Role of Intermolecular Interactions in the Catalytic Reaction of Formic Acid on Cu(111).

Formic acid (HCOOH) can be catalytically decomposed into H2 and CO2 and is a promising hydrogen storage material. As H2 production catalysts, Cu surfaces allow selective HCOOH decarboxylation; however, the on-surface HCOOH decomposition reaction pathway remains controversial. In this study, the temperature dependence of the HCOOH/Cu(111) adsorption structures is elucidated by scanning tunneling microscopy and non-contact atomic force microscopy, establishing the adsorbate chemical species using density functional theory. 2D HCOOH islands at 80 K, linear chains of HCOOH and monodentate formate at 150 K, chain-like assemblies of monodentate and bidentate formate at 200 K, and bidentate formate clusters at 300 K are observed. At each temperature, the adsorbates experience attractive interactions among themselves. Such aggregation stabilizes them against desorption and decomposition. Thus, accurate evaluation of intermolecular interactions is essential to understand catalytic reactivity.

Role of tip apices in scanning force spectroscopy on alkali halides at room temperature-chemical nature of the tip apex and atomic-scale deformations.

We have revealed processes of the tip apex distortion in the measurements of non-contact scanning force microscopy. High-spatial-resolution two-dimensional force mapping on KCl(100) surfaces for a large number of tips, seven tips, enabled us to see the complex behavior of the tip apex distortion. The tips are from Si without additional coating, but are altered by the tip-sample interaction and show the behavior of different atomic species. On the KCl(001) surfaces, the tip apex, consisting of K and Cl atoms or of Si, distorted several times while changing the distance even in a weak attractive region. There are variations in rigidity of the tip apex, but all tips distorted in the small attractive region. This complex behavior was categorized in patterns by our analyses. We compare the experimental force-distance data to atomistic simulations using rigid KCl-terminated tips and KCl-terminated tips with an additional KCl-pair designed to perform atomic jumps. We also compare the experimental force-distance data to first principles simulations using Si tips. We mainly find K-terminated tips and Si-terminated tips. We find that Si tips show only one force minimum whereas KCl-terminated tips show two force minima in line with the stronger rigidity of Si compared to KCl. At room temperature, the tip apex atoms can perform atomic jumps that change the atomic configuration of the tip apex.

Chemical Identification of the Foremost Tip Atom in Atomic Force Microscopy.

Chemical identification of individual surface atoms has been achieved by measuring the chemical bonds between tip and surface atoms using atomic force microscopy. On the other hand, the discrimination of chemical species at the tip apex is still a challenging task, even though the differences of the species have significant effects on atomic-scale contrast and atom manipulation. Here, we perform the chemical identification of a foremost tip atom using bond energies measured on precharacterized atomic species on a Si surface. We find that chemically different tips show different trends in the chemical bond energy on the sites and that Pauling's equation for polar covalent bonds well describes those trends. On the basis of this knowledge, in situ chemical identification becomes possible. Using the chemically identified (here, Si and Al) tips, we determine the electronegativity of locally formed silicon oxide solely by experiments. Previously such determination was difficult without the help of theoretical calculations. These successful results confirm the validity and versatility of Pauling's equation for application to atomic-scale objects.

Manipulable Metal Catalyst for Nanographene Synthesis.

Performing bottom-up synthesis by using molecules adsorbed on a surface is an effective method to yield functional polycyclic aromatic hydrocarbons (PAHs) and nanocarbon materials. The intramolecular cyclodehydrogenation of hydrocarbons is a critical process in this synthesis; however, thus far, its elementary steps have not been elucidated thoroughly. In this study, we utilize the metal tip of a low-temperature noncontact atomic force microscope as a manipulable metal surface to locally activate dehydrogenation for PAH-forming cyclodehydrogenation. This method leads to the dissociation of a H atom of an intermediate to yield the cyclodehydrogenated product in a target-selective and reproducible manner. We demonstrate the metal-tip-catalyzed dehydrogenation for both benzenoid and nonbenzonoid PAHs, suggesting its universal applicability as a catalyst for nanographene synthesis.

Detection of Spin Transfer from Metal to Molecule by Magnetoresistance Measurement.

Localized electronic spin state in molecules has a relatively long spin lifetime and has thus attracted much attention. In this study, we characterize the magnetoresistance of a system comprising Pt and Fe(II)-phthalocyanine (FePc) molecules. The magnetoresistance measurement with the weak antilocalization analysis reveals that a magnetic moment in FePc acts as magnetic impurities for conduction electrons in Pt. Moreover, we find that the magnetoresistance involves a component that possesses the same symmetry as spin-Hall magnetoresistance. These results reveal the spin-angular momentum transfer from metallic Pt to a magnetic moment in FePc molecules, which can be used as a spin torque in a molecular system.

