Extended X-ray absorption fine structure

Extended X-ray absorption fine structure (EXAFS), along with X-ray absorption near edge structure (XANES), is a subset of X-ray absorption spectroscopy (XAS). Like other absorption spectroscopies, XAS techniques follow Beer's law. The X-ray absorption coefficient of a material as a function of energy is obtained using X-rays of a narrow energy resolution are directed at a sample and the incident and transmitted x-ray intensity is recorded as the incident x-ray energy is incremented. When the incident x-ray energy matches the binding energy of an electron of an atom within the sample, the number of x-rays absorbed by the sample increases dramatically, causing a drop in the transmitted x-ray intensity. This results in an absorption edge. Every element has a set of unique absorption edges corresponding to different binding energies of its electrons, giving XAS element selectivity. XAS spectra are most often collected at synchrotrons because of the high intensity of synchrotron X-ray so

Magnetism and metal-organic self-assembly of rare-earth atoms on decoupling layers

Sébastien Reynaud

This thesis presents investigations of magnetic and structural properties of two dimensional metal-organic frameworks and of single atoms, both adsorbed on decoupling layers grown on metal surfaces, with focus on rare earth elements.We first report on a series of attempts at realizing self-assembled metal-organic networks on different decoupling layers, probed by scanning tunneling microscopy. The aim is to produce regular structures with high surface filling factors such that the magnetic properties of the rare earth atoms in the metal-organic networks can be investigated by X-ray ensemble measurements. The combinations of three molecular ligands (QDC, BDA, ZnTPyP) on three insulating layers (MgO, NaCl, graphene) with Tb as rare earth are reported. Of the three decoupling layers, only graphene is found to allow the synthesis of metal-organic structures. We successfully synthesized large islands of a rare earth-QDC coordination complex, with a majority of fivefold coordination of the rare earth atoms. The same structure is reproduced with Dy and Er.X-ray absorption spectroscopy, X-ray magnetic circular and linear dichroism measurements are then carried out on the Dy- and Er-QDC/gr/Ir(111) networks. Compared to single atoms on gr/Ir(111), both Dy and Er change their

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and change their easy axis of magnetization. Both species are paramagnetic when incorporated into the metal-organic structure. The last part of the thesis is devoted to the study of Dy, Ho, and Gd on NaCl thin films. All three atoms display

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occupancy of the gas phase. The top-Cl adsorption site is determined with scanning tunneling microscopy. The magnetic properties are probed with X-ray absorption spectroscopy, X-ray magnetic circular and linear dichroism. Ho and Gd are paramagnetic. Dy has out-of-plane anisotropy with open hysteresis at non zero magnetic field. However, thermally assisted quantum tunneling of the magnetization prevents remanence at zero field.

EPFL2022

Long Spin Lifetime in Rare-Earth Single-Atom Magnets at Surfaces

Boris Sorokin

Further miniaturisation of magnetic storage devices requires an advent of new types of magnets, since classical ferromagnetic materials show lack of remanence at nano- and subnanoscale. A single atom can represent the smallest possible bit of information. Even though the isolated single atoms are paramagnetic, the interaction of surface adsorbed atoms with a substrate can result in high magnetic anisotropy energy and long magnetisation lifetime. In this thesis the magnetic properties of surface supported rare-earth single atoms are investigated with X-ray absorption spectroscopy, X-ray magnetic circular dichroism and multiplet simulations. The first goal of the project was to find new adatom/substrate combinations that exhibit a long adatom magnetic lifetime, possibly extending the current limits of the atomic magnetic moment stability to higher temperatures and longer spin relaxation times. The second objective was to implement the external electric field control of the adatom magnetic properties.Firstly, we present the experimental and theoretical research on Dy and Ho single atoms deposited on BaO. A comparison of our results with similar studies sheds light on the impact of the substrate crystal field, in particular Dy-O bond covalency, on the magnetic stability of the rare-earth adatoms. Next, the detailed experimental investigation of Dy single atoms on ZnO is presented. This adatom/substrate pair is used as first attempt to implement the electric field control of the adatom magnetic properties. Lastly, we study the Dy adatoms on graphene layers grown on various metals. The vibrational modes of the metallic substrates are shown to strongly affect the Dy spin lifetime, while addition of a second graphene layer does not allow to significantly improve the adatom magnetic stability.

EPFL2022

Synchrotron Light Techniques for the Investigation of Advanced Nuclear Reactor Structural Materials

Didier Gavillet, Wolfgang Hoffelner, Manuel Alexandre Pouchon

In the frame of the Generation IV initiative, different structural material candidates are investigated at the Paul Scherrer Institute. These are oxide dispersion strengthened (ODS) steels, intermetallic materials and ceramic composite materials. The response of the material to different potential loads (irradiation, temperature …) is addressed in a multi-scale approach, both, modelling wise and also experimentally. The investigation of each scale delivers at least a qualitative understanding of possibly evolving damage in the material and also delivers a validation of the corresponding scale on the modelling side. From the experimental side, the lower end of the scale, the atomistic and structural level, can be investigated by conventional techniques, as for example transmission electron microscopy (TEM) and X-ray diffraction (XRD). However, the use of synchrotron radiation techniques offers an ideal, complementary way to investigate the material structure and other properties. This paper presents applications in the field of the ODS research, where the structural behaviour of the nanoscopic dispersoids can selectively be investigated, although only being present with roughly 5 wt % in the matrix. A study showing the structural behaviour of these oxide particles as a function of irradiation illustrates the potential of the extended X-ray absorption fine structure (EXAFS) technique. Using X-ray magnetic circular dichroism (XMCD), which is a difference-signal of two X-ray absorption spectra recorded for positive and negative helicities of the beam, the magnetic structure and some magnetic parameters, can be resolved. An example shows, how this can be applied to understand (Fe,Cr) systems, which is the base alloy of the investigated ODS steel. The results deliver an important crosscheck for modelling. Beside the presentation of these techniques, this paper shows how beamline techniques can serve nuclear research, with possibly activated materials. At the Paul Scherrer Institute, a sample holder for highly active materials has been developed, and has already served for EXAFS measurements at the Swiss Light Source (SLS). The set-up of this sample holder is briefly presented here.

Nuclear Energy Agency, Organisation for Economic Co-operation and Development2007

Magnetism and metal-organic self-assembly of rare-earth atoms on decoupling layers

Sébastien Reynaud

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occupancy from 4

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EPFL2022