Local electronic structure of phosphorus-doped ZnO films investigated by X-ray absorption near-edge spectroscopy

Using X-ray absorption near-edge structure spectroscopy (XANES), we investigate the local electronic structure of phosphorus (P) and its chemical valence in laser-ablated n-type (as-grown), and p-type (annealed) P-doped ZnO thin films. Both the P L ₁- and P L _2,3-edge XANES spectra reveal that the valence state of P is 3− (P³⁻) in the p-type as well as in the n-type P-doped ZnO. However, the peak intensity is stronger in the former than that in the latter, suggesting that P replaces O (O²⁻ sites with the P³⁻) after rapid thermal annealing. The Zn and O K-edges XANES spectra consistently demonstrate that, in the p-type state, P ions substitutionally occupy O sites in the ZnO lattice.     

NIR-VIS reflectivity spectra of some transition metal thiophosphates

Summary Room temperature optical-reflectivity measurements on some transition metal thiophosphates were carried out in the near infrared and visible regions. The resulting spectra, interpreted on the basis of the ?transition metal weakly interacting? model, agree well with earlier optical transmission measurements. Below the fundamental absorption edge, the observed features have been assigned to 3d–3d transitions occurring on the transition metal ion, while those observed at photon energies greater than the absorption threshold have been attributed to transitions from the valence bands to discrete 3d orbital levels or to the conduction bands. A more detailed information on the metal ion 3d levels energy distribution with respect to the valence band states belonging to the (P₂S₆)^4- cluster and a more precise determination of the MPS₃ absorption edge energy position have been obtained.     

Soft x-ray absorption of FePS3 and NiPS3

With the partial yield technique we measured the absorption spectra of several core levels in FePS₃ and NiPS₃. The M_{2, 3} spectra of Fe and Ni are interpreted as localized transitions 3p⁶3d^m?3p⁵ 3d^m+1 of the transition metal ion, split into a multiplet by final state multiconfiguration interaction. The P L_{2, 3}, S L_{2, 3}, and S L₁ spectra are similar to each other and are interpreted in terms of the projected density of states of the conduction bands derived from the states of the (P₂S₆)^4? cluster.     

Far-infrared spectral studies of magnesium and aluminum co-substituted lithium ferrites

Polycrystalline Mg_xAl_2xLi_0.5(1−x)Fe_2.5(1−x) O₄ (x = 0.0, 0.2, 0.5, 0.6 and 0.7) ferrites were prepared by standard ceramic method, and characterized by X-ray diffraction and infrared absorption spectroscopy. The spectra show two significant absorption bands in the wave number range of 400–1000 cm⁻¹ arising from interatomic vibrations in the tetrahedral and octahedral coordination compounds. The decrease in intensity and increase in broadness of bands with concentration (x) are explained on the basis of cation distribution. The force constants and bulk modulus are found to decrease with Mg-Al content (x) which suggested weakening of interatomic bonding. An alternate method for the determination of bulk modulus, longitudinal and transverse velocities is suggested. The magnetic and electrical properties of these compounds are explained in the light of structural and optical properties.     

Optical and IR study of Li2O–CuO–P2O5 glasses

Infrared (IR) and UV spectra of ternary Li₂O–CuO–P₂O₅ glasses in two series Li₂O(65−X)%–CuO(X%)–P₂O₅(35%), X = 20, 30, 40 and Li₂O(55−X)%–CuO(X%)–P₂O₅(45%), X = (10, 20, 30) were studied. Infrared (IR) investigations showed the metaphosphate and pyrophosphate structures and with increase of CuO content in metaphosphate glass, the skeleton of metaphosphate chains is gradually broken into short phosphate groups such as pyrophosphate. IR spectra showed one band at about 1,220 and 1,260 cm⁻¹ for P₂O₅(35%) and P₂O₅(45%) series, respectively, assigned to P=O bonds. For CuO additions ≤20 mol%, the glasses exhibit two bands in the frequency range 780–720 cm⁻¹ which are attributed to the presence of two P–O–P bridges in metaphosphate chain. But for CuO addition ≥30 mol%, the glasses exhibit only a single band at 760 cm⁻¹ which is assigned to the P–O–P linkage in pyrophosphate group. In optical investigations, absorption coefficient versus photon energy showed three regions: low energy side, Urbach absorption, and high energy side. In Urbach’s region, absorption coefficient depends exponentially on the photon energy. At high energy region, optical gap was calculated and investigations showed indirect transition in compounds and decreases in optical gap with increases of copper oxides contents that is because of electronic transitions and increasing of nonbridging oxygen content.     