Synthesis, Structures, and Properties of Core-Expanded Azacoronene Analogue: A Twisted π-System with Two N-Doped Heptagons.

A core-expanded, pyrrole-fused azacoronene analogue containing two unusual N-doped heptagons was obtained from commercially available octafluoronaphthalene and 3,4-diethylpyrrole in two steps as a heteroatom-doped nonplanar nanographene. Full fusion with the formation of the tetraazadipleiadiene framework and the longitudinally twisted structure was unambiguously confirmed by single-crystal X-ray diffraction analysis. The edge-to-edge dihedral angle along the acene moiety was 63°. This electron-rich π-system showed four reversible oxidation peaks. Despite the nonplanar structure, the Hückel aromaticity owing to a peripheral π-conjugation in the dicationic state was concluded from the bond-length alternation and nucleus-independent chemical shift (NICS) and anisotropy of the induced current density (ACID) calculations.

Torque-Induced Change in Configuration of a Single NO Molecule on Cu(110).

We demonstrated that a nitric oxide (NO) molecule on Cu(110) acts as an "ON-OFF-ON toggle switch" that can be turned on and off by repulsive force and electron injection, respectively. On the surface, NO molecules exist in three configurations: flat along the [001] direction (ON), upright (OFF), and flat along [001[over ¯]] (ON). An NO-functionalized tip, which was characterized by scanning tunneling microscopy and inelastic electron tunneling spectroscopy, can convert an upright NO adsorbate into a flat-lying NO. Atomic force microscopy and a simulation of the interactions between the NO molecules reveal that a repulsive force not aligned with the N-O bond provides the torque that detrudes the NO toggle; i.e., the upright NO adsorbate is tilted away from the tip. Therefore, the NO adsorbate behaves as a nonvolatile sensor for the detection of locally applied repulsive torque.

Effects of Pb Intercalation on the Structural and Electronic Properties of Epitaxial Graphene on SiC.

The effects of Pb intercalation on the structural and electronic properties of epitaxial single-layer graphene grown on SiC(0001) substrate are investigated using scanning tunneling microscopy (STM), noncontact atomic force microscopy, Kelvin probe force microscopy (KPFM), X-ray photoelectron spectroscopy, and angle-resolved photoemission spectroscopy (ARPES) methods. The STM results show the formation of an ordered moiré superstructure pattern induced by Pb atom intercalation underneath the graphene layer. ARPES measurements reveal the presence of two additional linearly dispersing π-bands, providing evidence for the decoupling of the buffer layer from the underlying SiC substrate. Upon Pb intercalation, the Si 2p core level spectra show a signature for the existence of PbSi chemical bonds at the interface region, as manifested in a shift of 1.2 eV of the bulk SiC component toward lower binding energies. The Pb intercalation gives rise to hole-doping of graphene and results in a shift of the Dirac point energy by about 0.1 eV above the Fermi level, as revealed by the ARPES measurements. The KPFM experiments have shown that decoupling of the graphene layer by Pb intercalation is accompanied by a work function increase. The observed increase in the work function is attributed to the suppression of the electron transfer from the SiC substrate to the graphene layer. The Pb intercalated structure is found to be stable in ambient conditions and at high temperatures up to 1250 °C. These results demonstrate that the construction of a graphene-capped Pb/SiC system offers a possibility of tuning the graphene electronic properties and exploring intriguing physical properties such as superconductivity and spintronics.

Interplay between Switching Driven by the Tunneling Current and Atomic Force of a Bistable Four-Atom Si Quantum Dot.

We assemble bistable silicon quantum dots consisting of four buckled atoms (Si4-QD) using atom manipulation. We demonstrate two competing atom switching mechanisms, downward switching induced by tunneling current of scanning tunneling microscopy (STM) and opposite upward switching induced by atomic force of atomic force microscopy (AFM). Simultaneous application of competing current and force allows us to tune switching direction continuously. Assembly of the few-atom Si-QDs and controlling their states using versatile combined AFM/STM will contribute to further miniaturization of nanodevices.

Accurate Extraction of Electrostatic Force by a Voltage-Pulse Force Spectroscopy.

The classification of interaction forces between two approaching bodies is important in a wide range of research fields. Here, we propose a method to unambiguously extract the electrostatic force (F(ele)), which is one of the most significant forces. This method is based on the measurement of the energy dissipation under applied voltage pulse between an atomic force microscopy (AFM) tip and sample. It allowed us to obtain F(ele) as a function of the tip-sample distance and voltage including the distance-independent part, to which conventional AFM is insensitive. The obtained F(ele) curves nicely fit the analytical model, enabling estimation of the geometry of the tip. The distance-dependent contact potential difference could also be correctly obtained by the measured F(ele), opening an alternative route to quantitative Kelvin probe force microscopy.

