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

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 $4f$ occupancy from 4 $f^n$ to $4f^{n-1}$ 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 $4f$ 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.

Magnetic properties of surface-adsorbed single rare earth atoms, molecules, and atomic scale clusters

Aparajita Singha

This thesis presents combined experimental and theoretical investigations of nanoscale, surface-supported magnets based on rare earths (RE) to understand and control the magnetic properties down to the scale of single atoms. We present the effects of adatom-substrate interaction on the magnetic properties of isolated single RE atoms using x-ray absorption spectroscopy (XAS), x-ray magnetic circular dichroism (XMCD), and multiplet analysis. Our systematic investigations of Dy, Ho, Er, and Tm adatoms adsorbed on Pt(111), Cu(111), Ag(100), and Ag(111), reveal that the REs can possess two types of 4f occupations, namely divalent 4f^n and trivalent 4f^(n-1). The trivalent state is realized in presence of low promotion energy of the RE and strong hybridization of their external spd shell with the surrounding environment. Notably, none of the REs exhibit magnetic hysteresis, suggesting that magnetic relaxation is faster than about 10 seconds. We also report on the effect of adatom-adatom interaction by studying the size-dependent magnetic properties of Er clusters adsorbed on Cu(111). Combining XMCD, scanning tunneling microscopy (STM), and mean-field nucleation theory we reveal that the adatom-adatom interaction dominates over the adatom-substrate interaction in Er clusters starting from the size of three atoms. Consequently the easy axis of Er changes from in-plane for the single atoms and dimers to out-of-plane for trimers and bigger clusters. In addition, the out-of-plane magnetic anisotropy of 2.9 meV/atom results in magnetic hysteresis at 2.5 K in all clusters starting from trimers. With a magnetic lifetime of approximately 2 minutes at 0.1 T, the Er trimers are one of the smallest metal-supported ferromagnetic clusters observed so far. The investigation of adatom-adatom interaction is further extended by studying 4f-3d heterodimers namely, Ho-Co adsorbed on thin insulating layers of MgO. Their magnetic easy axis is oriented out-of-plane. Using spin-polarized STM we have detected spin-excitations in these heterodimers at ±20 and ±8 meV. We have identified the origin behind these spin-excitations using an effective spin Hamiltonian model, which indicates that, given a ferromagnetic exchange interaction between Ho and Co, the most intense feature at ±20 meV corresponds to a transition in which the spin moment of Co is strongly diminished. This is further accompanied by an overall change of the total magnetic moment of the heterodimer, i.e., ¿J=-1. In contrast, the weaker transition at ±8 meV occurs following a change in the out-of-plane moment of Ho while the total moment of the heterodimer remains intact i.e., ¿J=0. Notably, we observe an effective g factor of 3.1 for the ±20 meV transition, which significantly exceeds the free electron value of 2. In addition, the ferromagnetic coupling between Ho and Co is very unusual compared to the ferrimagnetic exchange interaction known for the bulk 4f-3d compounds, especially those derived from the late lanthanides. Nonetheless, this marks the first evidence of spin-excitations in the smallest 4f containing cluster. The knowledge gained on the fundamental aspects of magnetism in surface-supported REs combined with the continued parallel search for magnetic stability down to single atoms, enabled us to achieve magnetic remanence in single adatoms with lifetimes of the order of 1000 s at 2.5 K. In addition we have achieved significantly enhanced hysteresis and magnetic lifetime in TbPc2.

