Atomically Resolved Chemical Reactivity of Small Fe Clusters

Small metal clusters have been investigated for decades due to their beneficial catalytic activity. It was found that edges are most reactive and the number of catalytic events increases with the cluster's size. However, a direct measurement of chemical reactivity of individual atoms within the clusters has not been reported yet. We combine the high-resolution capability of CO-terminated tips in scanning probe microscopy with their ability to probe chemical binding forces on single Fe atoms to study the chemical reactivity of atom-by-atom assembled Fe clusters from 1 to 15 atoms on the atomic scale. We find that the chemical reactivity of individual atoms within flat Fe clusters does not depend on the cluster size but on the coordination number of the investigated atom. Furthermore, we explain the atomic contrast of the investigated Fe clusters by relating the force spectra of individual atoms with atomic force microscopy images of the clusters

Response of the topological surface state to surface disorder in TlBiSe2_2

Through a combination of experimental techniques we show that the topmost layer of the topo- logical insulator TlBiSe$_2$ as prepared by cleavage is formed by irregularly shaped Tl islands at cryogenic temperatures and by mobile Tl atoms at room temperature. No trivial surface states are observed in photoemission at low temperatures, which suggests that these islands can not be re- garded as a clear surface termination. The topological surface state is, however, clearly resolved in photoemission experiments. This is interpreted as a direct evidence of its topological self-protection and shows the robust nature of the Dirac cone like surface state. Our results can also help explain the apparent mass acquisition in S-doped TlBiSe$_2$.Comment: 16 pages, 5 figure

Atom-by-Atom Assembly and Investigation of Small Fe Clusters with High-Resolution Atomic Force Microscopy

Small Fe clusters are important catalysts which are used in industry and nature. So far, their chemical reactivity was studied as a function of cluster size and mainly in the gas phase. However, a precise determination of their “active sites” – chemical most reactive locations within the clusters – was missing, so far. Within this thesis, the chemical reactivity of small Fe clusters is measured on the atomic scale by utilizing a combined scanning tunneling and atomic force microscope with CO-terminated tips operating at ultra-high vacuum and low temperature conditions. The first part of this work deals with the artificial creation of small Fe clusters in a controlled manner: First, the lateral manipulation of single Fe adatoms on the Cu(111) surface with monoatomic metal and CO-terminated tips is compared. Second, it is demonstrated that small Fe clusters can be assembled atom by atom using CO-terminated tips while the tip’s structure is preserved. Latter finding is specifically important as CO-terminated tips are quite flexible and relatively fragile. Using CO-terminated tips allows building up Fe clusters with atomic precision as they can also be used to image the Fe clusters in-between each enlargement step with atomic resolution. The second part of this thesis describes the interaction between the manually assembled Fe clusters and the CO-terminated tip. By approaching the CO-terminated tip towards the various Fe atoms of one cluster, it was found that the chemical interaction between a specific Fe cluster atom and the tip’s CO molecule decreases the bigger the coordination number of the Fe atom is. In this way, it was revealed that the Fe cluster corner atoms are most chemical reactive followed by the edge atoms. This finding is interpreted as a direct measurement of the chemical reactivity of small Fe clusters on the atomic scale

Lateral manipulation of single iron adatoms by means of combined atomic force and scanning tunneling microscopy using CO-terminated tips

CO-terminated tips currently provide the best spatial resolution obtainable in atomic force microscopy. Due to their chemical inertness, they allow us to probe interactions dominated by Pauli repulsion. The small size and inertness of the oxygen front atom yields unprecedented resolution of organic molecules, metal clusters, and surfaces. We study the capability of CO-terminated tips to laterally manipulate single iron adatoms on the Cu(111) surface with combined atomic force and scanning tunneling microscopy at 7 K. We find that even a slight asymmetry of the tip results in a distortion of the lateral force field. In addition, the influence of the tilt of the CO tip on the lateral force field is reversed compared to the use of a monoatomic metal tip which we can attribute to the inverted dipole moment of a CO tip with respect to a metal tip. Moreover, we demonstrate atom-by-atom assembly of iron clusters with CO tips while using the high-resolution capability of the CO tips in between to determine the arrangement of the individual iron atoms within the cluster. In all conducted experiments using CO tips within this study, the CO was never changed or lost from the tip's apex

