V. O. Yukhymchuk

Nanostructured Silver Substrates With Stable and Universal SERS Properties: Application to Organic Molecules and Semiconductor Nanoparticles

Nanostructured silver films have been prepared by thermal deposition on silicon, and their properties as SERS substrates investigated. The optimal conditions of the post-growth annealing of the substrates were established. Atomic force microscopy study revealed that the silver films with relatively dense and homogeneous arrays of 60–80-nm high pyramidal nanoislands are the most efficient for SERS of both organic dye and inorganic nanoparticles analytes. The noticeable enhancement of the Raman signal from colloidal nanoparticles with the help of silver island films is reported for the first time.

Local structure, paramagnetic properties, and porosity of natural coals: Spectroscopic studies

Using methods of the scanning electron microscopy, Raman scattering of light(RS), and electron paramagnetic resonance (EPR), consistent research of the local structure and magnetic features of different types of raw coal samples from Donetsk basin is carried out. It is established that the ratio of the main peak intensities of RS spectrum D and G is inversely related to the volatile substance amount Vdaf in the coal samples. The study of the kinetic behavior of the EPR line width in hydrogen, oxygen, and methane sorption-desorption processes in each coal sample helped determine that the diffusion coefficient value for hydrogen in coal at room temperature is equal to DН = (2 ÷ 7) × 10−5 cm2/s. It is demonstrated that the oxygen diffusion occurs with time according to two different exponential laws with diffusion coefficients DO,1 = 5 × 10−6 cm2/s and DO,2 = 5.5 × 10−7 cm2/s, respectively. The smaller coefficient corresponds to the diffusion caused by the hopping process. Finally, it is established that the...

Raman study of self-assembled SiGe nanoislands grown at low temperatures

We report on Raman scattering measurements on Si-capped Ge quantum structures grown by molecular beam epitaxy on Si(001) at low temperatures. We find a double band structure in the Ge–Ge frequency range for nanoislands grown at substrate temperatures ranging in the interval 300–500 °C. Complementary information has been obtained from performing Raman scattering experiments on annealed samples. The results are interpreted in terms of a model that considers quantum structures (hut clusters) composed of a strained Ge core and a more relaxed SiGe shell.

Fermi resonance in the phonon spectra of quaternary chalcogenides of the type Cu2ZnGeS4.

The experimental resonant and non-resonant Raman scattering spectra of the kesterite structural modification of Cu2ZnGeS4 single crystals are reported. The results are compared with those calculated theoretically within the density functional perturbation theory. For the majority of lines a good agreement (within 2-5 cm(-1)) is established between experimental and calculated mode frequencies. However, several dominant spectral lines, in particular the two intense fully symmetric modes, are found to deviate from the calculated values by as much as 20 cm(-1). A possible reason for this discrepancy is found to be associated with the Fermi resonant interaction between one and two-phonon vibrational excitations. The modelling of spectra, which takes into account the symmetry of interacting states, allows a qualitative description of the observed experimental findings. Due to the similarity of the vibrational spectra of Cu2A (II) B (IV) S4 (A  =  Zn, Mn, Cd; B  =  Sn, Ge, Si) chalcogenides, Fermi resonance is argued to be a general phenomenon for this class of compounds.

Tin induced a-Si crystallization in thin films of Si-Sn alloys

Effects of tin doping on crystallization of amorphous silicon were studied using Raman scattering, Auger spectroscopy, scanning electron microscopy, and X-ray fluorescence techniques. Formation of silicon nanocrystals (2–4 nm in size) in the amorphous matrix of Si1−xSnx, obtained by physical vapor deposition of the components in vacuum, was observed at temperatures around 300 °C. The aggregate volume of nanocrystals in the deposited film of Si1−xSnx exceeded 60% of the total film volume and correlated well with the tin content. Formation of structures with ∼80% partial volume of the nanocrystalline phase was also demonstrated. Tin-induced crystallization of amorphous silicon occurred only around the clusters of metallic tin, which suggested the crystallization mechanism involving an interfacial molten Si:Sn layer.

