Rapid combinatorial screening by synchrotron X-ray imaging

An X-ray imaging system, which does not require any scans of the sample or an X-ray beam and which, therefore, dramatically reduces the amount of time required, was employed to evaluate combinatorial libraries efficiently. Two-dimensional X-ray fluorescence (XRF) images of an 8 mm × 8 mm area were observed for combinatorial substrates of manganese-cobalt spinel MnCo₂O₄ and lithium ferrite LiFeO₂ via an exposure time of 1-3 s using synchrotron X-rays. Thus, XRF signals from a whole substrate could be observed at once in a short space of time. In order to observe the chemical environment simultaneously for all materials arranged on the substrate, the fluorescent X-ray absorption fine structure (XAFS) was measured by repeating the imaging during the monochromator scans across the absorption edge for metals. This is extremely efficient because XAFS spectra for all materials placed on the common substrate are obtained from only a single energy scan. One can determine the valence numbers, as well as other aspects of the chemical environment of the metal included in each material, from the differences in spectral features and the energy shifts. Hence, combinatorial libraries can be screened very rapidly, and therefore efficiently, using the X-ray imaging system.     

Transmission X-ray microscopy using X-ray magnetic circular dichroism

X-ray magnetic circular dichroism (X-MCD) was used as a large, element-specific and quantitative magnetic contrast mechanism in the soft X-ray microscopes at BESSY I (Berlin) and the ALS (Berkeley). The present state and potential of magnetic transmission X-ray microscopy (MTXM) is outlined. The possibility to record images in varying magnetic fields and the high spatial resolution down to 25 nm were used to image out-of-plane magnetized (4 ?Fe / 4 ?Gd)×75 systems. Magnetic domains could be studied in arrays of circular and square dots with lateral dimensions down to 180 nm. Hysteresis loops of individual dots were deduced using the direct proportionality of the X-MCD contrast to the sample magnetization. Images of a 3 nmCr / 50 nmFe / 6 nmCr film demonstrate for the first time that MTXM is also able to observe in-plane magnetized domains. In the future the possible applications of MTXM will be extended with regard to the strength of the external field, the available energy range and the sample conditions by building a dedicated transmission X-ray microscope for magnetic imaging at BESSY II. Received: 22 May 2001 / Accepted: 4 July 2001 / Published online: 5 October 2001     

Adsorption model determination of N2O/Ag(1 1 0) by theoretical studies of near-edge X-ray absorption fine structure

The nitrogen 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of the N₂O adsorbed on Ag(1 1 0) have been studied by the multiple-scattering cluster (MSC) and self-consistent field (SCF) DV-Xα methods. Two adsorption models, in which the N₂O molecule attached to the Ag substrate through the central nitrogen (N_C) atom and the terminal nitrogen (N_T) atom, respectively, have been checked up thoroughly. The MSC calculation and the R-factor analysis show that the N₂O molecule is attached to the Ag substrate through the terminal nitrogen atom with the adsorption height h = 3.4 ± 0.1 Å. In the overlayer the N₂O molecules arrange themselves into a tilted chain due to the interaction between the cations and the anions in the molecules. The physical cause of the resonances in the NEXAFS spectra mentioned above has been discussed by the DV-Xα method, which confirms the MSC calculations.     

Spin reorientation transition in Fe/CeH2 multilayers probed by soft X-ray resonant magnetic scattering

The magnetic domain configurations of Fe 3d spins in Fe/CeH₂ multilayers were measured by soft X-ray resonant magnetic scattering. The interface region could be probed by setting up X-ray standing waves due to the multilayer periodicity. By resolving first- and second-order magnetic scattering contributions, we show that the latter probe directly the magneto-crystalline anisotropy which is dominated by the Fe interface layers causing a spin reorientation transition when the temperature is lowered. Received: 30 May 2001 / Accepted: 4 July 2001 / Published online: 5 October 2001     

Electronic structure of CeAl2 thin films studied by X-ray absorption spectroscopy

We report X-ray absorption near edge structures (XANES) study of CeAl₂ thin films of various thicknesses, 40-120 nm, at Al K- and Ce L₃-edges. The threshold of the absorption features at the Al K-edge shifts to the higher photon energy side as film thickness decreases, implying a decreased in Al p-orbital charges. On the other hand, from Ce L₃-edge spectra, we observed a decrease in the 5d4f occupancy as the surface-to-bulk ratio increases. The valence of Ce in these thin films, as revealed by the Ce L₃-edge spectral results, is mainly trivalent. From a more detailed analysis we found a small amount of Ce⁴⁺ contribution, which increases with decreasing film thickness. Our results indicate that the surface-to-bulk ratio is the key factor which affects the electronic structure of CeAl₂ thin films. The above observations also suggest that charge transfer from Al to Ce is associated with the decrease of the film thickness.     

