Iraida N. Demchenko

Highly mismatched crystalline and amorphous GaN1−xAsx alloys in the whole composition range

Alloying is a commonly accepted method to tailor properties of semiconductor materials for specific applications. Only a limited number of semiconductor alloys can be easily synthesized in the full composition range. Such alloys are, in general, formed of component elements that are well matched in terms of ionicity, atom size, and electronegativity. In contrast there is a broad class of potential semiconductor alloys formed of component materials with distinctly different properties. In most instances these mismatched alloys are immiscible under standard growth conditions. Here we report on the properties of GaN1−xAsx, a highly mismatched, immiscible alloy system that was successfully synthesized in the whole composition range using a nonequilibrium low temperature molecular beam epitaxy technique. The alloys are amorphous in the composition range of 0.17<x<0.75 and crystalline outside this region. The amorphous films have smooth morphology, homogeneous composition, and sharp, well defined optical absorp...

Local atomic structure and magnetic ordering of iron in Fe-chitosan complexes.

The iron crosslinked chitosan (Ch-Fe-CL) and N-carboxylmethyl chitosan (N-CM-Ch-Fe) complexes were studied by complementary techniques: structurally sensitive Mössbauer and X-ray absorption methods, as well as static magnetic measurements. A detailed and consistent description of these complexes including, besides the overall magnetic behavior, the spin ordering and local atomic structure around Fe ions is presented. Fe atoms in the investigated samples are mostly penta-coordinated and appear in a high spin Fe (3+) ionic state. In Ch-Fe-CL, two kinds of Fe near neighbors are equally probable and several Fe atoms are situated in the second coordination sphere. The magnetic interactions between these Fe ions lead to a sperimagnetic-like ordering. In N-CM-Ch-Fe, only one Fe neighborhood was found. Other Fe atoms were identified neither in the first nor in the second coordination sphere, but the third coordination sphere indicates the presence of Fe atoms. The magnetic coupling between these atoms is antiferromagnetic, but the dominant part of Fe in this sample remains in a paramagnetic state.

Dielectric Function for Gold in Plasmonics Applications: Size Dependence of Plasmon Resonance Frequencies and Damping Rates for Nanospheres

Realistic representation of the frequency dependence of dielectric function of noble metals has a significant impact on the accuracy of description of their optical properties and farther applications in plasmonics, nanoscience, and nanotechnology. Drude-type models successfully used in describing material properties of silver, for gold are known to be not perfect above the threshold energy at 1.8 eV. We give the improved, simple dielectric function for gold which accounts for the frequency dependence of the interband transitions over 1.8 eV and, in addition, for the finite size effects in gold nanoparticles. On that basis, we provide the improved characterization of the spectral performance of gold nanoparticles. Furthermore, we give the direct size dependence of the resonance frequencies and total damping rates of localized surface plasmons of gold nanoparticles (retardation effects are taken into full account) in diverse dielectric environments. The results are compared to the data obtained experimentally for gold monodisperse colloidal nanospheres, as well with the experimental results of other authors.

Polarization dependent X-ray absorption studies of the chemical bonds anisotropy in wurtzite GaN grown at different conditions

Polarization-dependent X-ray absorption spectroscopy was used to examine the influence of crystal growth techniques and substrates type on the bond lengths and the bond structure of the single crystalline, wurtzite GaN in a form of bulk materials and epitaxial layers. The layers were grown by molecular beam epitaxy (MBE) and metalorganic chemical vapor deposition (MOCVD) on different substrates such as SiC, sapphire and GaN. From the observed X-ray absorption near edge structure (XANES) of the Ga K-edges, it was found that MOCVD introduces a stronger disorder around Ga atoms than MBE. Comparing the Ga and N K-edges of the epilayers and the bulk crystal, we found a prevailing contribution of N-vacancies in the layers and dominance of Ga-vacancies in the bulk crystal. The bonds along the c-axis are less perfect than the bonds in the c-plane for all investigated epilayers. The performed standard extended X-ray absorption fine structure analysis (EXAFS) resulted in a direct estimate of the bond lengths in the c-plane and along the c-axis.

X-ray absorption studies of phase formation in a Ti/TiN coating on cubic boron nitride

Abstract We report on the use of X-ray absorption spectroscopy as a tool for the identification of the phases formed in the technological process of composite preparation. A composite is a mixture of several compounds and, in many cases, the use of traditional X-ray diffraction to determine the phases can be difficult because of the small amount of phases present. X-ray absorption studies (XANES and EXAFS) of the c-BN Ti/TiN layered system are presented. These materials are models of the powdered composites used in industry for tool production. XANES and EXAFS analyses showed that, after annealing up to 1300 °C, a TiB 2 phase is formed, but the chemical bonding of the Ti atoms differs slightly from that of standard TiB 2 powder, showing the presence of defects in site occupancy. Assuming that the X-ray absorption spectral shape is a linear combination of the spectra of all the components, we estimated the kind and limits of other phase inclusions.