EPFL2017

Magnetism of individual adatoms and of epitaxial monolayers

Anne Lehnert

This thesis reports on the magnetism of low coordinated Fe and Co atoms in different chemical and electronic environments. The objective of this research was to contribute to the fundamental understanding of the magnetic properties, such as magneto-crystalline anisotropy energy (MAE), orbital and spin magnetic moment, of surface supported transition metal (TM) atoms and one atomic layer thick epitaxial TM films. A detailed knowledge on the interplay of electronic hybridization and magnetic properties is mandatory to elaborate new materials with high perpendicular magnetic anisotropy and acceptable writing field for future use in magnetic recording devices. The magnetic properties of the different experimental systems were investigated by x-ray absorption spectroscopy, x-ray magnetic circular dichroism, and magneto-optical Kerr effect (MOKE) and they were correlated to the morphology obtained by scanning tunneling microscopy (STM). The first part focuses on the effect of electronic hybridization between isolated 3d TM atoms and different kinds of substrates. First, we considered 4d and 5d TM substrates known for their high magnetic polarizability due to the close onset of ferromagnetism. Deposition of single Fe and Co atoms on Rh(111), Pd(111), and Pt(111) produces an increasing MAE going from Rh to Pd and finally to Pt that we directly correlate to the increasing spin-orbit constant of the substrate interlinking the induced magnetic moment and the MAE. Further we investigated single Fe and Co atoms on two different insulating layers, namely Al2O3/Ni3Al(111) and Cu2N/Cu(001), providing an efficient decoupling of the TM 3d states from the conduction electrons of the substrates. In case of the alumina film the absorption spectra of Fe and Co show a pronounced multiplet structure. On Cu2N the multiplet features of the adatoms are less defined due to the lower thickness of the screening layer. On both insulating layers we find a common out-of-plane easy axis, highly unquenched orbital moments, and giant MAE values of several meV/atom which are due to the formation of strong anisotropic bonds with the O and N atoms, respectively. The second part is dedicated to single atom thick layers of Fe and Co deposited on Pt(111) and Rh(111). We find the MAE to be strongly enhanced compared with bulk and we establish a direct proportionality between the induced magnetic moment of the topmost substrate layer and the MAE. The study of bimetallic Fe1-xCox alloys on platinum reveal a material with high MAE (0.5 meV at the equiatomic composition), large saturation magnetization (3μB to 2μB going from Fe to Co), and perpendicular magnetization easy axis. These characteristics hint at new possibilities for the further miniaturization of the grain size in recording devices. In the last part the theoretical description of the MOKE for ultra-thin films is extended to the transverse geometry and improved analytic formulae for the polar and longitudinal geometry are presented. This finding was used to optimize the Kerr signal for a new MOKE setup which is fully integrated in an ultrahigh vacuum chamber combining in situ MOKE and STM. The setup performance was demonstrated for a continuous film of 0.9 monolayers (ML) Co/Rh(111) with in-plane easy axis and for a superlattice of nanometric double layer Co islands on Au(11,12,12) with out-of-plane easy axis. The detection limit is 0.5 ML for transverse and 0.1 ML for polar Kerr geometry corresponding for island superlattices with the density of Co/Au(11,12,12) to islands composed of about 50 atoms. Moreover, the setup holds two independent ways to measure the MAE which is either by thermally induced magnetization reversal or by applying a torque onto the magnetization by turning the magnetic field. Both ways yield similar results for 1.1 ML Co/Au(11,12,12).

EPFL2009

Investigation and modification of the magnetism of epitaxial Fe structures

Diego Repetto

In this thesis, the magnetic and structural properties of layered epitaxial film systems and clusters are presented. A main achievement is the investigation of the direct correlation between magnetism and structural or morphological details of ultrathin films. For this purpose, the film structure has been accessed directly by means of surface science methods. The effect of structural changes on the magnetism were observed in-situ by magneto-optical techniques. First, epitaxial Fe films grown at low temperature (∼ 120K) on Cu(100) have been investigated. Such layers assume an fcc-crystal structure due to their interaction with the underlying Cu substrate. Within this work it is shown that the morphology of these films can be altered by annealing treatments. The thermally-induced morphological changes have direct consequences for domain wall propagation and result in increased coercivity and in modified surface anisotropy. Flat fcc-Fe layers on Cu(100) have been used as templates to form fcc-Fe/Cu/Fe trilayers with coupled perpendicular magnetization. Such systems might be of relevance for data storage applications. The perpendicular coupling is ascribed to the realignment of the magnetization of the bottom Fe layer within the stray field produced by the top Fe layer magnetization. The magnetic coupling has been investigated as a function of the thickness of the top and the bottom Fe layer as well as the Cu spacer thickness. It was found that the magneto-static interaction is a direct consequence of the fcc-structure of both Fe layers and the interface roughness. It is demonstrated that Fe films with fcc-structure and perpendicular magnetization can also be prepared on other fcc-templates, such as Pt substrates. Monatomic steps on the substrate surface are exploited to steer the growth of the film and with it the magnetism. Despite significant differences in the morphology and the atomic structure of Fe films on flat Pt(111) and stepped Pt(997), the critical thickness for the spin reorientation transition is similar on the two surfaces. However, the local atomic arrangement above three monolayer film thickness determines in-plane easy magnetization axis parallel to the step edges. For all layered systems investigated in this thesis, epitaxial strain is a the driving force which influences the film structure and triggers structural transitions. The strain dependence of the morphology and the magnetism was probed by a comparative study of Fe deposited on Pt substrates with and without a noble gas buffer layer. The formation of relaxed Fe clusters during Xe layer desorption is favored in the absence of the overlayer-substrate interaction. Striking differences in the magnetic anisotropy between the systems are attributed to magneto-elastic contributions. Measurements of the blocking temperature of the Fe clusters allow estimating the cluster size. All samples have been investigated under ultra high vacuum conditions. The study of the sample magnetic properties study was done by in-situ magneto-optical Kerr effect measurements and Kerr microscopy. Structural characterization was done by low energy electron diffraction and, in collaboration with other scientists, by scanning tunnelling microscopy.

EPFL2006