X-Ray Spectral Studies of the Interface Interaction in CuO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/MWCNTs Nanocomposite

Results of a comprehensive study of the interface interaction of a nanostructured CuO_x and multiwalled carbon nanotubes (MWCNTs) in CuO_x/MWCNT nanocomposite by X-ray absorption spectroscopy (XANES, NEXAFS) and X-ray photoelectron spectroscopy (XPS) methods using a synchrotron radiation are presented. It is established that a nanostructured CuO_x in CuO_x/MWCNT nanocomposite is predominantly formed by CuO and has the form of flakelike particles 200–500 nm in size uniformly dispersed over an array of nanotubes. A chemical interaction of CuO_x and nanotubes with formation of covalent carbon–oxygen bonds, which does not lead to a significant destruction of the outer layers of carbon nanotubes, is observed at the interfaces of the nanocomposite.     

Transformation of the electronic structure of the SnO2 − x /MWCNT nanocomposite under high-vacuum annealing conditions

The transformation of the structural phase state and the electronic structure of the SnO_{2 ? x} /MWCNT composite has been studied using X-ray spectroscopy and high-resolution transmission electron microscopy. It has been shown that the character of the interaction of the metal-oxide component of the composite with the array of carbon nanotubes depends on the structural state of tin oxide in globules of the metal-oxide component. In the initial composite with a large content of amorphous tin oxide, covalent functionalization of the MWCNT surface occurs. High-vacuum annealing results in the formation of a nanocrystalline structure in globules of the metal-oxide component and is accompanied by changes in the character of its interaction with carbon tubes.     

Chemical and phase compositions of multilayer nanoperiodic <Emphasis Type="Italic">a</Emphasis>-SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/ZrO<Subscript>2</Subscript> structures subjected to high-temperature annealing

The chemical and the phase compositions of multilayer nanoperiodic SiO _x /ZrO₂ structures prepared by vacuum evaporation from separated sources and subjected to high-temperature annealing have been studied by X-ray photoelectron spectroscopy with a layer-by-layer etching. It is found that, under deposition conditions used, the silicon suboxide layers had the stoichiometric coefficient x ~1.8 and the zirconium-containing layers were the stoichiometric zirconium dioxide. It was found, using X-ray photoelectron spectroscopy, that annealing of the multilayer structures at 1000°C leads to mutual diffusion of the components and chemical interaction between ZrO₂ and SiO _x with predominant formation of zirconium silicate at heteroboundaries of the structures. The SiO _x layers of the annealed nanostructures contained ~5 at % elemental silicon as a result of the phase separation and the formation of fine silicon nanocrystals.     

Low-temperature method of cleaning <Emphasis Type="Italic">p</Emphasis>-GaN(0001) surfaces for photoemitters with effective negative electron affinity

The changes in the chemical composition, atomic structure, and electronic properties of the p-GaN(0001) surface upon chemical treatment in an HCl-isopropanol solution and vacuum annealing are investigated by x-ray photoelectron spectroscopy, high-resolution electron energy-loss spectroscopy, and low-energy electron diffraction. It is demonstrated that a considerable part of the surface gallium oxide is removed upon chemical treatment of the GaN surface. Subsequent annealing of the surface under vacuum at temperatures of 400–450°C leads to a decrease in the residual carbon and oxygen contamination to 3–5% of the monolayer. The preparation of a clean p-GaN(0001) surface with a (1×1) structure identical to that of the bulk unit cells is confirmed by the low-energy electron diffraction data. The cesium adsorption on the clean p-GaN surface results in a decrease in the work function by ～2.5 eV and the appearance of an effective negative electron affinity on the surface. The quantum efficiency of the GaN photocathode at a wavelength of 250 nm is equal to 26%.     

XANES and XPS studies of processes initiated by high-vacuum annealing in SnO x /MWCNT composite layers

The initial and thermally treated composites based on SnO _x /MWCNT have been studied by the XANES and XPS methods using the equipment of the BESSY II Russian-German beamline of synchrotron radiation and by the AES and HRTEM methods. The characteristic mechanisms of chemical and structural transformations in the SnO _x phase have been determined depending on the vacuum annealing temperature. It has been found that the basic process in the metal-oxide component at annealing temperatures not exceeding 500°C is the tin monoxide SnO disproportionation reaction with the formation of the dioxide SnO₂ phase and metallic tin. An increase in the annealing temperature to 800°C results in the activation of carbothermal reduction of metallic tin in contact areas of oxide clusters and MWCNT, as well as in the formation of nanocrystalline structures in the metal-oxide component of composite.     