Photoemission study of EuS/PbS electronic structure

Abstract The ultraviolet photoemission and resonant photoemission spectroscopy were used to study the electronic structure of EuS/PbS multilayers with the contribution of europium’s 4f orbitals to the density of states of the valence band. The valence band photoemission spectra of galena and europium monosulfide layers show good agreement with theoretical density of state computations. The relative ratio of Eu 3+ and Eu 2+ ions located at the surface of EuS layer strongly depends on conditions of preparation procedures of the sample surface. For the buried EuS layer only Eu 2+ ions were observed.

X-ray absorption studies of chlorine valence and local environments in borosilicate waste glasses

Chlorine (Cl) is a constituent of certain types of nuclear wastes and its presence can affect the physical and chemical properties of silicate melts and glasses developed for the immobilization of such wastes. Cl K-edge X-ray absorption spectra (XAS) were collected and analyzed to characterize the unknown Cl environments in borosilicate waste glass formulations, ranging in Cl-content from 0.23 to 0.94 wt.%. Both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data for the glasses show trends dependent on calcium (Ca) content. Near-edge data for the Ca-rich glasses are most similar to the Cl XANES of CaCl2, where Cl is coordinated to three Ca atoms, while the XANES for the Ca-poor glasses are more similar to the mineral davyne, where Cl is most commonly coordinated to two Ca in one site, as well as Cl and oxygen nearest-neighbors in other sites. With increasing Ca content in the glass, Cl XANES for the glasses approach that for CaCl2, indicating more Ca nearest-neighbors around Cl. Reliable structural information obtained from the EXAFS data for the glasses is limited, however, to ClACl, ClAO, and ClANa distances; ClACa contributions could not be fit to the glass data, due to the narrow k-space range available for analysis. Structural models that best fit the glass EXAFS data include ClACl, ClAO, and ClANa correlations, where ClAO and ClANa distances decrease by approximately 0.16 Å as glass Ca content increases. XAS for the glasses indicates Cl is found in multiple sites where most Cl-sites have Ca neighbors, with oxygen, and possibly, Na second-nearest neighbors. EXAFS analyses suggest that ClACl environments may also exist in the glasses in minor amounts. These results are generally consistent with earlier findings for silicate glasses, where Cl was associated with Ca and Na in network modifier sites. 2010 Elsevier B.V. All rights reserved.

The electronic structure of homogeneous ferromagnetic (Ga, Mn)N epitaxial films

X-ray Absorption Fine Structure (XAFS) techniques, namely, X-ray Near Edge Structure (XANES), Extended XAFS (EXAFS), and Anomalous X-ray Diffraction (AXRD) were used to investigate the local atomic and electronic structure of (Ga, Mn)N magnetic layers with Mn concentrations of up to 10% grown by Molecular Beam Epitaxy. The XANES and AXRD analysis prove the Mn incorporation on substitutional GaN lattice sites. EXAFS results indicate the good quality of the structure under examination, although 0.5 nitride atom vacancies were found. The Wien2k code was applied to interpret the XANES spectra quantitatively, i.e., to determine the electronic structure of the Mn atoms. It was shown that accounting for the core-hole effect is necessary to reconstruct effectively the XANES spectra. Conducted charge density analysis based on DFT calculations identified the valency of Mn atom to be of 2.4+.

Inner-shell photofragmentation of Cl2

We report an extensive study on partial-ion-yield spectroscopy around the Cl 1s and 2p ionization thresholds for Cl-2. All positive ion channels, several with the same mass/charge ratio, which could be distinguished by taking the advantage of the Cl-37 isotope, have been measured at a photon resolution of nearly 6500. At the Cl 1s ionization threshold, no significant differences are reported between the absorption and the partial-ion yields. In contrast, near the 2p ionization thresholds, we detect large variations in the fragmentation patterns following excitations to the Rydberg series when comparing the atomic fragment ions to the molecular fragment ions. We attribute the different behaviours to the more-or-less diffuse nature of Rydberg states with different angular momenta.

XANES: observation of quantum confinement in the conduction band of colloidal PbS quantum dots

The presented investigations aimed at development of inexpensive method for synthesized materials suitable for utilization of solar energy. This important issue was addressed by focusing, mainly, on electronic local structure studies with supporting x-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis of colloidal galena nano-particles (NPs) and quantum dots (QDs) synthesized using wet chemistry under microwave irradiation. Performed x-ray absorption near edge structure (XANES) analysis revealed an evidence of quantum confinement for the sample with QDs, where the bottom of the conduction band was shifted to higher energy. The QDs were found to be passivated with oxides at the surface. Existence of sulfate/sulfite and thiosulfate species in pure PbS and QDs, respectively, was identified.