Fundamental crystal field excitations in magnetic semiconductor SnO2: Mn, Fe, Co, Ni.

Directly measuring elementary electronic excitations in dopant 3d metals is essential to understanding how they function as part of their host material. Through calculated crystal field splittings of the 3d electron band it is shown how transition metals Mn, Fe, Co, and Ni are incorporated into SnO2. The crystal field splittings are compared to resonant inelastic X-ray scattering (RIXS) experiments, which measure precisely these elementary dd excitations. The origin of spectral features can be determined and identified via this comparison, leading to an increased understanding of how such dopant metals situate themselves in, and modify the host's electronic and magnetic properties; and also how each element differs when incorporated into other semiconducting materials. We found that oxygen vacancy formation must not occur at nearest neighbour sites to metal atoms, but instead must reside at least two coordination spheres beyond. The coordination of the dopants within the host can then be explicitly related to the d-electron configurations and energies. This approach facilitates an understanding of the essential link between local crystal coordination and electronic/magnetic properties.

Transition from Reconstruction toward Thin Film on the (110) Surface of Strontium Titanate.

The surfaces of metal oxides often are reconstructed with a geometry and composition that is considerably different from a simple termination of the bulk. Such structures can also be viewed as ultrathin films, epitaxed on a substrate. Here, the reconstructions of the SrTiO3 (110) surface are studied combining scanning tunneling microscopy (STM), transmission electron diffraction, and X-ray absorption spectroscopy (XAS), and analyzed with density functional theory calculations. Whereas SrTiO3 (110) invariably terminates with an overlayer of titania, with increasing density its structure switches from n × 1 to 2 × n. At the same time the coordination of the Ti atoms changes from a network of corner-sharing tetrahedra to a double layer of edge-shared octahedra with bridging units of octahedrally coordinated strontium. This transition from the n × 1 to 2 × n reconstructions is a transition from a pseudomorphically stabilized tetrahedral network toward an octahedral titania thin film with stress-relief from octahedral strontia units at the surface.

Adjacent Fe-Vacancy Interactions as the Origin of Room Temperature Ferromagnetism in (In(1-x)Fe(x))2O3.

Dilute magnetic semiconductors (DMSs) show great promise for applications in spin-based electronics, but in most cases continue to elude explanations of their magnetic behavior. Here, we combine quantitative x-ray spectroscopy and Anderson impurity model calculations to study ferromagnetic Fe-substituted In2O3 films, and we identify a subset of Fe atoms adjacent to oxygen vacancies in the crystal lattice which are responsible for the observed room temperature ferromagnetism. Using resonant inelastic x-ray scattering, we map out the near gap electronic structure and provide further support for this conclusion. Serving as a concrete verification of recent theoretical results and indirect experimental evidence, these results solidify the role of impurity-vacancy coupling in oxide-based DMSs.

Measuring partial fluorescence yield using filtered detectors.

Typically, X-ray absorption near-edge structure measurements aim to probe the linear attenuation coefficient. These measurements are often carried out using partial fluorescence yield techniques that rely on detectors having photon energy discrimination improving the sensitivity and the signal-to-background ratio of the measured spectra. However, measuring the partial fluorescence yield in the soft X-ray regime with reasonable efficiency requires solid-state detectors, which have limitations due to the inherent dead-time while measuring. Alternatively, many of the available detectors that are not energy dispersive do not suffer from photon count rate limitations. A filter placed in front of one of these detectors will make the energy-dependent efficiency non-linear, thereby changing the responsivity of the detector. It is shown that using an array of filtered X-ray detectors is a viable method for measuring soft X-ray partial fluorescence yield spectra without dead-time. The feasibility of this technique is further demonstrated using α-Fe2O3 as an example and it is shown that this detector technology could vastly improve the photon collection efficiency at synchrotrons and that these detectors will allow experiments to be completed with a much lower photon flux reducing X-ray-induced damage.

Electronic structure of spinel-type nitride compounds Si3N4, Ge3N4, and Sn3N4 with tunable band gaps: application to light emitting diodes.