Kinetics of the photoconductivity and absorption in the D −(A +) bands in doped silicon

The photoconductivity (PC) spectra and the induced absorption of background radiation in the energy range 10–40 meV are investigated in weakly compensated B-, Ga-, and As-doped silicon at 4.2 K. It is shown that dips corresponding to the photoionization of long-lived excited states of B and As are observed in the PC spectra on the D ⁻(A ⁺) bands. It is found that the frequency dependence of the PC spectra corresponds to excitation relaxation times of the order of 10⁻⁴ s for the states in the D ⁻ (A ⁺) bands. It is established that in electric fields E>100 V/cm the PC decreases sharply, while the induced absorption of the background radiation changes very little. This confirms the conclusion that the excitation of the D ⁻ (A ⁺) itself makes the main contribution to the PC. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 4, 224–227 (25 August 1997)     

Electronic structure of titanium dichalcogenides TiX<Subscript>2</Subscript> (X = S,Se, Te)

The electronic structure and the chemical bond in titanium dichalcogenides TiX₂ (X = S, Se, Te), which are promising electrode materials for lithium batteries, are studied experimentally and theoretically. It is found that the X-ray photoelectron spectra of the valence bands and the core levels of titanium and its X-ray L _{2, 3} absorption spectra demonstrate a change in the ionic and covalent components of the chemical bond in these compounds. The densities of states in these compounds are calculated by the full-potential augmented-plane-wave method, and multiplet calculations of the X-ray L _{2, 3} absorption spectra of titanium are performed. It is shown that, in the row TiS₂-TiSe₂-TiTe₂, the covalence increases, the ionicity of the chemical bond decreases, and the effect of the crystal field of a ligand is weakened.     

Transition metal oxide perovskites by photoelectron and x-ray absorption spectroscopy

X-ray and ultraviolet photoelectron spectroscopy as well as x-ray absorption spectroscopy have been employed to investigate transition metal oxide perovskites of the general formula ABO₃ (A = La or rare-earth ion, B=trivalent transition metal ion). Systematics in the core levels and in the valence bands in the series of LaBO₃ compounds have been discussed. Lanthanum chemical shifts in the x-ray absorption spectra in this series show interesting trends. Photoelectron spectra of the solid solutions, LaNi_1−x Co _x O₃, LaNi_1−x Fe _x O₃ and LaFe_1−x Co _x O₃ show that the rigid band model is applicable to these systems. It is shown that x-ray photoelectron spectroscopy can be employed to identify multiple oxidation states of transition metal ions in oxide perovskites. Communication No. 30 from the Solid State and Structural Chemistry Unit. An erratum to this article is available at .     

Model for primary electron transfer and coupling of electronic states at reaction centers of purple bacteria

A detailed derivation is presented for relations making it possible to describe the effect of temperature on the halfwidth of the P960 and P870 absorption bands and also on the electron transfer (ET) rate at reaction centers (RCs) of the purple bacteria Rps. viridis and Rb. sphaeroides. Primary electron transfer is considered as a resonant nonradiative transition between P* and P⁺B _L ⁻ states (where P is a special pair, B_L is an additional bacteriochlorophyll in the L branch of the reaction center). It has been shown that the vibrational h_α mode with frequency 130–150 cm⁻¹ controls primary electron transfer. It has been found that the matrix element of the electronic transition between the states P* and P⁺B _L ⁻ is equal to 12.7 ± 0.9 and 12.0 ± 1.2 cm⁻¹ for Rps. viridis and Rb. sphaeroides respectively. The mechanism is discussed for electron transport from P* and B_L and then to bacteriopheophytin H_L. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 294–303, May–June, 2006.     

Infrared absorption spectra of 2,3- and 3,5-dichloroaniline

The infrared absorption spectra of 2,3- and 3,5-dichloroanilines have been recorded in the region 250–4000 cm⁻¹. The spectra of the latter are recorded in solid phase (KBr and Nujol mull) and in CS₂/CCl₄ and CHCl₃ solutions while that of the former in thin film only. The spectra have been analysed assuming C ₃ and C_2v point group symmetry respectively and a tentative assignment of the observed bands to different fundamental modes has been made.     

