Defects in room-temperature ferromagnetic Cu-doped ZnO films probed by x-ray absorption spectroscopy

We report a comprehensive study of the defects in room-temperature ferromagnetic (RTFM) Cu-doped ZnO thin films using x-ray absorption spectroscopy. The films are doped with 2 at.% Cu, and are prepared by reactive magnetron sputtering (RMS) and pulsed laser deposition (PLD), respectively. The results reveal unambiguously that atomic point defects exist in these RTFM thin films. The valence states of the Cu ions in both films are 2(+). In the film prepared by PLD, the oxygen vacancies (V(O)) form around both Zn ions and Cu ions in the hexagonal wurtzite structure. Upon annealing of the film in O(2), the V(O) population reduces and so does the RTFM. In the film prepared by RMS, the V(O)s around Cu ions are not detected, and the V(O) population around Zn ions is also smaller than in the PLD-prepared film. However, zinc vacancies (V(Zn)) are evidenced. Given the low doping level of spin-carrying Cu ions, these results provide strong support for defect-mediated ferromagnetism in Cu-doped ZnO thin films.     

Isotope and temperature effects in liquid water probed by x-ray absorption and resonant x-ray emission spectroscopy

High-resolution x-ray absorption and emission spectra of liquid water exhibit a strong isotope effect. Further, the emission spectra show a splitting of the 1b1 emission line, a weak temperature effect, and a pronounced excitation-energy dependence. They can be described as a superposition of two independent contributions. By comparing with gas phase, ice, and NaOH/NaOD, we propose that the two components are governed by the initial state hydrogen bonding configuration and ultrafast dissociation on the time scale of the O 1s core hole decay.     

Nearest-neighbor configuration in (GaIn)(NAs) probed by x-ray absorption spectroscopy

Ga(1-x)In(x)N(y)As(1-y) is a promising material system for the fabrication of inexpensive "last-mile" optoelectronic components. However, details of its atomic arrangement and the relationship to observed optical properties is not fully known. Particularly, a blueshift of emission wavelength is observed after annealing. In this work, we use x-ray absorption fine structure to study the chemical environment around N atoms in the material before and after annealing. We find that as-grown molecular beam epitaxy material consists of a nearly random distribution of atoms, while postannealed material shows segregation of In toward N. Ab initio simulations show that this short-range ordering creates a more thermodynamically stable alloy and is responsible for blueshifting the emission.     

Ultrafast core-hole-induced dynamics in water probed by x-ray emission spectroscopy

The isotope effect and excitation-energy dependence have been measured in the oxygen K-edge x-ray emission spectrum (XES). The use of XES to monitor core decay processes provides information about molecular dynamics (MD) on an ultrafast time scale through the O1s lifetime of a few femtoseconds. Different nuclear masses give rise to differences in the dynamics and the observed isotope effect in XES is direct evidence of the importance of such processes. MD simulations show that even the excitation-energy dependence in the XES is mainly related to differences in core-excited-state dynamics.     

Observing photochemical transients by ultrafast x-ray absorption spectroscopy

Accurate determination of the transient electronic structures, which drive photochemical reactions, is crucial in chemistry and biology. We report the detection of transient chemical changes on the picosecond time scale by x-ray-absorption near-edge structure of photoexcited aqueous [Ru(bpy)(3)](2+). Upon ultrashort laser pulse excitation a charge transfer excited state having a 300 ns lifetime is formed. We detect the change of oxidation state of the central Ru atom at its L3 and L2 edges, at a temporal resolution of 100 ps with the zero of time unambiguously determined.     

Ground state of the quasi-1D compound BaVS3 resolved by resonant magnetic x-ray scattering

Resonant magnetic x-ray scattering near the vanadium L2,3-absorption edges has been used to investigate the low temperature magnetic structure of high quality BaVS3 single crystals. Below T(N)=31 K, the strong resonance revealed a triple-incommensurate magnetic ordering at the wave vector (0.226 0.226 ξ) in hexagonal notation, with ξ=0.033. The azimuthal-angle dependence of the scattering signal and time-dependent density functional theory simulations indicate an antiferromagnetic order within the ab plane with the spins polarized along a in the monoclinic structure.     

