Spectroscopic manifestations of the Kondo effect on single adatoms

The present topical review focuses on recent advances concerning an intriguing phenomenon in condensed matter physics, the scattering of conduction electrons at the localized spin of a magnetic impurity: the Kondo effect. Spectroscopic signatures of this effect have been observed in the past by high-resolution photoemission which, however, has the drawback of averaging over a typical surface area of 1 mm(2). By combining the atomic-scale spatial resolution of the scanning tunneling microscope (STM) with an energy resolution of a few tens of mu eV achievable nowadays in scanning tunneling spectroscopy (STS), and by exposing the magnetic adatom to external magnetic fields, our understanding of the interaction of a single magnetic impurity with the conduction electrons of the nonmagnetic host has been considerably deepened. New insight has emerged by taking advantage of quantum size effects in the metallic support and by decoupling the magnetic adatom from the supporting host metal, for instance by embedding it inside a molecule or by separating it by an ultrathin insulating film from the metal surface. In this way, Kondo resonances and Kondo temperatures can be tailored and manipulated by changing the local density of states of the environment. In the weak coupling limit between a Kondo impurity and a superconductor only a convolution of tip and sample DOS is observed while for strongly coupled systems midgap states appear, indicating superconducting pair breaking. Magnetic impurities with co-adsorbed hydrogen on metallic surfaces show pseudo-Kondo resonances owing to very low-energy vibrational excitations detected by inelastic tunneling spectroscopy. One of the most recent achievements in the field has been the clarification of the role of magnetic anisotropy in the Kondo effect for localized spin systems with a spin larger than S = 1/2.

Scanning tunneling spectroscopy at the single atom scale

Markus Ternes

This thesis reports measurements at the single atom scale by using low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS). Different sample systems where analyzed with normal conducting and superconducting tips. Chapter 2 presents the theoretical aspects which have to be taken into account for a detailed analysis and a consistent interpretation of the STS measurements. In chapter 3 the creation of a hexagonally ordered superlattice of single Ce adatoms on Ag(111) is reported and understood within a scattering model of the surface state electrons with the adatoms. Furthermore, the change in the local density of states of the surface state in ordered and slightly disordered superlattices is measured and theoretically explained within a tight-binding model which allows to understand the creation and stability of the superlattice by an energy gain of the participating surface-state electrons. Because Ce atoms have a non-vanishing magnetic moment which is expected to interact with the continuous states of the supporting surface leading to a Kondo resonance, chapter 4 presents measurements on single Ce adatoms on different Ag surfaces. This chapter shows the difficulties to interpret the obtained data. For instance, bistable Ce adatoms are detected on Ag(100) which show drastical changes in their apparent height and spectral signature depending on the tunneling conditions. The possible physical processes behind these phenomena are discussed. While the results presented in the first chapters were obtained with a normal conducting tip, chapter 5 intensively discusses the opportunities superconducting tips offer in low-temperature STS measurements. Novel insight in and thorough understanding of Andreev reflection processes are obtained by using the unique possibility of having different superconducting gaps in the tip and the sample. Detailed analyses of the supercurrent at low tunneling resistances reveal tunneling currents which are not described within the standard resistivity shunted junction model, and are presumably due to self-induced tunneling or due to an additional quasiparticle tunneling channel which only exist in asymmetric junctions. Furthermore, the influence of single magnetic Co atoms inbetween the superconducting tunnel junction on the obtained spectrum is discussed.

EPFL2006

The role of magnetic anisotropy in the Kondo effect

Harald Brune, Markus Ternes

In the Kondo effect, a localized magnetic moment is screened by forming a correlated electron system with the surrounding conduction electrons of a non-magnetic host1. Spin S D 1=2 Kondo systems have been investigated extensively in theory and experiments, but magnetic atoms often have a larger spin2. Larger spins are subject to the influence of magnetocrystalline anisotropy, which describes the dependence of the magnetic moment’s energy on the orientation of the spin relative to its surrounding atomic environment3,4. Here we demonstrate the decisive role of magnetic anisotropy in the physics of Kondo screening. A scanning tunnelling microscope is used to simultaneously determine the magnitude of the spin, the magnetic anisotropy and the Kondo properties of individual magnetic atoms on a surface. We find that a Kondo resonance emerges for large-spin atoms only when the magnetic anisotropy creates degenerate ground-state levels that are connected by the spin flip of a screening electron. The magnetic anisotropy also determines how the Kondo resonance evolves in a magnetic field: the resonance peak splits at rates that are strongly direction dependent. These rates are well described by the energies of the underlying unscreened spin states.