Formation mechanisms of nanocomposite layers based on multiwalled carbon nanotubes and non-stoichiometric tin oxide

Nanocomposite layers based on multiwalled carbon nanotubes (MWCNTs) and non-stoichiometric tin oxide (SnO _x ) have been grown by magnetron deposition and CVD methods. In the case of the CVD method, the study of the structure and phase composition of obtained nanocomposite layers has shown that a tin oxide “superlattice” is formed in the MWCNT layer volume, fixed by SnO _x islands on the MWCNT surface. During magnetron deposition, the MWCNT surface is uniformly coated with tin oxide islands, which causes a change in properties of individual nanotubes. Electrical measurements have revealed the sensitivity of nanocomposite layers to (NO₂)⁻ molecule adsorption, which is qualitatively explained by a change in the conductivity of the semiconductor fraction of p-type MWCNTs.     

Synthesis and gas sensing characteristic based on metal oxide modification multi wall carbon nanotube composites

A new type of gas sensing material based on metal oxide modification multi wall carbon nanotube (MO/MWCNT) composites is presented since the interface between the composites enhance the carrier density so as to improve the gas sensitivity. Three kinds of MO/MWCNT composite materials, such as ZnO/MWCNT, SnO₂/MWCNT and TiO₂/MWCNT, have been acquired in situ growth using catalytic pyrolysis method. The MO nano particles have decorated on side of MWCNTs, whereas the introduction of SnO₂ nano particles makes part of MWCNT showing two-dimensional form of carbon nano-wall structure. Among four kinds of cathode of ZnO/MWCNTs, SnO₂/MWCNTs, TiO₂/MWCNTs and pure MWCNT composite film, TiO₂/MWCNTs composite has the lowest threshold electric field required to draw current of 12 μA has been found to be ∼1.2 V/μm, and also TiO₂/MWCNTs composite has the highest sensitivity of 16% to ethanol. The TiO₂/MWCNTs composite is superior to the others both in vacuum electron transportation and gas sensitivity.     

Short-Range order of TlIn<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Sn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript>2</Subscript> thin films

The formation of the short-range order structure of amorphous nanometer-thick TlIn_1–x Sn _x Te₂ films (х = 0.02–0.09) obtained via vacuum deposition onto substrates of fresh KCl and KJ chips and celluloid at a temperature below Т = 213 K is studied by high-energy electron diffraction. Both freshly deposited films and films held in vacuum (10^–2 Pa) at room temperature in darkness for several months are studied. The effect of the tin concentration on the interatomic distances, the coordination numbers, and the time of amorphous phase stability of TlIn_1–x Sn _x Te₂ films due to a great spread in bond lengths and bond angles is established.     

Soft X-ray absorption spectroscopy of titanium dioxide nanopowders with cobalt impurities

The charge states of the cobalt ions in TiO₂ nanopowders with the anatase lattice are studied by soft X-ray absorption spectroscopy. It is found that, at a low cobalt impurity concentration (1.8 at %), the cobalt ions with an oxidation state 2+ are mainly located in the tetrahedral (T _d ) environment of oxygen ions. Amorphous titanium dioxide exists on the sample surface before heat treatment. Annealing in vacuum or hydrogen leads to the enrichment of the nanoparticle surfaces with Co²⁺ ions, a change in the coordination of the remaining part of cobalt ions from octahedral to tetrahedral, stabilization of the anatase structure, and the disappearance of the amorphous phase. The crystal lattice of the samples with a relatively high cobalt concentration (12 at %) is distorted, and annealing does not cause the disappearance of the amorphous phase of TiO₂. Cobalt is reduced to its metallic state upon hydrogen annealing of the samples with a high cobalt concentration.     

Efficient electrochromic device based on sol–gel prepared WO<Subscript>3</Subscript> films

Tungsten oxide (WO₃) films were prepared on indium–tin oxide (ITO) glass by sol–gel method. The influence of annealing temperature on the structural, morphological, optical, electrochemical, and electrochromic properties has been investigated. The film annealed at 250 °C with an amorphous structure exhibits a noticeable electrochromic performance, such as the highest optical modulation of 58.5 % at 550 nm, high electrochemical stability, and excellent reversibility (Q _b/Q _c?=?96.3 %). An electrochromic (EC) device based on WO₃/NiO complementary structure shows improved performance. It exhibits high optical transmittance modulation of 62 % at 550 nm, excellent cycling stability, and relatively fast electrochromic response time (10 s for coloration and 19 s for bleaching).     

Structure and Properties of SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Films Prepared by Chemical Etching of Amorphous Alloy Ribbons

The structure and the physical properties of amorphous SiO _x films prepared by chemical etching of an iron-based amorphous ribbon alloy have been studied. The neutron diffraction and also the atomicforce and electron microscopy show that the prepared visually transparent films have amorphous structure, exhibit dielectric properties, and their morphology is similar to that of opals. The samples have been studied by differential scanning calorimetry, Raman and IR spectroscopy before and after their heat treatment. It is found that annealing of the films in air at a temperature of 1273 K leads to a change in their chemical compositions: an amorphous SiO₂ compound with inclusions of SiO₂ nanocrystals (crystobalite) forms.     