Metal-insulator transitions in Cr-doped V2O3 by x-ray and ultraviolet photoelectron spectroscopy

X-ray and ultraviolet photoelectron spectroscopy have been employed to investigate the high temperature metal-insulator transitions in V₂O₃ and (V_0.99Cr_0.01)₂O₃. The high temperature transitions are associated with more gradual changes in the 3d bands compared to the low-temperature transitions. Communication No. 20 from Solid State & Structural Chemistry Unit.     

Properties of liquid silicon observed by time-resolved x-ray absorption spectroscopy

Time-resolved x-ray spectroscopy at the Si L edges is used to probe the electronic structure of an amorphous Si foil as it melts following absorption of an ultrafast laser pulse. Picosecond temporal resolution allows observation of the transient liquid phase before vaporization and before the liquid breaks up into droplets. The melting causes changes in the spectrum that match predictions of molecular dynamics and ab initio x-ray absorption codes.     

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 .     

Co dimers observed by extended x-ray absorption fine structure spectroscopy

Cobalt was introduced into a silver matrix by ion implantation and observed by extended x-ray absorption fine structure (EXAFS) spectroscopy. In the range 0.10--0.70 at. % evidence of Co dimers dispersed in the matrix was found. The dimers are somewhat contracted with respect to the bulk Co nearest neighbor distance and distributed in a chainlike configuration with each dimer at 90 degrees from each other along opposite square faces of the Ag fcc lattice.     

X-ray absorption near the edge structure and x-ray photoelectron spectroscopy studies on pyrite prepared by thermally sulfurizing iron films

This paper reports how pyrite films were prepared by thermal sulfurization of magnetron sputtered iron films and characterized by x-ray absorption near edge structure spectra and x-ray photoelectron spectroscopy on a 4B9B beam line at the Beijing Synchrotron Radiation Facility. The band gap of the pyrite agrees well with the optical band gap obtained by a spectrophotometer. The octahedral symmetry of pyrite leads to the splitting of the d orbit into t_{\rm 2g} and e_{\rm g} levels. The high spin and low spin states were analysed through the difference of electron exchange interaction and the orbital crystal field. Only when the crystal field splitting is higher than 1.5 eV, the two weak peaks above the white lines can appear, and this was approved by experiments in the present work.     

Bonding in liquid carbon studied by time-resolved x-ray absorption spectroscopy

Even the most basic properties of liquid carbon have long been debated due to the challenge of studying the material at the required high temperature and pressure. Liquid carbon is volatile and thus inherently transient in an unconstrained environment. In this paper we use a new technique of picosecond time-resolved x-ray absorption spectroscopy to study the bonding of liquid carbon at densities near that of the solid. As the density of the liquid increases, we see a change from predominantly sp-bonded atomic sites to a mixture of sp, sp2, and sp3 sites and compare these observations with molecular dynamics simulations.     

Characterization of fluorinated multiwalled carbon nanotubes by x-ray absorption spectroscopy

The C 1s and F 1s x-ray absorption spectra of fluorinated multiwalled carbon nanotubes with different fluorine contents and reference compounds (highly oriented pyrolytic graphite crystals and “white” graphite fluoride) were measured using the equipment of the Russian-German beamline at the BESSY II storage ring with a high energy resolution. The spectra obtained were analyzed with the aim of characterizing multiwalled carbon nanotubes and their products formed upon treatment of the nanotubes with fluorine at a temperature of 420°C. It was established that, within the probing depth (～15 nm) of carbon nanotubes, the process of fluorination occurs uniformly and does not depend on the fluorine concentration. The interaction of fluorine atoms with multiwalled carbon nanotubes in this case proceeds through the covalent attachment of fluorine atoms to graphene layers of the graphite skeleton and is accompanied by a change in the hybridization of the 2s and 2p valence electron states of the carbon atom from the trigonal (sp ²) to tetrahedral (sp ³) hybridization.     

5f Localization in light actinide compounds studied by L3-edge x-ray absorption

L₃-edge x-ray absorption spectroscopy was applied to electronic structure studies in compounds of U, Np, and Pu. Single-peaked white lines are observed at the L₃ thresholds, which exhibit shifts up to 6 eV to lower energies for the monopnictides and monochalcogenides relative to the tetravalent dioxides. These chemical shifts increase systematically from U to Np and Pu, reflecting an increasing localization of the 5f states.