ABSTRACT
In order to optimize the performance of devices based on porphyrin thin films it is of great importance to gain a physical understanding of the various factors which affect their charge transport and light-harvesting properties. In this work, we have employed a multi-technique approach to study vacuum deposited zinc octaethyl porphyrin (ZnOEP) thin films with different degrees of long-range order as model systems. An asymmetrical stretching of the skeletal carbon atoms of the porphyrin conformer has been observed and attributed to ordered molecular stacking and intermolecular interactions. For ordered films, a detailed fitting analysis of the X-ray absorption near edge structure (XANES) using the MXAN code establishes a symmetry reduction in the molecular conformer involving the skeletal carbon atoms of the porphyrin ring; this highlights the consequences of increased π-π stacking of ZnOEP molecules adopting the triclinic structure. The observed asymmetrical stretching of the π conjugation network of the porphyrin structure can have significant implications for charge transport and light harvesting, significantly influencing the performance of porphyrin based devices.
ABSTRACT
We report a detailed study of the K-edge X-ray absorption spectra of four transition metal phthalocyanines (MPc, M = Fe, Co, Cu and Zn). We identify the important single and multiple scattering contributions to the spectra in the extended energy range and provide a robust treatment of thermal damping; thus, a generally applicable model for the interpretation of X-ray absorption fine structure spectra is proposed. Consistent variations of bond lengths and Debye Waller factors are found as a function of atomic number of the metal ion, indicating a variation of the metal-ligand bond strength which correlates with the spatial arrangement and occupation of molecular orbitals. We also provide an interpretation of the near edge spectral features in the framework of a full potential real space multiple scattering approach and provide a connection to the local electronic structure.
ABSTRACT
We describe a soft x-ray appearance potential spectroscopy apparatus, which uses a windowless hyperpure Ge detector operated in the photon counting mode. Direct comparisons of recorded spectra with the self-convolution of x-ray absorption spectra and with ab initio simulations in the multiple scattering framework are reported and discussed.
ABSTRACT
A SrF(2) ultrathin barrier layer on Si(001) is used to form a sharp interface and block reactivity and intermixing between the semiconductor and a Yb(2)O(3) overlayer. Yb(2)O(3)/Si(001) and Yb(2)O(3)/SrF(2)/Si(001) interfaces grown in ultra high vacuum by molecular beam epitaxy are studied by photoemission and x-ray absorption fine structure. Without the fluoride interlayer, Yb(2)O(3)/Si(001) presents an interface reacted region formed by SiO(x) and/or silicate compounds, which is about 9 Å thick and increases up to 14-15 Å after annealing at 500-700 °C. A uniform single layer of SrF(2) molecules blocks intermixing and reduces the oxidized Si region to 2.4 Å after deposition and to 3.5 Å after annealing at 500 °C. In both cases we estimate a conduction band offset and a valence band offset of â¼ 1.7 eV and 2.4 eV between the oxide and Si, respectively. X-ray absorption fine structure measurements at the Yb L(III) edge suggest that the Yb oxide films exhibit a significant degree of static disorder with and without the fluoride barrier. Sr K edge measurements indicate that the ultrathin fluoride films are reacted, with the formation of bonds between Si and Sr; the Sr-Sr and Sr-F interatomic distances in the ultrathin fluoride barrier film are relaxed to the bulk value.
ABSTRACT
The bonding environment of oxygen implanted in GaN is studied using near edge X-ray absorption fine structure spectroscopy at the O-K-edge. The 70 keV oxygen ions form a 200 nm-thick subsurface layer that is highly defective or amorphous depending on the implantation fluence which ranges from 1 x 10(15) cm-2 to 1 x 10(17) cm(-2). The information depth of the fluorescence photons varies from 50 to 63 nm, depending on the angle of incidence. The spectra are simulated using the FEFF8 code and assuming various models, e.g., O interstitial, O substitutional in N sites, Ga and N vacancies, and various polymorphs of Ga2O3. The lattice disorder is modelled by displacing atoms from their equilibrium positions by adding to their Cartesian coordinates random numbers that belong to normal distributions. The simulation results reveal that at the low fluence limit, the O atoms occupy interstitial sites preferentially in the empty channels aligned to the c-axis and in the atomic planes containing the Ga atoms. When the fluence is equal to 1 x 10(16) cm(-2) the O atoms substitute N while at 1 x 10(17) cm(-2) they form mixed GaO(x)N(y) phases with the N/O ratio decreasing with increasing depth, i.e., as we approach the peak of the implanted O profile.
ABSTRACT
In order to provide a structural basis for a physical understanding of exchange bias in metal/magnetic-oxide interfaces, we have determined the structure of the Fe/NiO(001) interface by means of x-ray absorption spectroscopy and ab initio density functional theory calculations. A Fe-Ni alloyed phase on top of an interfacial FeO planar layer is formed. The FeO layer exhibits a 7% expanded interlayer distance and a 0.3 A buckling; its presence is predicted to increase the spin magnetic moment of the interface Fe atoms by 0.6 mu(B), compared to the ideally abrupt interface.
ABSTRACT
Garnets in lower crustal mafic and ultramafic rocks usually contain rare-earth elements (REE) in trace concentrations. Direct characterization of REE at trace levels in natural garnets is not available in the literature because of the difficulty of obtaining structural information by means of conventional diffraction methods. Here, the characterization of Nd at trace levels (176-1029 p.p.m.) in a set of natural garnets performed by means of Nd K-edge X-ray absorption near-edge structure spectroscopy is presented, showing the capability of high-energy XANES for REE in trace structural determinations.
ABSTRACT
The experimental apparatus for anomalous wide-angle X-ray scattering (AWAXS) on the GILDA beamline at the ESRF is described. The main features are the high beam stability and reproducibility which allow anomalous scattering effects to be resolved also on dilute elements, the large spectral range which allows AWAXS experiments at the K edges of heavy elements, and the use of a high-efficiency detection system. The apparatus has been tested in extreme conditions by performing AWAXS experiments at the Eu K edge in Eu-doped Sr metaphosphate glasses.
ABSTRACT
The performance of a dynamical sagittal-focusing monochromator for hard X-rays is described. It consists of a flat first crystal and a diamond-shaped ribbed second crystal which is clamped by its central rib and dynamically bent by applying a force on its two apices. The system has proved to perform very well on the GILDA beamline at the ESRF. The horizontal acceptance varies with energy and with focusing geometry as predicted theoretically; the total available horizontal fan of radiation (3.6 mrad) is in fact collected in the 1:3 geometry. The system is routinely run in a dynamical focusing mode for XAFS spectroscopy in the energy range 5-30 keV with Si(311) crystals, with a constant spot size FWHM ~1 mm on the sample and without degradation of energy resolution or reproducibility. Using simple geometrical considerations we calculate the variations of the horizontal profile of the reflected beam during rocking-curve scans in different focusing geometries and find them in agreement with observed ones. Not only is this is a practical aid in alignment but it illustrates the X-ray optics of sagittal focusing in an elegant way.