Difference between chemical structures of the interface at the Al-oxide tunneling barrier prepared by plasma or by radical oxidation

We have studied chemical structures of the interface between the Al-oxide tunneling barrier and the underlying Co₉₀Fe₁₀ layer in magnetic tunnel junctions when a 1-nm thick metallic Al barrier was oxidized by two different methods: plasma oxidation and radical oxidation. Our chemical analyses confirmed that the underlying CoFe layer was unavoidably attacked by oxygen during the oxidation and that this left different oxide states at the AlO_x/CoFe interface, depending on the oxidation method. The radical oxidation required long oxidation time for optimizing tunneling performance and resulted in a large amount of oxygen at the interface, which, in turn, resulted in the formation of mostly α-Fe₂O₃ and Al₂O₃. Conversely, the plasma oxidation required a relatively short oxidation time for optimization and left FeO as a dominant phase at the interface. Our results also show that the thermal treatment helped AlO_x, an oxygen-deficient phase, to be re-oxidized and transformed into Al₂O₃, the thermodynamically stable stoichiometric phase. The oxygen that diffused from the reduced CoFe layer into the barrier is likely responsible for this oxygen enrichment. We show that such differences in the chemical structure of the interface are critical clues to understanding what causes the change in tunneling properties of magnetic tunnel junctions.     

Co/C and W/Si multilayers deposited by ion-beam sputtering for the soft X-ray range

We deposited Co/C multilayer mirrors for a wavelength of 4.77 nm and W/Si multilayer mirrors for a wavelength of 1.77 nm by use of ion-beam sputtering. The small-angle diffraction spectrum was used to analyze the structure of the multilayers. With a combination of the experimental diffraction spectra and Apeles’ theory for calculation of the interfacial roughnesses of the multilayers, the interfacial roughnesses of Co/C and W/Si are 0.80 nm and 0.60 nm, respectively, which are lower than that of the substrate. The reflectivity of the Co/C multilayer is measured to be about 20% and that of the W/Si multilayer about 1% at the grazing incidence angle of about 12°. Received: 30 May 2000 / Accepted: 1 August 2000 / Published online: 11 February 2002     

Structure and dynamics of clean and adsorbate-covered crystal surfaces studied by surface X-ray diffraction

Received: 24 March 1998/Accepted: 21 August 1998     

O2 plasma oxidation effect on magnetic properties of spin valves

The use of nano-oxide to improve the performance of spin valves has been extensively studied. But most of the investigations so far have been carried out on different samples. This may make some of the conclusions drawn from the experiments inconsistent because of the fluctuation in deposition conditions and device structures. In this work, the effect of nano-oxide on the properties of spin valves has been investigated through post-growth oxidation of the same sample in oxygen plasma for different rf powers and durations. The sample investigated was a bottom spin valve with the structure Si/SiO₂/Ta/NiFe/IrMn/CoFe/Cu/CoFe/Ta. A relative increase of 20% and 12% was obtained in the giant magnetoresistance (GMR) ratio of as-deposited and annealed samples, respectively. It was found that, at a fixed rf power, there is a peak of the GMR ratio as the oxidation time increases. A higher peak value of the GMR ratio was obtained for lower rf power, although the required oxidation time is longer. This result can be well understood by considering both the enhanced specularity at the insulator/metal interface and the loss of magnetic effective thickness of the free layer by the oxidation. Magnetic parameters such as the interlayer coupling field (H₀) and the coercivity of the free layer (H_cf) were also greatly influenced by the oxidation process. When only the Ta layer was oxidized, H₀ increases very slightly, and H_cf increases with the oxidation time. However, when the CoFe free layer was oxidized, a significant increase was found for H₀, and H_cf changes to decreasing. These results can be explained based on the Néel and RKKY coupling models. Received: 25 October 2001 / Accepted: 21 December 2001 / Published online: 3 June 2002     

Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) study of melt-spun Fe85Ga15 ribbons

The local structure in melt-spun Fe₈₅Ga₁₅ ribbons with a width ∼3 mm and thickness ∼60 μm produced in argon atmosphere was studied by analyzing EXAFS and XANES data. The following results were obtained: Ga–Ga bonds were not detected excluding the tendency to form clusters of Ga atoms; Ga substitutes Fe creating a local strain of about +1% on the first shell Fe–Ga bond, whereas on the second Fe–Ga shell strain quickly relaxes down to +0.3%; XANES spectra are compatible with a random substitution of Fe atoms by Ga atoms in the A2 structure. From the AFM investigation, we observed that at the surface (free side) of the ribbon the particles are elongated along the ribbon (∼2 μm×∼5 μm) and each particle is formed by small grains of average size of 200 nm.     