In this Letter using experimental and theoretical methods, we show that the solid solutions of group 14 nitrides having spinel structure (γ-M3N4 where M=Si, Ge, Sn) exhibit mainly direct electronic band gaps with values that span the entire visible wavelength region, making these hard and thermally stable materials suitable for optoelectronic devices and, in particular, lighting applications. Using the simulated band structure, we also calculate the exciton binding energy. The combination of large exciton binding energies and the tunable electronic band gaps in the visible range makes these binary spinel nitrides and their solid solutions a new class of multifunctional materials with optoelectronic properties that can be engineered to suit the desired application.

Comparative theoretical and experimental study of the radiation-induced decomposition of glycine.

The radiation-induced decomposition of glycine is studied using a combination of near-edge X-ray absorption fine structure (NEXAFS) measurements and DFT calculations. The measured spectra show strong dose- or time-dependent effects consistent with a complex, multistep decomposition. Principal component analysis was used to determine the number of distinct molecules that were needed to explain the observed changes in the measured spectra, and the emerging absorption features are assigned to various product molecules through comparison with simulated spectra of several model compounds. It is clear from the experiment that the major effect of soft X-ray irradiation is the fragmentation of the molecule, primarily at the carbonyl sites. Peptide formation is shown to occur under irradiation; a condensation reaction initiated by the removal of a carbonyl oxygen is the proposed mechanism. This study utilizes a novel approach to the study of radiation damage that can occur during measurements and suggests that it may be possible to use simulated model spectra to correct for these effects in measured spectra.

Co and Al co-doping for ferromagnetism in ZnO:Co diluted magnetic semiconductors.

Co and Al co-doped ZnO diluted magnetic semiconductors are fabricated by a pulsed laser deposition and their electronic structure is investigated using x-ray absorption and emission spectroscopy. The Zn(0.895)Co(0.100)Al(0.005)O thin films grown under oxygen-rich conditions exhibit ferromagnetic behavior without any indication of Co clustering. The Co L-edge and O K-edge x-ray absorption and emission spectra suggest that most of the Co dopants occupy the substitutional sites and the oxygen vacancies are not responsible for free charge carriers. The spectroscopic results and first principles calculations reveal that the ferromagnetism in Co and Al co-doped ZnO semiconductors mainly arises from Al interstitial defects and their hybridization with Co substitutional dopants.

Probing interfacial characteristics of rubrene/pentacene and pentacene/rubrene bilayers with soft X-ray spectroscopy.

The electronic structure of rubrene/pentacene and pentacene/rubrene bilayers has been investigated using soft X-ray absorption spectroscopy, resonant X-ray emission spectroscopy, and density-functional theory calculations. X-ray absorption and emission measurements reveal that it has been possible to alter the lowest unoccupied and the highest occupied molecular orbital states of rubrene in rubrene/pentacene bilayer. In the reverse case, one gets p* molecular orbital states originating from the pentacene layer. Resonant X-ray emission spectra suggest a reduction in the hole-transition probabilities for the pentacene/rubrene bilayer in comparison to reference pentacene layer. For the rubrenepentacene structure, the hole-transition probability shows an increase in comparison to the rubrene reference. We also determined the energy level alignment of the pentacene-rubrene interface by using X-ray and ultraviolet photoelectron spectroscopy. From these comparisons, it is found that the electronic structure of the pentacene-rubrene interface has a strong dependence on interface characteristics which depends on the order of the layers used.

Post-annealing effect on the electronic structure of Mn atoms in Ga(1-x)Mn(x)As probed by resonant inelastic x-ray scattering.

The electronic structure of as-grown and post-annealed Ga(1-x)Mn(x)As epilayers (x≈0.055) has been investigated using resonant inelastic x-ray scattering. Mn L2,3 x-ray emission spectra show that the integral intensity ratio of Mn L2 to L3 emission lines increases with annealing temperature and comes close to that of manganese oxide. The oxygen K-emission/absorption spectra of post-annealed Ga0.945Mn0.055As show 1.5-3.0 times higher degree of oxidation on the film surface than that of the as-grown sample. These experimental findings are attributed to the diffusion of Mn impurity atoms from interstitial positions in the GaAs host lattice to the surface where they are passivated by oxygen.

