graphene, i.e. to produce carbon buffer layer free bi-layer graphene on SiC(0 0 0 1). This process is shown to be reversible, so the initial monolayer graphene plus carbon buffer layer situation is recreated after heating to a temperature of about 950 °C. A tentative model of hydrogen intercalation is suggested to explain this single to bi-layer graphene transformation mechanism. Our findings are of relevance and importance for various potential applications based on graphene-SiC structures and hydrogen storage.     

Epitaxial growth of cadmium telluride films on silicon with a buffer silicon carbide layer

An epitaxial 1–3-μm-thick cadmium telluride film has been grown on silicon with a buffer silicon carbide layer using the method of open thermal evaporation and condensation in vacuum for the first time. The optimum substrate temperature was 500°C at an evaporator temperature of 580°C, and the growth time was 4 s. In order to provide more qualitative growth of cadmium telluride, a high-quality ~100-nm-thick buffer silicon carbide layer was previously synthesized on the silicon surface using the method of topochemical substitution of atoms. The ellipsometric, Raman, X-ray diffraction, and electron-diffraction analyses showed a high structural perfection of the CdTe layer in the absence of a polycrystalline phase.

     

Electrical properties of Cd,Zn and S ion-implanted layers in GaAs

The electrical properties of cadmium, zinc, and sulfur ion-implanted layers in gallium arsenide have been measured by the van der Pauw-Hall technique. Ion implantation was performed with the substrates held at room temperature. The dependence of sheet resistivity, surface carrier concentration, and mobility on ion dose and on post-implantation anneal temperature was determined. In the case of 60 keV Cd⁺ ions implanted into n-type substrates, a measurable p-type layer resulted when samples were annealed for 10 minutes at a temperature in the range 600—900°C. After annealing at 300—900°C for 10 minutes, 100 per cent electrical activity of the Cd ions resulted for ion doses ≤ 10¹⁴/cm².

The properties of p-type layers produced by implantation of 85 keV Zn⁺ ions were similar to those of the 60 keV cadmium-implanted layers, in that no measurable p-type behavior was observed in samples annealed below a relatively high temperature. However, in samples implanted with 20 keV Zn⁺ ions a p-type layer was observed after annealing for 10 minutes at temperatures as low as 300°C.

Implantation of sulfur ions into p-type GaAs substrates at room temperature resulted in the formation of a high resistivity n-type layer, evcn before any annealing was performed. Annealing at temperatures up to 200°C or above 600°C lowered the resistivity of the layer, while annealing in the range 300—500°C eliminated the n-type layer.