Shigeki Kawai

Atomically controlled substitutional boron-doping of graphene nanoribbons

Boron is a unique element in terms of electron deficiency and Lewis acidity. Incorporation of boron atoms into an aromatic carbon framework offers a wide variety of functionality. However, the intrinsic instability of organoboron compounds against moisture and oxygen has delayed the development. Here, we present boron-doped graphene nanoribbons (B-GNRs) of widths of N=7, 14 and 21 by on-surface chemical reactions with an employed organoboron precursor. The location of the boron dopant is well defined in the centre of the B-GNR, corresponding to 4.8 atom%, as programmed. The chemical reactivity of B-GNRs is probed by the adsorption of nitric oxide (NO), which is most effectively trapped by the boron sites, demonstrating the Lewis acid character. Structural properties and the chemical nature of the NO-reacted B-GNR are determined by a combination of scanning tunnelling microscopy, high-resolution atomic force microscopy with a CO tip, and density functional and classical computations.

Superlubricity of graphene nanoribbons on gold surfaces.

A golden opportunity for graphene Reducing friction can limit wear and improve the energy efficiency of mechanical devices. Graphene is a promising lubricant because the friction between sheets is minuscule under certain circumstances. Kawai et al. show that the same ultra-low frictional properties extend to other surfaces. They find ultralow friction when dragging graphene nanoribbons across a gold surface using an atomic force microscope. This discovery sets up the potential for developing nanographene frictionless coatings. Science, this issue p. 957 Experiments reveal ultralow friction when graphene nanoribbons slide across an oriented gold surface. The state of vanishing friction known as superlubricity has important applications for energy saving and increasing the lifetime of devices. Superlubricity, as detected with atomic force microscopy, appears when sliding large graphite flakes or gold nanoclusters across surfaces, for example. However, the origin of the behavior is poorly understood because of the lack of a controllable nanocontact. We demonstrated the superlubricity of graphene nanoribbons when sliding on gold with a joint experimental and computational approach. The atomically well-defined contact allows us to trace the origin of superlubricity, unraveling the role played by ribbon size and elasticity, as well as by surface reconstruction. Our results pave the way to the scale-up of superlubricity and thus to the realization of frictionless coatings.

Clean TiC(001) surface and oxygen chemisorption studied by work function measurement, angle-resolved X-RAY photoelectron spectroscopy, ultraviolet photoelectron spectroscopy and ion scattering spectroscopy

Abstract The clean surface of TiC(001) prepared by flash-heating at ~ 1500°C shows a 1 × 1 ordered atomic structure. No gradient of chemical composition exists over the shallow surface region of ~15 A. The work function of the clean surface is 3.8 ± 0.1 eV at room temperature. The features of oxygen chemisorption are similar to those of noble metals such as Ag and Cu; the average sticking probability is about two order of magnitude less than those of Ti and W metals, and the work-function change is also small. The oxygen atoms are preferentially chemisorbed on the carbon sites at the topmost layer, which is responsible for the small change in work function.

Towards atomic force microscopy up to 100 MHz

An atomic force microscope for nanocantilevers measuring from a few 100 nm to a few μm in length was implemented. The natural frequencies of the nanocantilevers lie in the range of 1 MHz to 1 GHz, and optical detection schemes adapted to their size and frequency range was selected. A helium neon laser with a beat frequency of 890 MHz was used as the laser source. The beat was shifted to 1090 MHz by an acousto-optical-modulator, and used as the carrier for heterodyne laser Doppler measurement. This enabled velocity measurement up to around 100 MHz. The probe beam of the Doppler interferometer was guided to the nanocantilever by a single mode polarization-maintaining optical fiber terminated by a collimating lens, a quarter wave plate, and a focusing lens. Reflected light was collected by the same optics and mixed with the reference beam. Self-excitation of the nanocantilever at its lowest natural frequency was implemented for an amplitude of 1 nmp-p at 36 MHz. The Q factor of the cantilever was 8000. Noise...