Nature Publishing Group2008

Magnetism of Single Adatoms and Small Adsorbed Clusters Investigated by Means of Low-Temperature STM

Quentin Dubout

This thesis works reports on the magnetic properties of single transition metal atoms and hydrogenated compounds adsorbed on crystal surfaces. It is an experimental study, based on scanning tunneling microscopy (STM), initiated by the project of demonstrating the existence of magnetic remanence for single adsorbed atoms (adatoms). All the measurements have been performed with a scanning tunneling microscope operating at 0.4 K and equipped with 8.5 T superconducting coils. The investigated systems are cobalt atoms, pure and hydrogenated (cobalt hydrides), adsorbed on Pt(111) and graphene on Pt(111) surfaces. In the first case, we have immediately been confronted to the presence of cobalt hydrides on the surface. Three types of hydrides (CoH, CoH2, and CoH3) have been identified, quite different from the clean adatoms, and readily distinguished by their tunnel spectrum (STS). Twoofthesehydridesdisplaylow-energyvibrationalmodes(1−30meV),identifiedbytheir absence of response to a magnetic field, the effect of an isotopic substitution, and by comparison with known systems. The three hydrides can be deprotonated applying a sufficient voltage between tip and sample. CoH2 on Pt(111) presents a Kondo resonance, due to a half-integer spin (S = 3/2) and a peculiar magnetic anisotropy. This system corresponds to the first demonstration of the appearance of the Kondo effect upon hydrogen adsorption. The results of several attempts to observe remanence for single cobalt adatoms on Pt(111) with spin-polarized scanning tunneling microscopy (SP-STM) are also presented and discussed. The second system differs from the first one in the presence of a graphene layer on the Pt surface. The first experimental determination of the magnetic moment and magnetic anisotropy of adatoms on graphene is reported in this thesis. A magnetic moment of (2.2 ± 0.4) μB was measured by spin-excitation spectroscopy (SES), as well as a hard magnetization axis with an anisotropy energy of 8.1 ± 0.4 meV. This value, comparable to the record value of single cobalt atoms on Pt(111), has been mainly attributed to the strong hybridization between cobalt and graphene. Ab initio calculations confirmed our observations. Graphene thus represents an extremely promising substrate for future applications in nanoscale magnetism and spintronics. This system also exhibits three different cobalt hydrides in addition to the clean atoms. Their respective chemical composition, CoH, CoH2, and CoH3, was determined by direct comparison between high resolution STM images and simulated images obtained from ab initio calculated atomic structures. A controlled deprotonation method is presented. CoH3 is the only hydride to display spin excitations. Its magnetic moment is comparable to that of clean cobalt, it presents a hard magnetization axis as well, however, its magnetic anisotropy energy is sensibly lower, 1.7 ± 0.05 meV. The other two hydrides display vibrational excitations only. The effect of hydrogen on the magnetic properties of metal adatoms is therefore very strong in this system as well, and must be taken into account in future studies, hydrogen being a very common contaminant in ultra-high vacuum set-ups. Finally, a detailed study of the structure graphene mono- and bilayers on Ru(0001) was realized. Two different stackings, AB and AA, have been identified for the bilayers, the last one not observed to date for this system. The moiré structure of monolayer graphene and of this last type of bilayer has been determined: (11.57×11.57)R4.3◦ and (10.54×10.54)R4.7◦, respectively. Moreover, C-C bond distortions of more than 10%, observed in the STM images, have been studied in detail. A quantitative comparison with ab initio calculations allowed to identify their origin as the tilt of the graphene π-orbitals. These distortions are therefore purely artificial. This is an important result for future scanning tunneling microscopy studies of graphene.