Electronic Structure of Amorphous SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> with Variable Composition

The heights of barriers for the injection of electrons and holes from silicon in SiO_x have been calculated in the tight binding approximation without any fitting parameters. The dependence of the electronic structure of silicon-enriched amorphous silicon oxide SiO_x on the degree of enrichment has been found. The calculations have been performed with the parameterization of the matrix elements of the tight binding Hamiltonian proposed in our previous work. This parameter involves a change in the localization region of valence electrons of an insulated atom at its introduction into a solid. It has been shown that the inclusion of this change makes it possible to calculate the electronic structure without fitting parameters using the parameters of individual atoms as initial data. This circumstance allows the calculation in the absolute energy scale with zero corresponding to the energy of the electron in vacuum.     

Electronic band structure and x-ray spectra of boron nitride polytypes

The electronic band structures of boron nitride crystal modifications of the graphite (h-BN), wurtzite (w-BN), and sphalerite (c-BN) types are calculated using the local coherent potential method in the cluster muffin-tin approximation within the framework of the multiple scattering theory. The specific features of the electronic band structure of 2H, 4H, and 3C boron nitride polytypes are compared with those of experimental x-ray photoelectron, x-ray emission, and K x-ray absorption spectra of boron and nitrogen. The features of the experimental x-ray spectra of boron nitride in different crystal modifications are interpreted. It is demonstrated that the short-wavelength peak revealed in the total densities of states (TDOS) in the boron nitride polytypes under consideration can be assigned to the so-called outer collective band formed by 2p electrons of boron and nitrogen atoms. The inference is made that the decrease observed in the band gap when changing over from wurtzite and sphalerite to hexagonal boron nitride is associated with the change in the coordination number of the components, which, in turn, leads to a change in the energy location of the conduction band bottom in the crystal.     

Influence of surface properties on the structure of granular silver films and excitation of localized plasmons

Granular silver films deposited on a thin insulating film of amorphous hydrogenated carbon (a-C:H) and transparent conducting electrode (polycrystalline indium tin oxide (ITO) layer) have been investigated by spectroscopy and microscopy methods. The extinction spectra of silver films on the surface of these materials are found to be significantly different. An annealing of silver films causes a blue shift of the peak of plasmon resonance band in the spectrum of silver nanoparticles: by 16 nm on the a-C:H surface and by 94 nm on the ITO surface. Silver films on the surface of a-C:H films are characterized by a narrower band in the extinction spectrum, which is peaked at 446 nm. The changes observed in the optical density of Ag films are related to the change in size and area of nanoparticles. The results of spectral studies of Ag films are in agreement with the data on the nanostructure obtained by scanning electron microscopy and statistical image processing. The spectra of granular silver films are shown to correlate well with the nanoparticle distribution function over the film area.     

Fabrication of composite based on GeSi with Ag nanoparticles using ion implantation

Comparative analysis of the structural and optical properties of composite layers fabricated with the aid of implantation of single-crystalline silicon (c-Si) using Ge⁺ (40 keV/1 × 10¹⁷ ions/cm²) and Ag⁺ (30 keV/1.5 × 10¹⁷ ions/cm²) ions and sequential irradiation using Ge⁺ and Ag⁺ ions is presented. The implantation of the Ge⁺ ions leads to the formation of Ge: Si fine-grain amorphous surface layer with a thickness of 60 nm and a grain size of 20–40 nm. The implantation of c-Si using Ag⁺ ions results in the formation of submicron porous amorphous a-Si structure with a thickness of about 50 nm containing ion-synthesized Ag nanoparticles. The penetration of the Ag⁺ ions in the Ge: Si layer stimulates the formation of pores with Ag nanoparticles with more uniform size distribution. The reflection spectra of the implanted Ag: Si and Ag: GeSi layers exhibit a sharp decrease in the intensity in the UV (220–420 nm) spectral interval relative to the intensity of c-Si by more than 50% owing to the amorphization and structuring of surface. The formation of Ag nanoparticles in the implanted layers gives rise to a selective band of the plasmon resonance at a wavelength of about 820 nm in the optical spectra. Technological methods for fabrication of a composite based on GeSi with Ag nanoparticles are demonstrated in practice.     