Sub-ps laser microstructuring of soft X-ray Mo/Si multilayer gratings

The sub-picosecond laser microstructuring of multilayer gratings is presented in this paper. A micromachining system operating with a 0.5 ps KrF laser at 248 nm was used to etch grating structures with a groove width of 1–2 μm in Mo/Si and Si/Mo multilayers. Atomic force microscopy, scanning electron microscopy and X-ray reflectivity were used to characterize the microetched patterns. The ω-scans around the 1st Bragg maximum show symmetric satellites up to 3rd order, with positions corresponding to the grating period. The use of sub-picosecond laser pulses minimizes the thermally affected zone and enhances the quality of the etched features. Short pulse laser processing is advantageous for the fabrication of high spatial resolution microstructures required in X-ray optics. Received: 21 May 2002 / Accepted: 19 August 2002 / Published online: 15 January 2003 RID="*" ID="*"Corresponding author. Email: dpapa@iesl.forth.gr     

Local coordination geometry around Cu and Cu ions in silicate glasses: an X-ray absorption near edge structure investigation

We present an X-ray absorption near edge structure (XANES) study on Cu⁺ and Cu²⁺ ions in silicate glasses at the Cu K-edge, aimed to determine the geometry of the local structure around the metal. This study is based on the comparison between experimental data and theoretical calculations made in the framework of multiple scattering theory. The XANES signals relative to several clusters are simulated on the basis of known crystalline structures involving Cu⁺ and Cu²⁺ ions in silicate matrices. Concerning the Cu²⁺ in glass, the simulations suggest the presence of a square coordination of oxygen atoms around the absorber, with a possible presence of metal ions in the second shell. As for the Cu⁺ ions, the metal clustering is excluded and a linear O-Cu-O coordination is evidenced. Received 30 April 1999     

X-ray absorption spectroscopic and magnetic characterization of cobalt-doped zinc oxide nanocrystals prepared by the molten-salt method

The local atomic arrangement and electronic structure of the Co-doped Zn_1−xCo_xO nanocrystal have been quantitatively examined along with its magnetic properties. According to our analysis using powder X-ray diffraction, electron microscopy, and Zn K-edge X-ray absorption spectroscopy (XAS), phase-pure wurzite-structured Zn_1−xCo_xO nanocrystals have been successfully synthesized via the molten-salt method. The Co K-edge XAS analysis clearly demonstrates that all the Co²⁺ ions are substituted for the tetrahedral Zn sites of the Wurzite structure with a coordination number of 3.9 and a bond distance of 1.97 Å, ruling out the presence of magnetic impurity phase and Co-metal cluster. Magnetization measurements reveal that the present Zn_1−xCo_xO sample does not show any ferromagnetic transition down to 2 K. In this regard, we can conclude that Co-doped zinc oxide is not ferromagnetic but the previously reported ferromagnetism in this phase would be an extrinsic property.     

Anisotropy of the optical and magneto-optical response of Au/Co/Au/Cu multilayers grown on vicinal Si (111) surfaces

The optical and magneto-optical second harmonic reflectivity response of Au/Co/Au/Cu multilayers grown on vicinal Si (111) substrates has been studied. These azimuthal optical non-linear experiments check the uniaxial character of the crystallinity of the Au buffer layer and the magnetic behavior of the ultrathin Co films in the metallic multilayer. They clearly show the strong dependence of the growth parameters and the misorientation of the vicinal surface on the SHG reflectivity signals. This uniaxial behavior is also correlated to linear MOKE experiments on the magnetic anisotropy with an easy magnetization axis parallel to the step edges. Received: 16 October 2001 / Published online: 29 May 2002     

Grazing-incidence X-ray diffraction from multilayers, taking into account diffuse scattering from rough interfaces

Received: 21 May 1997: Accepted 30 July 1997     

Phase transition and extended X-ray absorption fine structure of melt-spun amorphous Fe100−xYx alloys