Very weak bonds to artificial atoms formed by quantum corrals

We explored the bonding properties of the quantum corral (a circle of 48 iron atoms placed on a copper surface) reported by Crommie et al. in 1993, along with variants, as an artificial atom using an atomic force microscope (AFM). The original corral geometry confines 102 electrons to 28 discrete energy states, and we found that these states can form a bond to the front atom of the AFM with an energy of about 5 millielectron volts. The measured forces are about 1/1000 of typical forces in atomically resolved AFM. The confined electrons showed covalent attraction to metal tips and Pauli repulsion to CO-terminated tips. The repulsion at close distance was evident from the response of corral states created by deliberately placing single iron atoms inside the corral. The forces scaled appropriately with a 24-atom corral

Chemical bond formation showing a transition from physisorption to chemisorption

Surface molecules can transition from physisorption through weak van der Waals forces to a strongly bound chemisorption state by overcoming an energy barrier. We show that a carbon monoxide (CO) molecule adsorbed to the tip of an atomic force microscope enables a controlled observation of bond formation, including its potential transition from physisorption to chemisorption. During imaging of copper (Cu) and iron (Fe) adatoms on a Cu(111) surface, the CO was not chemically inert but transited through a physisorbed local energy minimum into a chemisorbed global minimum, and an energy barrier was seen for the Fe adatom. Density functional theory reveals that the transition occurs through a hybridization of the electronic states of the CO molecule mainly with s-, p(z)-, and d(z)(2)-type states of the Fe and Cu adatoms, leading to chemical bonding

Achieving μeV tunneling resolution in an in-operando scanning tunneling microscopy, atomic force microscopy, and magnetotransport system for quantum materials research

Research in new quantum materials requires multi-mode measurements spanning length scales, correlations of atomic-scale variables with a macroscopic function, and spectroscopic energy resolution obtainable only at millikelvin temperatures, typically in a dilution refrigerator. In this article, we describe a multi-mode instrument achieving a mu eV tunneling resolution with in-operando measurement capabilities of scanning tunneling microscopy, atomic force microscopy, and magnetotransport inside a dilution refrigerator operating at 10 mK. We describe the system in detail including a new scanning probe microscope module design and sample and tip transport systems, along with wiring, radio-frequency filtering, and electronics. Extensive benchmarking measurements were performed using superconductor-insulator-superconductor tunnel junctions, with Josephson tunneling as a noise metering detector. After extensive testing and optimization, we have achieved less than 8 mu eV instrument resolving capability for tunneling spectroscopy, which is 5-10 times better than previous instrument reports and comparable to the quantum and thermal limits set by the operating temperature at 10 mK

Edge channels of broken-symmetry quantum Hall states in graphene visualized by atomic force microscopy

The quantum Hall (QH) effect, a topologically non-trivial quantum phase, expanded the concept of topological order in physics bringing into focus the intimate relation between the “bulk” topology and the edge states. The QH effect in graphene is distinguished by its four-fold degenerate zero energy Landau level (zLL), where the symmetry is broken by electron interactions on top of lattice-scale potentials. However, the broken-symmetry edge states have eluded spatial measurements. In this article, we spatially map the quantum Hall broken-symmetry edge states comprising the graphene zLL at integer filling factors of ν=0,±1 across the quantum Hall edge boundary using high-resolution atomic force microscopy (AFM) and show a gapped ground state proceeding from the bulk through to the QH edge boundary. Measurements of the chemical potential resolve the energies of the four-fold degenerate zLL as a function of magnetic field and show the interplay of the moiré superlattice potential of the graphene/boron nitride system and spin/valley symmetry-breaking effects in large magnetic fields