X-ray absorption linear dichroism at the Ti K-edge of rutile (001) TiO2 single crystal

X-ray absorption linear dichroism of rutile TiO2 at the Ti K-edge provides information about the electronic states involved in the pre-edge transitions. Here, linear dichroism with high energy resolution is analyzed in combination with ab initio finite difference method calculations and spherical tensor analysis. It provides an assignment of the three pre-edge peaks beyond the octahedral crystal field splitting approximation and estimates the spatial extension of the corresponding final states. It is then discussed for the first time the X-ray absorption (XAS) of pentacoordinated titanium atoms due to oxygen vacancies and it is found that, similarly to anatase TiO2, rutile is expected to exhibit a transition on the low-energy side of peak A3. Its apparent absence in the experiment is related to the degree of p-d orbital mixing which is small in rutile due to its centrosymmetric point group. A recent XAS linear dichroism study on anatase TiO2 single crystals has shown that peak A2 has an intrinsic origin and is due to a quadrupolar transition to the 3d energy levels. In rutile, due to its centrosymmetric point group, the corresponding peak A2 has a small dipole moment explaining the weak transition. The results are confronted with recent picosecond X-ray absorption spectroscopy on rutile TiO(2 )nanoparticles.

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

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

X-ray absorption linear dichroism at the Ti K edge of anatase TiO2 single crystals

Camila Bacellar Cases Da Silveira, Oliviero Cannelli, Majed Chergui, Dominik Kinschel, Giulia Fulvia Mancini, Thomas Charles Henry Rossi, Jérémy Raymond Jean Maurice Rouxel

Anatase TiO2 (a-TiO2) exhibits a strong x-ray absorption linear dichroism in the pre-edge, the XANES and the EXAFS at the titanium K edge. In the pre-edge region, the behavior of the A1-A3 and B peaks originating from the 1s - 3d transitions is due to the strong p-orbital polarization and strong p - d orbital mixing. An unambiguous assignment of the pre-edge peak transitions is made in the monoelectronic approximation with the support of ab initio finite difference method calculations and spherical tensor analysis in quantitative agreement with the experiment. Our results suggest that several previous studies relying on octahedral crystal field splitting assignments are in accurate due to the significant p-d orbital hybridization induced by the broken inversion symmetry in a-TiO2. It is found that Al is mostly an on-site 3d - 4p hybridized transition, while peaks A3 and B are nonlocal transitions, with A3 being mostly dipolar and influenced by the 3d - 4p intersite hybridization, while B is due to interactions at longer range. Peak A2, which was previously assigned to a transition involving pentacoordinated titanium atoms, is shown to exhibit a quadrupolar angular evolution with incidence angle, which implies that its origin is primarily related to a transition to bulk energy levels of a-TiO2 and not to defects, in agreement with theoretical predictions [Vorwerk et al., Phys. Rev. B 95, 155121 (2017)]. Finally, ab initio calculations show that the occurence of an enhanced absorption at peak A2 in defect-rich a-TiO2 materials originates from defect-related p density of states due to the formation of doubly ionized oxygen vacancies. The formation of peak A2 at almost the same energy for single crystals and nanomaterials is a coincidence while the origin is different. These results pave the way to the use of the pre-edge peaks at the Ti K edge of a-TiO2 to characterize the electronic structure of related materials and in the field of ultrafast x-ray absorption spectroscopy where the linear dichroism can be used to compare the photophysics along different axes.

AMER PHYSICAL SOC2019