Probing atomic structure and Majorana wavefunctions in mono-atomic Fe chains on superconducting Pb surface

Motivated by the striking promise of quantum computation, Majorana bound states (MBSs) in solid-state systems have attracted wide attention in recent years. In particular, the wavefunction localization of MBSs is a key feature and crucial for their future implementation as qubits. Here, we investigate the spatial and electronic characteristics of topological superconducting chains of iron atoms on the surface of Pb(110) by combining scanning tunneling microscopy (STM) and atomic force microscopy (AFM). We demonstrate that the Fe chains are mono-atomic, structured in a linear fashion, and exhibit zero-bias conductance peaks at their ends which we interprete as signature for a Majorana bound state. Spatially resolved conductance maps of the atomic chains reveal that the MBSs are well localized at the chain ends (below 25 nm), with two localization lengths as predicted by theory. Our observation lends strong support to use MBSs in Fe chains as qubits for quantum computing devices.

Image Distortions of a Partially Fluorinated Hydrocarbon Molecule in Atomic Force Microscopy with Carbon Monoxide Terminated Tips

The underlying mechanisms of image distortions in atomic force microscopy (AFM) with CO-terminated tips are identified and studied in detail. AFM measurements of a partially fluorinated hydrocarbon molecule recorded with a CO-terminated tip are compared with state-of-the-art ab initio calculations. The hydrogenated and fluorinated carbon rings in the molecule appear different in size, which primarily originates from the different extents of their π-electrons. Further, tilting of the CO at the tip, induced by van der Waals forces, enlarges the apparent size of parts of the molecule by up to 50%. Moreover, the CO tilting in response to local Pauli repulsion causes a significant sharpening of the molecule bonds in AFM imaging.

An ultrasmall amplitude operation of dynamic force microscopy with second flexural mode

Selective detection of short-range interaction forces was carried out with the second flexural mode of a commercially available dynamic mode cantilever. A higher mode has a higher spring constant and a lower mechanical quality factor, which are suitable for the small amplitude operation in dynamic force microscopy. With 0.70A amplitude of the second flexural mode, atomically resolved constant frequency shift images of the Si(111)−7×7 reconstructed surface were obtained. The ultrasmall amplitude operation enabled imaging with high stability, due to the detection of the interaction force gradients at relatively long distances from the sample surface, and is an effective way to observe reactive surfaces while avoiding modifications and damaging of the tip and the sample.

Functionalized Truxenes: Adsorption and Diffusion of Single Molecules on the KBr(001) Surface

In this work, we have studied the adsorption and diffusion of large functionalized organic molecules on an insulating ionic surface at room temperature using a noncontact atomic force microscope (NC-AFM) and theoretical modeling. Custom designed syn-5,10,15-tris(4-cyanophenylmethyl)truxene molecules are adsorbed onto the nanoscale structured KBr(001) surface at low coverages and imaged with atomic and molecular resolution with the NC-AFM. The molecules are observed rapidly diffusing along the perfect monolayer step edges and immobilized at monolayer kink sites. Extensive atomistic simulations elucidate the mechanisms of adsorption and diffusion of the molecule on the different surface features. The results of this study suggest methods of controlling the diffusion of adsorbates on insulating and nanostructured surfaces.

Atomic-Scale Mechanical Properties of Orientated C60 Molecules Revealed by Noncontact Atomic Force Microscopy

In this work, the mechanical properties of C(60) molecules adsorbed on Cu(111) are measured by tuning-fork-based noncontact atomic force microscopy (nc-AFM) and spectroscopy at cryogenic conditions. Site-specific tip-sample force variations are detected above the buckyball structure. Moreover, high-resolution images obtained by nc-AFM show the chemical structure of this molecule and describes unambiguously its orientations on the surface.

Van der Waals interactions and the limits of isolated atom models at interfaces

Van der Waals forces are among the weakest, yet most decisive interactions governing condensation and aggregation processes and the phase behaviour of atomic and molecular matter. Understanding the resulting structural motifs and patterns has become increasingly important in studies of the nanoscale regime. Here we measure the paradigmatic van der Waals interactions represented by the noble gas atom pairs Ar–Xe, Kr–Xe and Xe–Xe with a Xe-functionalized tip of an atomic force microscope at low temperature. Individual rare gas atoms were fixed at node sites of a surface-confined two-dimensional metal–organic framework. We found that the magnitude of the measured force increased with the atomic radius, yet detailed simulation by density functional theory revealed that the adsorption induced charge redistribution strengthened the van der Waals forces by a factor of up to two, thus demonstrating the limits of a purely atomic description of the interaction in these representative systems.