P. M. Korusenko

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 (SnOx) 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 SnOx 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.

Effect of pulsed ion irradiation on the electronic structure of multi-walled carbon nanotubes

The effect of pulsed ion irradiation and vacuum annealing on the ratio of sp2- and sp3-hybridized orbitals of carbon atoms in the layers of oriented multi-walled carbon nanotubes has been studied by analyzing the photoemission spectra of the C1s core level and the valence band of carbon, which were obtained using the equipment of the BESSY II Russian-German beamline of synchrotron radiation and a Riber analytical system. It has been shown that the ion irradiation leads to a significant decrease in the fraction of atoms with the sp3 hybridization of electrons. On the contrary, the annealing reduces the fraction of the sp3-component in the spectra of carbon. Typical features of the valence band of multi-walled carbon nanotubes in the annealed and irradiated states have been established.

Fabrication of por-Si/SnOx nanocomposite layers for gas microsensors and nanosensors

Two-phase nanocomposite layers based on porous silicon and nonstoichiometric tin oxide were fabricated by various methods. The structure, as well as elemental and phase composition, of the obtained nanocomposites were studied using transmission and scanning electron microscopy, Raman spectroscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy. The results obtained confirm the formation of nanocomposite layers with a thickness as large as 2 μm thick and SnOx stoichiometry coefficients x = 1.0–2.0. Significant tin diffusion into the porous silicon matrix with Deff ≈ 10−14 cm2 s−1 was observed upon annealing at 770 K. Test sensor structures based on por-Si/SnOx nanocomposite layers grown by magnetron deposition showed fairly high stability of properties and sensitivity to NO2.

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 SnO2 − 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.

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 SnOx/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 SnOx 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.

Interfacial interaction in a composite based on multi-walled carbon nanotubes and amorphous tin oxide

The specific features of changes in the electronic structure of multi-walled carbon nanotubes (MWCNTs) due to the interaction with an amorphous tin oxide in the SnOx/MWCNT composite formed by magnetron sputtering have been investigated using X-ray spectroscopy. It has been shown that the formation of chemical bonds responsible for significant changes in the local and electronic structures of the outer layers of MWCNTs occurs at the boundaries of the “amorphous oxide/MWCNT” contacts. The vacuum annealing of the composite leads to the disturbance of the chemical interaction at interfaces of the composite and to a partial recovery of the local structure of the outer layers of MWCNTs. A decrease in the amount of oxygen in the tin oxide under vacuum annealing conditions causes an increase in the number of unpaired Sn 5s electrons, which, in turn, enhances the charge transfer through the interfaces in the composite and leads to a splitting of the π*-subsystem of the outer layers of MWCNTs.

Origin of the low-frequency band in Raman spectra of multi-walled carbon nanotubes synthesized by the CVD method

The origin of the low-frequency band (250–300 cm−1) in the Raman spectra of multi-walled carbon nanotubes (MWCNTs) produced by the CVD method has been studied. The studies performed by Raman spectroscopy, transmission electron microscopy, Auger spectroscopy, and X-ray photoelectron spectroscopy after chemical and thermal treatments allow the assumption that this band belongs to radial vibrations of carbon atoms in internal walls of MWCNTs.

Formation of por-Si/SnOx nanocomposite by high-power ion beams of nanosecond duration

Layers of por-Si/SnOx nanocomposite formed by high-power ion beam irradiation with nanosecond duration have been studied. The results of structural and elemental analyses of these layers are presented. The high sensitivity of this nanocomposite to low NO2 concentrations at room temperature has been revealed.

Electronic structure of nitrogen-containing carbon nanotubes irradiated with argon ions: XPS and XANES studies

Using the methods of X-ray photoelectron (XPS) and X-ray absorption near edge structure (XANES) spectroscopies with synchrotron radiation, data on changes in the electronic structure and chemical composition of nitrogen-containing multiwalled carbon nanotubes (N-MWCNTs) upon their exposure to the radiation of argon ions with an energy of 5 keV are obtained. It is found that the exposure leads to an increase in the degree of defectiveness of the N-MWCNTs structure and to the carbon oxidation with formation of various oxygen-containing groups (C–OH, C=O/COOH, C–O–C/O–C–O, and CO3). The presence of carbon–oxygen bonds on the surface of carbon nanotubes is associated with the formation of radiation defects. It is shown that an increase in the fraction of nitrogen atoms present in the substituting configuration in the N-MWCNTs wall structure due to the irradiation does not give rise to an increase in the density of the occupied states near the Fermi level against the background of an increase in the degree of structure defectiveness, carbon oxidation, and a decrease in the total nitrogen concentration. The obtained results show that the irradiation of N-MWCNTs with argon ions allows one to successfully functionalize their surface.

Oxidation of the porous silicon surface under the action of a pulsed ionic beam: XPS and XANES studies

The changes in the electronic structure and phase composition of porous silicon under action of pulsed ionic beams have been studied by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy (XANES) using synchrotron radiation. The Si 2p and O 1s core photoemission spectra for different photoelectron collection angles, valence band photoemission spectra, and X-ray absorption near-edge fine structure spectrain the region of Si L2,3 edges of the initial and irradiated samples have been analyzed. It has been found that, as a result of the irradiation, a thin oxide film consisting predominantly of higher oxide SiO2 is formed on the porous silicon surface, which increases the energy gap of the silicon oxide. Such film exhibits passivation properties preventing the degradation of the composition and properties of porous silicon in contact with the environment.