Epitaxial growth and structure of cobalt ferrite thin films with large inversion parameter on Ag(001).

Cobalt ferrite ultrathin films with the inverse spinel structure are among the best candidates for spin filtering at room temperature. High-quality epitaxial CoFe2O4 films about 4 nm thick have been fabricated on Ag(001) following a three-step method: an ultrathin metallic CoFe2 alloy was first grown in coherent epitaxy on the substrate and then treated twice with O2, first at room temperature and then during annealing. The epitaxial orientation and the surface, interface and film structure were resolved using a combination of low-energy electron diffraction, scanning tunnelling microscopy, Auger electron spectroscopy and in situ grazing-incidence X-ray diffraction. A slight tetragonal distortion was observed, which should drive the easy magnetization axis in-plane due to the large magneto-elastic coupling of such a material. The so-called inversion parameter, i.e. the Co fraction occupying octahedral sites in the ferrite spinel structure, is a key element for its spin-dependent electronic gap. It was obtained through in situ resonant X-ray diffraction measurements collected at both the Co and Fe K edges. The data analysis was performed using FDMNES, an ab initio program already extensively used to simulate X-ray absorption spectroscopy, and shows that the Co ions are predominantly located on octahedral sites with an inversion parameter of 0.88 (5). Ex situ X-ray photoelectron spectroscopy gives an estimation in accordance with the values obtained through diffraction analysis.

Simulation of Surface Resonant X-ray Diffraction.

We present an ab initio numerical tool to simulate surface resonant X-ray diffraction experiments. The crystal truncation rods and the spectra around a given X-ray absorption edge are calculated at any position of the reciprocal space. Density functional theory is used to determine the resonant scattering factor of an atom within its local environment and to calculate the diffraction peak intensities for surfaces covered with a thin film or with one or several adsorbed layers. Besides the sample geometry, the collected data also depend on several parameters, such as beam polarization and incidence and exit angles. In order to account for these factors, a numerical diffractometer mimicking the experimental operation modes has been created. Finally two case studies are presented in order to compare our simulations with experimental spectra: (i) a magnetite thin film deposited on a silver substrate and (ii) an electrochemical interface consisting of bromine atoms adsorbed on copper.

Growth mechanisms of Pd nanofilms electrodeposited onto Au(111): an in situ grazing incidence X-ray diffraction study.

Electrochemical deposition of ultra-thin Pd films onto Au(111) single crystals in a solution containing chloride was studied with in situ surface X-ray diffraction measurements. We report a detailed description of the growth mode, as well as film morphology and lattice parameters as a function of thickness, from 2 up to 10 monolayers (ML) as equivalent thickness. An almost ideal layer-by-layer pseudomorphic growth is observed up to two deposited ML. For higher thicknesses, it is followed by the growth of large 3D Pd bulk-like islands. They are about 20 ± 5 ML high and ∼220 Å in diameter for the Pd4ML film and occupy only about 20% of the surface. Their height increases faster than their size with the Pd deposited amount. We could clearly show that chlorides do not play any role in inhibiting the three-dimensional growth of Pd/Au(111) films. We could also unequivocally correlate the features observed by electrochemical surface characterisation in an acidic medium with the detailed structure obtained by diffraction.

Strain driven monoclinic distortion of ultrathin CoO films in the exchange-coupled CoO/FePt/Pt(0 0 1) system.

The structure and strain of ultrathin CoO films grown on a Pt(0 0 1) substrate and on a ferromagnetic FePt pseudomorphic layer on Pt(0 0 1) have been determined with in situ and real time surface x-ray diffraction. The films grow epitaxially on both surfaces with an in-plane hexagonal pattern that yields a pseudo-cubic CoO(1 1 1) surface. A refined x-ray diffraction analysis reveals a slight monoclinic distortion at RT induced by the anisotropic stress at the interface. The tetragonal contribution to the distortion results in a ratio [Formula: see text], opposite to that found in the low temperature bulk CoO phase. This distortion leads to a stable Co(2+) spin configuration within the plane of the film.

Evidence of the substrate effect in hydrogen electroinsertion into palladium atomic layers by means of in situ surface X-ray diffraction.

In this work, we report an in situ surface X-ray diffraction study of the hydrogen electroinsertion in a two-monolayer equivalent palladium electrodeposit on Pt(111). The role of chloride in the deposition solution in favoring layer-by-layer film growth is evidenced. Three Pd layers are necessary to describe the deposit structure correctly, but the third-layer occupancy is quite low, equal to about 0.22. As a major result, resistance to hydriding of the two atomic Pd layers closest to the Pt interface is observed, which is linked to a strong effect of the Pt(111) substrate. As a consequence, we observe the lowering of the total hydride stoichiometry compared to bulk Pd. Our measurements also reveal good reversibility of the deposit structure, at least toward one hydrogen insertion-desorption cycle.