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.

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 [Formula: see text] 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.

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 µeV 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 µeV 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.

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.

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.