X-ray spectroscopic study of amorphous and polycrystalline PbO films, α-PbO, and ß-PbO for direct conversion imaging.

We investigated the electronic structure of Lead Oxide (PbO) - one of the most promising photoconductor materials for direct conversion x-ray imaging detectors, using soft x-ray emission and absorption spectroscopy. Two structural configurations of thin PbO layers, namely the polycrystalline and the amorphous phase, were studied, and compared to the properties of powdered α-PbO and ß-PbO samples. In addition, we performed calculations within the framework of density functional theory and found an excellent agreement between the calculated and the measured absorption and emission spectra, which indicates high accuracy of our structural models. Our work provides strong evidence that the electronic structure of PbO layers, specifically the width of the band gap and the presence of additional interband and intraband states in both conduction and valence band, depend on the deposition conditions. We tested several model structures using DFT simulations to understand what the origin of these states is. The presence of O vacancies is the most plausible explanation for these additional electronic states. Several other plausible models were ruled out including interstitial O, dislocated O and the presence of significant lattice stress in PbO.

Bulk vs. Surface Structure of 3d Metal Impurities in Topological Insulator Bi2Te3.

Topological insulators have become one of the most prominent research topics in materials science in recent years. Specifically, Bi2Te3 is one of the most promising for technological applications due to its conductive surface states and insulating bulk properties. Herein, we contrast the bulk and surface structural environments of dopant ions Cr, Mn, Fe, Co, Ni, and Cu in Bi2Te3 thin films in order to further elucidate this compound. Our measurements show the preferred oxidation state and surrounding crystal environment of each 3d-metal atomic species, and how they are incorporated into Bi2Te3. We show that in each case there is a unique interplay between structural environments, and that it is highly dependant on the dopant atom. Mn impurities in Bi2Te3 purely substitute into Bi sites in a 2+ oxidation state. Cr atoms seem only to reside on the surface and are effectively not able to be absorbed into the bulk. Whereas for Co and Ni, an array of substitutional, interstitial, and metallic configurations occur. Considering the relatively heavy Cu atoms, metallic clusters are highly favourable. The situation with Fe is even more complex, displaying a mix of oxidation states that differ greatly between the surface and bulk environments.

Experimental and theoretical investigation of the electronic structure of 5-fluorouracil compounds.

We present a comparison between experimental and theoretical X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) of 5-fluorouracil compounds, with an emphasis on the effects of the inclusion of nickel in the structure. By focusing on the 1s thresholds of carbon, nitrogen, oxygen, and fluorine it was possible to provide a complete picture of the occupied and unoccupied partial density of states of the 5-fluorouracil systems. Spectra calculated using density functional theory are compared to experimental results. Most experimental results agree well with our theoretical calculations for the XAS and XES of the compounds. All spectral features are assigned. Our results reveal that the nickel in the compound is coordinated with the nitrogen sites of the 5-fluorouracil ligands.

Combined X-ray absorption spectroscopy and density functional theory examination of ferrocene-labeled peptides.

A combination of soft X-ray absorption spectroscopy (XAS) measurements and StoBe density functional theory (DFT) calculations has been used to study the electronic structures of the ferrocene-labeled peptides Fc-Pro(n)-OBz (n = 1-4). Excellent agreement between the measured and the simulated data is observed in all cases, and the origin of all major spectral features was assigned. The breaking of the degeneracy of the ferrocene 3e(2u)-like unoccupied molecular orbital under the influence of a substituent attached to a Cp ring was observed experimentally. The influence of the bonding environment on the O 1s and N 1s XAS spectra was examined. A corrected assignment of one of the major features in the Fe 2p XAS spectra of ferrocene is proposed and supported by the DFT simulations, as well as the measured spectra.

Influence of graphite addition on the reactivity of Ti powder with H2 under ball milling.

The effect of graphite addition on the mechanism of hydrogen uptake by titanium during mechanochemical activation in hydrogen flow was studied using kinetic, structural, microscopic, and spectroscopic techniques. As was found, already a small graphite admixture of about 0.5 wt % changed the kinetics of mechanically induced H2 sorption and significantly stimulated Ti-H2 interaction. Two new types of occupation sites available for hydrogen were observed, which are characterized by low H2 desorption temperatures: about 650 and 750 K instead of 1000 K.