Quantum degeneracy in atomic point contacts revealed by chemical force and conductance.

Quantum degeneracy is an important concept in quantum mechanics with large implications to many processes in condensed matter. Here, we show the consequences of electron energy level degeneracy on the conductance and the chemical force between two bodies at the atomic scale. We propose a novel way in which a scanning probe microscope can detect the presence of degenerate states in atomic-sized contacts even at room temperature. The tunneling conductance G and chemical binding force F between two bodies both tend to decay exponentially with distance in a certain distance range, usually maintaining direct proportionality G∝F. However, we show that a square relation G∝F2 arises as a consequence of quantum degeneracy between the interacting frontier states of the scanning tip and a surface atom. We demonstrate this phenomenon on the Si(111)-(7×7) surface reconstruction where the Si adatom possesses a strongly localized dangling-bond state at the Fermi level.

Chemical identification of individual surface atoms by atomic force microscopy.

Scanning probe microscopy is a versatile and powerful method that uses sharp tips to image, measure and manipulate matter at surfaces with atomic resolution. At cryogenic temperatures, scanning probe microscopy can even provide electron tunnelling spectra that serve as fingerprints of the vibrational properties of adsorbed molecules and of the electronic properties of magnetic impurity atoms, thereby allowing chemical identification. But in many instances, and particularly for insulating systems, determining the exact chemical composition of surfaces or nanostructures remains a considerable challenge. In principle, dynamic force microscopy should make it possible to overcome this problem: it can image insulator, semiconductor and metal surfaces with true atomic resolution, by detecting and precisely measuring the short-range forces that arise with the onset of chemical bonding between the tip and surface atoms and that depend sensitively on the chemical identity of the atoms involved. Here we report precise measurements of such short-range chemical forces, and show that their dependence on the force microscope tip used can be overcome through a normalization procedure. This allows us to use the chemical force measurements as the basis for atomic recognition, even at room temperature. We illustrate the performance of this approach by imaging the surface of a particularly challenging alloy system and successfully identifying the three constituent atomic species silicon, tin and lead, even though these exhibit very similar chemical properties and identical surface position preferences that render any discrimination attempt based on topographic measurements impossible.

Seeing how ice breaks the rule.

Basic defects in ice monolayers are seen using a microscope.

On-surface synthesis of hydroxy-functionalized graphene nanoribbons through deprotection of methylenedioxy groups.

We demonstrate on-surface deprotection of methylenedioxy groups which yielded graphene nanoribbons (GNRs) with edges functionalized by hydroxy groups. While anthracene trimer precursors functionalized with hydroxy groups did not yield GNRs, it was found that hydroxy groups are first protected as methylenedioxy groups and then deprotected during the cyclo-dehydrogenation process to form GNRs with hydroxy groups. The X-ray photoemission spectroscopy and non-contact atomic force microscopy studies revealed that ∼20% of the methylenedioxy turned into hydroxy groups, while the others were hydrogen-terminated. The first-principles density functional theory (DFT) study on the cyclo-dehydrogenation process was performed to investigate the deprotection mechanism, which indicates that hydrogen atoms emerging during the cyclo-dehydrogenation process trigger the deprotection of methylenedioxy groups. The scanning tunneling spectroscopy study and DFT revealed a significant charge transfer from hydroxy to the Au substrate, causing an interface dipole and the HOMO being closer to the Fermi level when compared with hydrogen-terminated GNR/Au(111). This result demonstrates on-surface deprotection and indicates a possible new route to obtain GNRs with desired edge functionalization, which can be a critical component for high-performance devices.

Mechanically induced single-molecule helicity switching of graphene-nanoribbon-fused helicene on Au(111).

Helicene is a functional material with chirality caused by its characteristic helical geometry. The inversion of its helicity by external stimuli is a challenging task in the advanced control of the molecular chirality. This study fabricated a novel helical molecule, specifically a pentahelicene-analogue twisted aromatic hydrocarbon fused with a graphene nanoribbon, via on-surface synthesis using multiple precursors. Noncontact atomic force microscopy imaging with high spatial resolution confirmed the helicity of the reaction products. The helicity was geometrically converted by pushing a CO-terminated tip into the twisted framework, which is the first demonstration of helicity switching at the single-molecule scale.

Quality control of on-surface-synthesised seven-atom wide armchair graphene nanoribbons.

