Publication

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

Sébastien Reynaud
2022
Thèse EPFL
Résumé

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 4f4f occupancy from 4fnf^n to 4fn14f^{n-1} 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 4f4f 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.

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