The phase diagram and local structure of melt-spun amorphous (a-) Fe_100−xY_x (22?x?62) alloys were investigated using AC and DC magnetic and extended X-ray absorption fine structure (EXAFS) measurements. The a-Fe–Y system shows reentrant spin glass (RSG) behavior for 42?x?58 and spin glass (SG) behavior for 60?x. Two SG transition temperatures, T_g and T_f, were obtained in the RSG state. The T_g, T_f and Curie temperature T_C decrease with increasing x, and the T_C and T_g vanish at x=60. A new magnetic phase diagram for the melt-spun a-Fe_100−xY_x alloys was obtained from magnetic measurements for higher Y concentration. The magnetic states of the a-Fe_100−xY_x alloys change remarkably around x=60 and an EXAFS study revealed that the average atomic distance between nearest-neighboring Fe atoms changes at approximately x=60.     

Local probing of the surface chemical bond using X-ray emission spectroscopy

2 and CO on Ni(100), benzene on Ni(100) and Cu(110), and glycine adsorbed on Cu(110). New types of molecular states are observed which are directly related to the surface chemical bond. The long-accepted Blyholder model which is based on a frontier orbital concept cannot explain our results for N₂ and CO chemisorption. We find it necessary to offer a new picture where changes in the whole molecular orbital framework have to be considered. We show that both π and σ type interactions are important in describing the bonding in benzene to metal surfaces. The future prospect is illustrated by the adsorption of the simplest amino acid, glycine, on Cu(110). The adsorbate has four different atomic centers where X-ray emission spectra are obtained, providing a unique view of the local electronic structure. Accepted: 6 March 1997     

Synchrotron X-ray diffraction and absorption studies of CeM2X2 (M=Cu, Ni and X=Si, Ge) at high pressure

The equations of state of CeCu₂Si₂ and CeCu₂Ge₂ to about 60 GPa, as well as that of CeNi₂Ge₂ to 22 GPa and the valence state of Ce in CeCu₂Ge₂ to 20 GPa have been studied at room temperature in a diamond-anvil cell using synchrotron radiation sources. In each compound, the ambient-pressure phase (tetragonal ThCr₂Si₂-type structure) persisted to the highest pressure studied. The unit cell volumes of CeNi₂Ge₂ at ∼5 GPa and CeCu₂Ge₂ at ∼7 GPa, respectively, approached that of CeCu₂Si₂ taken at ambient pressure. From the equation-of-state data, the bulk modulus was derived to be 112.0±5.1 GPa for CeCu₂Si₂, 125.6±4.3 GPa for CeCu₂Ge₂, and 178.4±14.3 GPa for CeNi₂Ge₂. The valence state of Ce in CeCu₂Ge₂ remained trivalent throughout the pressure range investigated.     

Extended X-ray absorption fine-structure (EXAFS) of a complex oxide structure: a full multiple scattering analysis of the Au L3-edge EXAFS of Au2O3

Crystalline Au₂O₃ was obtained by hydrothermal synthesis at 3000 atm and its extended X-ray absorption fine-structure (EXAFS) at the Au L₃-edge was measured at room temperature. A detailed full multiple scattering (MS) analysis using FEFF8 theory shows that only a small number of scattering paths contribute significantly to the EXAFS of Au₂O₃. Because of the complex unit cell (low local symmetry) of the Au₂O₃ structure, contributions of MS paths are almost negligible. The results indicate that FEFF8 theory provides a good reference for the analysis of Au-O phases.     

Magnetic interface polarization of the La-5d states in Fe/LaHx multilayers

For rare-earth (RE)-hydrides (REHx), a metal-to-insulator transition is observed if the hydrogen concentration is increased from the dihydride (x=2) towards the trihydride (x=3). This transition provides an object for studies of the magnetic interface polarization in layered ferromagnet/insulator structures. For different samples with a fixed Fe and varied LaH_x sublayer thickness t_LaHx ([15 ? Fe/t? LaH_x]xn), the H concentration x in the LaH_x sublayer is gradually increased in the experiment. Starting from the as prepared dihydride REH_2-δ, the modification of the magnetic polarization of the La-5d states at the Fe/La_x interface is studied across the transition by magnetic circular dichroism measurements at the La-L₂ and L₃ edges. The experiments reveal an induced magnetic polarization of the La-5d hole states on a length scale of 9 ? that is independent of the altered electronic structure of the La-5d states. Received: 23 May 2001 / Accepted: 4 July 2001 / Published online: 5 October 2001