On-surface synthesis is a powerful method for fabricating atomically precise graphene nanoribbons (GNRs), but the products always include defective structures. In this study, scanning tunnelling microscopy and atomic force microscopy were used to determine the length distribution of armchair-edge GNRs with a width of seven carbon atoms (7-AGNRs) synthesised on Au(111) and to characterise defective structures. The product quality was improved by increasing the precursor deposition amount because of a preference for intermolecular polymerisation over intramolecular cyclodehydrogenation at a high coverage. However, the annealing rate had a complex effect on the quality, with a low rate elongating 7-AGNRs but degenerating the length uniformity. These insights advance the understanding of the critical parameters for obtaining high-quality products in high yield by on-surface synthesis.

New insights on atomic-resolution frequency-modulation Kelvin-probe force-microscopy imaging of semiconductors.

We present dynamic force-microscopy experiments and first-principles simulations that contribute to clarify the origin of atomic-scale contrast in Kelvin-probe force-microscopy (KPFM) images of semiconductor surfaces. By combining KPFM and bias-spectroscopy imaging with force and bias-distance spectroscopy, we show a significant drop of the local contact potential difference (LCPD) that correlates with the development of the tip-surface interatomic forces over distinct atomic positions. We suggest that variations of this drop in the LCPD over the different atomic sites are responsible for the atomic contrast in both KPFM and bias-spectroscopy imaging. Our simulations point towards a relation of this drop in the LCPD to variations of the surface local electronic structure due to a charge polarization induced by the tip-surface interatomic interaction.

Ultrahigh-resolution imaging of water networks by atomic force microscopy.

Local defects in water layers growing on metal surfaces have a key influence on the wetting process at the surfaces; however, such minor structures are undetectable by macroscopic methods. Here, we demonstrate ultrahigh-resolution imaging of single water layers on a copper(110) surface by using non-contact atomic force microscopy (AFM) with molecular functionalized tips at 4.8 K. AFM with a probe tip terminated by carbon monoxide predominantly images oxygen atoms, whereas the contribution of hydrogen atoms is modest. Oxygen skeletons in the AFM images reveal that the water networks containing local defects and edges are composed of pentagonal and hexagonal rings. The results reinforce the applicability of AFM to characterize atomic structures of weakly bonded molecular assemblies.

Electronegativity determination of individual surface atoms by atomic force microscopy.

Electronegativity is a fundamental concept in chemistry. Despite its importance, the experimental determination has been limited only to ensemble-averaged techniques. Here, we report a methodology to evaluate the electronegativity of individual surface atoms by atomic force microscopy. By measuring bond energies on the surface atoms using different tips, we find characteristic linear relations between the bond energies of different chemical species. We show that the linear relation can be rationalized by Pauling's equation for polar covalent bonds. This opens the possibility to characterize the electronegativity of individual surface atoms. Moreover, we demonstrate that the method is sensitive to variation of the electronegativity of given atomic species on a surface due to different chemical environments. Our findings open up ways of analysing surface chemical reactivity at the atomic scale.

The local electronic properties of individual Pt atoms adsorbed on TiO2(110) studied by Kelvin probe force microscopy and first-principles simulations.

Noble metal nanostructures dispersed on metal oxide surfaces have applications in diverse areas such as catalysis, chemical sensing, and energy harvesting. Their reactivity, chemical selectivity, stability, and light absorption properties are controlled by the interactions at the metal/oxide interface. Single-atom metal adsorbates on the rutile TiO2(110)-(1 × 1) surface have become a paradigmatic model to characterize those interactions and to understand the unique electronic properties of these supported nanostructures. We combine Kelvin probe force microscopy (KPFM) experiments and density functional theory (DFT) calculations to investigate the atomic-scale variations in the contact potential difference of individual Pt atoms adsorbed on a hydroxylated (h) TiO2(110)-(1 × 1) surface. Our experiments show a significant drop in the local contact potential difference (LCPD) over Pt atoms with respect to the TiO2 surface, supporting the presence of an electron transfer from the Pt adsorbates to the substrate. We have identified two characteristic regimes by LCPD spectroscopy. At far tip-sample distances, LCPD values show a weak distance dependence and can be attributed to the intrinsic charge transfer from Pt to the oxide support. Beyond the onset of short-range chemical interactions, LCPD values exhibit a strong distance dependence that we ascribe to the local structural and charge rearrangements induced by the tip-sample interaction. These findings also apply to other electropositive adsorbates such as potassium and the hydrogen atoms forming the OH groups that are present on the h-TiO2(110) surface, promoting KPFM as a suitable tool for the understanding of electron transfer in catalytically active materials.