Dependence of DNA electronic structure on environmental and structural variations.

We present experimental and theoretical evidence that varying the local environment and physical structure of dried DNA has a direct impact on its electronic structure. By preparing samples of DNA in various solutions, it was possible to alter the type of ions present during the production of the DNA samples. These variations resulted in differences in the local chemical environment of the dried DNA molecules. X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) were used to probe the variations in the electronic structure of DNA samples. DFT calculations of a stack of 10 adenine (A)-thymine (T) nucleobase pairs show that slight structural variations in stacking height have a direct influence on the electronic structure and result in changes to the HOMO-LUMO gap. The effects of these differences in the local environment on the electronic structure are discussed and are related to the results of conductivity measurements of DNA.

Clustering of impurity atoms in Co-doped anatase TiO(2) thin films probed with soft x-ray fluorescence.

The electronic structure of Co-doped anatase TiO(2) epitaxial thin films grown at different partial oxygen pressures is investigated using soft x-ray emission spectroscopy. The resonantly excited Co L(2,3) x-ray emission spectra of ferromagnetic Ti(0.96)Co(0.04)O(2) samples for the oxygen-deficient regime show that the ratio of integral intensities for Co L(2) and L(3) emission lines significantly decreases with respect to nonmagnetic samples in the oxygen-rich regime. This is due to L(2)L(3)M(4,5) Coster-Kronig transitions and suggests that ferromagnetic Ti(0.96)Co(0.04)O(2) samples have n-type charge carriers and Co-Co bonds between substitutional and interstitial Co atoms are present while Co-O bonds are dominant in nonmagnetic Ti(0.96)Co(0.04)O(2) samples in the oxygen-rich regime. Electronic structure calculations show that the presence of free charge carriers and Co segregation play a crucial role in strong ferromagnetism at room temperature in Co-doped TiO(2).

An x-ray emission and density functional theory study of the electronic structure of Zn(1-x)Mn(x)S.

Mn 3d electronic states in the dilute magnetic semiconductor Zn(1-x)Mn(x)S (x = 0.1-0.3) are studied using soft x-ray emission (XES) measurements and density functional theory (DFT). Mn L(2,3) emission spectra of Zn(1-x)Mn(x)S (x = 0.1-0.3) suggest that the Mn impurities do not form clusters in the host ZnS lattice, in agreement with previous models. A shift in the position of a Mn L(3) XES feature suggests a change in the nature of the hybridization between the Mn 3d(3/2) and S 3p states as a function of x. Our DFT calculations reproduce the weak interatomic exchange interaction, as well as the strong intra-atomic exchange splitting that is expected from observations of Zeeman splitting in such materials.

Electronic structure of the nucleobases.

We present a comparison between experimental and calculated soft X-ray spectra of DNA's nucleobases, adenine (A), guanine (G), cytosine (C), and thymine (T) using X-ray absorption spectroscopy (XAS) and soft X-ray emission spectroscopy (XES). Spectra of the 1s thresholds of carbon, nitrogen, and oxygen give a complete picture of the occupied and unoccupied partial density of states of the nucleobases. A combination of both Hartree-Fock and density functional theory calculations are used in the comparison to experimental results. Most experimental results agree well with our theoretical calculations for the XAS and XES of all bases. All spectral features are assigned. A comparison of the experimental highest occupied molecular orbital-lowest unoccupied molecular orbital energy gaps is made to the diverse values predicted in the literature.

Electronic structure and spin trapping in LiMnAs and LiFeAs:Mn.

The electronic structure of insulating antiferromagnetic LiMnAs is investigated using soft x-ray spectroscopy and compared to the electronic structure of metallic LiFeAs. Our calculations support the experimentally observed insulating antiferromagnetic order in LiMnAs. The x-ray absorption and resonant inelastic x-ray scattering spectra in LiFeAs and LiMnAs are adequately explained by the electronic structure alone, although it is possible that LiMnAs has significant electronic correlations driven by Hund's J coupling. Finally, we show evidence of a possible spin trap in Li(Fe0.95Mn0.05)As.