Studying the electronic structure of Cr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ti<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript>2</Subscript> by X-ray resonance and absorption spectroscopy

Cr _x Ti_{1 − x} Se₂ (x = 0–0.83) solid solutions have been synthesized. Single crystals have been grown in the range of concentrations x = 0–0.83. Structural studies of samples have revealed that chromium atoms substitute titanium in the TiSe₂ matrix. The X-ray photoelectron spectra of the core levels, the resonance spectra of the valence bands in 1T-Cr _x Ti_{1 − x} Se₂, and the X-ray absorption spectra of titanium and chromium are studied. The titanium and chromium atoms are shown to have oxidation numbers of +4 and +3, respectively, in an identical octahedral environment. The local density of chromium states has been calculated. The results of the calculation agree well with the experimental data and indicate that the electronic 3d states of chromium substituting titanium in the matrix are spin-polarized and the density of chromium states is halfmetal magnet in behavior.     

Infrared absorption spectra of pure and doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystals

Several weak absorption bands have been observed in the optical absorption spectra of pure and rare-earth-doped YAl₃(BO₃)₄ single crystals in the 3350– 3650 cm⁻¹ wave number region. Two of them, peaking at about 3377 cm⁻¹ and 3580 cm⁻¹ in the 8 K spectra, appear in most of the samples. They are tentatively attributed to the stretching mode of OH⁻ ions incorporated in the crystal during the growth. An additional absorption band at about 5250 cm⁻¹ at 8 K has also been detected in almost all samples. The temperature and polarization dependences of these bands, and their possible origin, are discussed.     

Electronic excitations in ZnWO4 and ZnxNi1?xWO4 (x = 0.1 ? 0.9) using VUV synchrotron radiation

The photoluminescence spectra and luminescence excitation spectra of pure microcrystalline and nano-sized ZnWO₄ as well as the Zn _x Ni_1−x WO₄ solid solutions were studied using vacuum ultraviolet (VUV) synchrotron radiation. The samples were also characterized by x-ray powder diffraction. We found that: (i) the shape of the photoluminescence band at 2.5 eV, being due to radiative electron transitions within the [WO₆]⁶⁻ anions, becomes modulated by the optical absorption of Ni²⁺ ions in the Zn _x Ni_1−x WO₄ solid solutions; and (ii) no significant change in the excitation spectra of Zn_0.9Ni_0.1WO₄ is observed compared to pure ZnWO₄. At the same time, a shift of the excitonic bands to smaller energies and a set of peaks, attributed to the one-electron transitions from the top of the valence band to quasi-localized states, were observed in the excitation spectrum of nano-sized ZnWO₄.     

X-ray absorption near edge structure (XANES) for KCl

The cluster calculations of K and L_2,3 edge XANES of K and Cl in KCl within the multiple scattering theory formalism using nonlocal HF potentials with abd without consideration of core hole field were performed. For K spectra the influence of the core hole potential is rather weak and the results are similar to those obtained with Xα potentials. For L_2,3 spectra, particularly for that of K⁺, core hole field leads to a radical redistribution of oscillator strength caused mainly by the spatial rearrangement of d like states. Calculated XANES curves show good over-all agreement with the experimental spectra (the L_2,3 absorption of K⁺ in KCl was measured using the synchrotron radiation of the USSR Academy of Sciences storage ring VEPP-2M in Novosibirsk).     

Correlation of magnetic properties with the local features of the electronic and crystal structure in the Ce2Fe17 ? xMnx intermetallide: XAFS data analysis

The rearrangement of the local environment of cerium has been examined using extended X-ray absorption fine structure spectroscopy above the K-Ce absorption edge for various manganese contents and temperatures in Ce₂Fe_{17 − x} Mn _x intermetallics (x = 0, 1, 2). The valence state of cerium has been studied simultaneously by X-ray absorption near-edge structure spectroscopy above the L ₃-Ce absorption under the same conditions. A correlation has been revealed between the changes observed in the local electronic and crystal structure of Ce₂Fe_{17 − x} Mn _x compounds and the types of magnetic states in them.     

Local Moment of Ir in Fe,Co and Ni Hosts Probed by Ir L 2,3 Edge X-Ray Magnetic Circular Dichroism

The formation of an induced 5d magnetic moment on Ir in Fe₉₇Ir₃, Co₉₅Ir₅ and Ni₉₅Ir₅ alloys has been investigated by X-ray magnetic circular dichroism (XMCD) and X-ray absorption spectra (XAS) measurements at Ir L _2,3 edges. Using a sum rule which relates the integrals of these spectra with the ground state expectation value of the orbital angular momentum 〈L _Z 〉 of the probed atom, the orbital moment m _orb of Ir could be determined as −0.071(2) μ _B in an Fe host, −0.067(2) μ _B in a Co host and −0.041(1) μ _B in a Ni host. The spin magnetic moment m _spin of Ir is also found to be the maximal in Fe and the minimal in Ni. The total moment of Ir is found to be approximately 1/5 of total moment of Fe, 2/13 of the total moment of Co, and 1/4 of the total moment of Ni. This revised version was published online in September 2006 with corrections to the Cover Date.     