Synthesis and properties of porous SiC ceramics

Porous silicon carbide (SiC) ceramics are produced using carbon matrices derived from natural wood. Such material is especially promising as it is environmentally friendly with attractive physical properties, including a high level of biocompatibility, chemical inertness, and mechanical strength. We have developed a forced impregnation process with further synthesis of SiC using natural wood as well as a variety of industrial carbon materials and compared the properties of these ceramics. The structure and composition of the materials obtained were investigated by Raman scattering spectroscopy. The hardness of the samples was estimated using the Vickers technique. It was shown that the phase composition and mechanical properties of synthesized SiC ceramics can be effectively controlled by the initial Si contents and temperature of the synthesis process. A large variety of options are demonstrated for materials development taking into account an optimal porosity selection for various practical applications.

Optical properties of quaternary kesterite-type Cu2Zn(Sn1−xGex)S4 crystalline alloys: Raman scattering, photoluminescence and first-principle calculations

The transformation of the vibrational spectrum of Cu2Zn(Sn1−xGex)S4 single crystals over the entire composition range (0 ≤ x ≤ 1) is studied experimentally by low-temperature Raman scattering and photoluminescence spectroscopies, as well as theoretically in the framework of density functional theory (DFT). It is shown that unlike “classic” mixed binary II–VI and III–V compounds, which are characterized by either one- or two-mode behavior of spectra transformation upon composition variation, the vibrational modes of the quaternary semiconductor Cu2Zn(Sn1−xGex)S4 exhibit both types of behavior within the same alloy system. DFT calculations reveal that the two-mode transformation is in fact observed for the vibrational modes, which possess a very small dispersion across the Brillouin zone, that is typical for a molecular crystal. These modes are due to the “breathing” motion of sulfur within GeS4 and SnS4 tetrahedra. The effects of structural (positional) disorder of mixed crystals are analyzed based on Raman scattering as well as photoluminescence results.

Optical and photoelectrical properties of GeSi nanoislands

Raman and lateral photoconductivity spectra of self-assembled SiGe nanoislands with heights of ~1 to 2 nm and bases of 10?20 nm were studied. Investigated heterostructures formed at a temperature 300 ?C after deposition of Ge with a nominal layer thickness of dGe ? 8 monolayers have the shape of the so-called hut clusters. It was estimated that the value of elastic deformation (?xx) is ?0.028 ? 0.002 (?zz = 0.015 ? 0.002), the germanium content in islands (x) is 0.87 ? 0.05. It was determined that the value of the valence band energy offset in the heterojunction between the strained Si0.13Ge0.87 layer of nanoislands and adjacent stretched Si is ~0.47 eV.

Determination of the Structural and Optical Characteristics of Cu 2 ZnSnS 4 Semiconductor Thin Films

The results of X-ray diffraction and optical studies of Cu2ZnSnS4 films produced by the flash evaporation of binary sulfide compounds under different technological conditions is reported. It is shown that it is possible to produce Cu2ZnSnS4 films, rather perfect in structural and optical respects, by choosing the optimal annealing temperatures at different Ar vapor pressures. The lattice parameters of the compounds are determined. The systematic shift in the photoluminescence bands under variations in the excitation level is established. It is found that the characteristics of the bands depend to a large extent on the annealing temperature, the Ar pressure during thermal treatment, and the resultant stoichiometry composition of the samples. It is shown that Raman studies and luminescence measurements can be used to assess the quality of the synthesized Cu2ZnSnS4 films and to obtain data on the energy structure of defects in the band gap.

Raman spectroscopy of Cu-Sn-S ternary compound thin films prepared by the low-cost spray-pyrolysis technique.

Cu-Sn-S (CTS) thin films were deposited onto bare and molybdenum (Mo) coated glass substrates by means of the spray pyrolysis technique under different conditions. The CTS thin films obtained are shown, by means of Raman spectroscopy, to consist of two main phases: Cu2SnS3 and Cu3SnS4 as well as of the secondary phase of Cu2-xS. The electrical conductivity of the spray-deposited p-type CTS thin films under investigation is determined by two shallow acceptor levels: Ev+0.07  eV at T<334  K and Ev+0.1  eV at T>334  K. The material of the CTS thin films was established to be a direct-band semiconductor with the bandgap Eg=1.89  eV. The SEM and x-ray energy dispersive analysis show the surface and cross section of the CTS thin film deposited onto molybdenum-coated glass ceramics substrate with the actual atomic ratios of Cu:Sn:S being 2.9:1:2.64, which is in good agreement with the Raman spectra. Also, a small content of residual Cl atoms was found in the CTS thin films under investigation as the by-product of the pyrolytic reactions.