Carbon–metal interfaces analyzed by aberration-corrected TEM: How copper and nickel nanoparticles interact with MWCNTs

Experimental confirmation for the stronger interaction of Ni with multi-walled carbon nanotubes (MWCNTs) compared to Cu with MWCNTs is presented. The interfaces between Cu (Ni) nanoparticles side-on oriented onto MWCNTs are analyzed with high spatial resolution electron energy-loss spectroscopy (EELS) of the carbon K-edge. The EEL spectra reveal a rehybridization from sp² to sp³ hybridized carbon of the outermost MWCNT layer at the Ni interface, but no such rehybridization can be observed at the Cu interface. The EELS results are supported by transmission electron microscopy (TEM) images, which show a better wetting behavior of Ni and a smaller gap at the Ni–MWCNT interface, as compared to the corresponding Cu interfaces. The different behavior of Cu and Ni can be explained in terms of differing valence d-orbital occupancy. For the successful experimental demonstration of this effect the use of a soft chemical metal deposition technique is crucial.     

Charge accumulation layer in Cs,Ba/<Emphasis Type="Italic">n</Emphasis>-GaN(0001) ultrathin interfaces: Electronic and photoemission properties

Experimental studies and theoretical calculations of the photoemission from Cs/n-GaN(0001) and Ba/n-GaN(0001) ultrathin interfaces were carried out. The electronic properties of the interfaces were studied in situ using threshold photoemission spectroscopy under vacuum at a residual pressure of P ～ 5 × 10^?11 Torr. A new effect was revealed, namely, photoemission with a high quantum yield under excitation with light in the transparency region of GaN. It was shown that adsorption of Cs or Ba on n-GaN brings about the formation of a quasi-two-dimensional electron channel, i.e., a charge accumulation layer directly near the surface. The dependences of the photoemission spectra and work function on the thickness of Cs and Ba coatings were investigated. It was established that adsorption of Cs and Ba leads to a sharp decrease in the work function by ～1.45 and ～1.95 eV, respectively. The photoemission spectra were calculated, and parameters of the accumulation layer, such as the energy position of the layer below the Fermi level for different Cs and Ba coverages, were determined. It was demonstrated that the energy parameters of the accumulation layer on the n-GaN(0001) surface can be controlled by properly varying the Cs or Ba coverage. The layer thickness was found to reach a maximum for a cesium coverage of ～0.5 monolayer.     

Spezifische Wärme und magnetische Suszeptibilität supraleitender,binärer komplexer Phasen von Übergangsmetallen

Measurements of the electronic specific heat in the normal and superconducting state of 15 superconducting binary complex phases of theσ- andχ-structure are presented. The alloys have been prepared under high vacuum in an electron-beam melting apparatus described in detail. In the investigated range between 6 and 7 valence-electrons, the obvious correlation betweenT _c, the superconducting critical temperature, andγ, the coefficient of the electronic specific heat, leads to agreement with the empirical rules, found byMatthias. Recently,Morel andAnderson andGarland have calculated the values of the deviation of the normal isotope-effect. With these values it is possible to relate the observedT _c-data for most of the transition metal alloys investigated so far to the density of states at the Fermi level and to a systematically varying electron-phonon interaction parameter. In the superconducting state, an exponential dependence of the electronic specific heat on 1/T is found in the range betweenT _c/2 andT _c/6. However the parameters are somewhat different from those predicted by theory. The values ofγ observed also account for the lack of any correlation between the total magnetic susceptibility and the superconducting critical temperature for these phases.     

Reduced graphene oxide/MWCNT hybrid sandwiched film by self-assembly for high performance supercapacitor electrodes

A reduced graphene oxide/multiwalled carbon nanotube (RGO/MWCNT) hybrid sandwiched film with different MWCNTs content was prepared by vacuum-assisted self-assembly from a complex dispersion of graphene oxide (GO) and MWCNTs followed by heat-treating at 200 °C for 1 h in a vacuum oven to reduce the GO into RGO. The free-standing RGO/MWCNT hybrid sandwiched film before heat-treatment showed a layered structure with an entangled network of MWCNTs sandwiched between the GO sheets. This unique structure not merely contribute to remove the oxygen-containing groups in GO during the heat-treatment, but also decrease the defects for electron transfer between RGO layers, which enhances the electrochemical capacitive performances of graphene-based films. A specific capacitance up to 379 F/g was achieved based on RGO/MWCNT with 30 % MWCNTs mass fraction at 0.1 A/g in a 6 M KOH electrolyte. The excellent performance of RGO/MWCNT hybrid sandwiched film signifies the importance of controlling the surface chemistry and sandwiched nanostructure of graphene-based materials.     

Phase transformations and ordering effects in nanocrystalline carbon-containing silicon films

The phase composition, surface morphology, and crystal structure of carbon-containing Si layers obtained on silicon surface by chemical conversion are discussed. The effect of structural ordering in the grains formed in the growth figures on an epitaxial surface has been studied for the 3C-SiC/Si(111) system. The possibility of Si_{1 ? x} C _x → 3C-SiC phase transitions in a layer upon structure annealing during growth is considered.