Changes in Auger spectra of Mg and Fe due to oxidation

Auger electron spectra of clean Mg and Fe surfaces have been investigated under UHV conditions. The main Auger peaks in the low energy Auger spectra of these elements are identified as due to L_2,3VV and M_2,3VV transitions for Mg and Fe respectively. Changes in the low energy spectra of these clean surfaces of Mg and Fe due to chemisorption of residual oxygen in the UHV system, were also studied. The results indicate that for each oxidised surface new larger Auger peaks appear at energies lower than the original main peaks in the clean spectra. The changes in the spectra are believed to be due to the energy shifts of inner energy levels and valence bands involved in the Auger transitions as an oxide is formed.     

Spectral-luminescent and proton-acceptor properties of 9-11-dehydrogenated 8-azasteroid

Methods of quantum chemistry (including the method of intermediate neglect of differential overlap (INDO)) are used to calculate and to interpret the absorption and fluorescence spectra of the 9-11-dehydroderivative 2,3-dimethoxy-8-aza-D-homogon-1,3,5(10),13-tetraene-12,17a-dion (DA-1) molecule in aproton and proton-donor solvents. The electronic structure and spectra of electronically excited states of the isolated molecule and its complexes with water and proton solvates are calculated. It is demonstrated that bands in the absorption spectra are complex; they are formed by two or more electron transitions. It is established that only the charged DA-1 + H ₅ O ₂ ⁺ and DA-1 + 2H ₃ O ⁺ complexes can fluoresce. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 3–9, June, 2006.     

XANES and USXES studies of interatomic interactions in (Co41Fe39B20)x(SiO2)1 ? x nanocomposites

The electronic structure and phase composition of (Co₄₁Fe₃₉B₂₀) _x (SiO₂)_{1 − x} nanocomposites are studied by x-ray absorption near-edge spectroscopy, which is extremely sensitive to the chemical environment of elements in multicomponent compounds. An analysis of the recorded Fe L _{2, 3}, Co L _{2, 3}, B K, Si L _{2, 3}, and O K absorption spectra demonstrates interatomic interactions between the elements of the metallic and dielectric components of the nanocomposites. As a result of these interatomic interactions, a complex multiphase system, whose electronic structure should determine the transport and magnetic properties of the nanocomposites, forms. In particular, the transformation of the fine structure of the iron L _{2, 3} spectra reflects a change in the ratio of divalent to trivalent iron in its oxides and/or silicates. CoO and complex boron oxides are found to exist in the nanocomposites. The electrical conductivity of a FeO · F₂O₃ · CoO grain embedded in the silicate-oxide medium of the nanocomposites is controlled by electron exchange between Co²⁺, Fe²⁺, and Fe³⁺ ions. The dielectric component consists of a mixture of silicon oxide and the silicates/borosilicates of transition metals. Original Russian Text ? é.P. Domashevskaya, S.A. Storozhilov, S.Yu. Turishchev, V.M. Kashkarov, V.A. Terekhov, O.V. Stogneĭ, Yu.E. Kalinin, A.V. Sitnikov, S.L. Molodtsov, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 1, pp. 135–141.     

A study of theXVV auger line shape of Fe−Ni alloys

Summary A comparison is performed between theoretical and experimental shapes of theXVV (X=M _2,3 andL ₃) Auger spectra of ferromagnetic Fe _x −Ni_1−x alloys forx=0.48 and 0.27 in order to check if recent theories, which take into account the Coulomb correlation between the two final Auger holes, would be able to reproduce shape and position of the experimental peaks in an accurate way. For the case under investigation, it seems that, at least for the low-energy (M _2,3 VV) spectra and notwithstanding the usual neglecting of matrix element effects, the theory gives results in close agreement with the experimental data. The comparison with the high-energyL ₃ VV spectra is somewhat hampered by an asymmetric broadening of the experimental data on the low kinetic-energy side due to satellite structures, but still gives good agreement on the high kinetic-energy side. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.