Visualization of Alternating Triangular Domains of Charge Density Waves in 2H-NbSe_{2} by Scanning Tunneling Microscopy.

The charge density wave (CDW) state of 2H-NbSe_{2} features commensurate domains separated by domain boundaries accompanied by phase slips known as discommensurations. We have unambiguously visualized the structure of CDW domains using a displacement-field measurement algorithm on a scanning tunneling microscopy image. Each CDW domain is delimited by three vertices and three edges of discommensurations and is designated by a triplet of integers whose sum identifies the types of commensurate structure. The observed structure is consistent with the alternating triangular tiling pattern predicted by a phenomenological Landau theory. The domain shape is affected by crystal defects and also by topological defects in the CDW phase factor. Our results provide a foundation for a complete understanding of the CDW state and its relation to the superconducting state.

Head-to-Tail Oligomerization by Silylene-Tethered Sonogashira Coupling on Ag(111).

On-surface synthesis is a powerful method for the fabrication of π-conjugated nanomaterials. Herein, we demonstrate chemoselective Sonogashira coupling between (trimethylsilyl)ethynyl and chlorophenyl groups in silylethynyl- and chloro-substituted partially fluorinated phenylene ethynylenes (SiCPFPEs) on Ag(111). The desilylative Sonogashira coupling occurred with high chemoselectivity up to 75 %, while the competing Ullmann and desilylative Glaser homocoupling reactions were suppressed. A combination of bond-resolved scanning tunneling microscopy/atomic force microscopy (STM/AFM) and DFT calculations revealed that the oligomers were obtained by the formation of intermolecular silylene tethers (-Me2 Si-) through CH3 -Si bond activation at 130 °C and subsequent elimination of the tethers at an elevated temperature of 200 °C.

Emergence of metallic surface states and negative differential conductance in thinß-FeSi2films on Si(001).

The electronic properties of the surface ofß-FeSi2have been debated for a long. We studied the surface states ofß-FeSi2films grown on Si(001) substrates using scanning tunnelling microscopy (STM) and spectroscopy (STS), with the aid of density functional theory calculations. STM simulations using the surface model proposed by Romanyuket al(2014Phys. Rev.B90155305) reproduce the detailed features of experimental STM images. The result of STS showed metallic surface states in accordance with theoretical predictions. The Fermi level was pinned by a surface state that appeared in the bulk band gap of theß-FeSi2film, irrespective of the polarity of the substrate. We also observed negative differential conductance at ∼0.45 eV above the Fermi level in STS measurements performed at 4.5 K, reflecting the presence of an energy gap in the unoccupied surface states ofß-FeSi2.

Graphene growth on a Pt(111) substrate by surface segregation and precipitation.

We report on the fabrication of a sizable graphene sheet on a carbon-doped Pt(111) substrate through surface segregation and precipitation. Scanning Auger electron spectroscopy (AES) reveals that the graphene covered more than 98% of the substrate surface. Our graphene consists of single-layer graphene across the substrate with fractions of several micrometer wide bi- and tri-layer graphene islands. We also show that the number of graphene layers can be precisely determined by analyzing AES data. While Raman spectroscopy is usually used to study graphene on SiO2, we show that AES is a powerful tool to characterize graphene grown on metal substrates.

Manipulation of Spin Polarization in Boron-Substituted Graphene Nanoribbons.

The design of magnetic topological states due to spin polarization in an extended π carbon system has great potential in spintronics application. Although magnetic zigzag edges in graphene nanoribbons (GNRs) have been investigated earlier, real-space observation and manipulation of spin polarization in a heteroatom substituted system remains challenging. Here, we investigate a zero-bias peak at a boron site embedded at the center of an armchair-type GNR on a AuSiX/Au(111) surface with a combination of low-temperature scanning tunneling microscopy/spectroscopy and density functional theory calculations. After the tip-induced removal of a Si atom connected to two adjacent boron atoms, a clear Kondo resonance peak appeared and was further split by an applied magnetic field of 12 T. This magnetic state can be relayed along the longitudinal axis of the GNR by sequential removal of Si atoms.

Silicon adatom switching and manipulation on Si(111)-7 x 7.

We report on a multiple-state switching behavior in the tip height or tunneling current of scanning tunneling microscopy on the Si(111)-7 x 7 surface. This switching is caused by displacement of silicon adatoms under the influence of energetic tunneling electrons. When the tip is fixed over a center adatom, five well-defined levels appear in the measured tip height and tunneling current. These levels are attributed to different electronic structures, depending on the configuration of the center adatoms in the unit cell. We also demonstrate manipulations of the center adatoms by controlling the sample bias.

Active nanocharacterization of nanofunctional materials by scanning tunneling microscopy.

Recent developments in the application of scanning tunneling microscopy (STM) to nanofabrication and nanocharacterization are reviewed. The main focus of this paper is to outline techniques for depositing and manipulating nanometer-scale structures using STM tips. Firstly, the transfer of STM tip material through the application of voltage pulses is introduced. The highly reproducible fabrication of metallic silver nanodots and nanowires is discussed. The mechanism is thought to be spontaneous point-contact formation caused by field-enhanced diffusion to the apex of the tip. Transfer through the application of z-direction pulses is also introduced. Sub-nanometer displacement pulses along the z-direction form point contacts that can be used for reproducible nanodot deposition. Next, the discovery of the STM structural manipulation of surface phases is discussed. It has been demonstrated that superstructures on Si(001) surfaces can be reverse-manipulated by controlling the injected carriers. Finally, the fabrication of an atomic-scale one-dimensional quantum confinement system by single-atom deposition using a controlled point contact is presented. Because of its combined nanofabrication and nanocharacterization capabilities, STM is a powerful tool for exploring the nanotechnology and nanoscience fields.

Importance of bulk states for the electronic structure of semiconductor surfaces: implications for finite slabs.

We investigate the influence of slab thickness on the electronic structure of the Si(1 0 0)- p([Formula: see text]) surface in density functional theory (DFT) calculations, considering both density of states and band structure. Our calculations, with slab thicknesses of up to 78 atomic layers, reveal that the slab thickness profoundly affects the surface band structure, particularly the dangling bond states of the silicon dimers near the Fermi level. We find that, to precisely reproduce the surface bands, the slab thickness needs to be large enough to completely converge the bulk bands in the slab. In the case of the Si(1 0 0) surface, the dispersion features of the surface bands, such as the band shape and width, converge when the slab thickness is larger than 30 layers. Complete convergence of both the surface and bulk bands in the slab is only achieved when the slab thickness is greater than 60 layers.

Atomic species identification at the (101) anatase surface by simultaneous scanning tunnelling and atomic force microscopy.

Anatase is a pivotal material in devices for energy-harvesting applications and catalysis. Methods for the accurate characterization of this reducible oxide at the atomic scale are critical in the exploration of outstanding properties for technological developments. Here we combine atomic force microscopy (AFM) and scanning tunnelling microscopy (STM), supported by first-principles calculations, for the simultaneous imaging and unambiguous identification of atomic species at the (101) anatase surface. We demonstrate that dynamic AFM-STM operation allows atomic resolution imaging within the material's band gap. Based on key distinguishing features extracted from calculations and experiments, we identify candidates for the most common surface defects. Our results pave the way for the understanding of surface processes, like adsorption of metal dopants and photoactive molecules, that are fundamental for the catalytic and photovoltaic applications of anatase, and demonstrate the potential of dynamic AFM-STM for the characterization of wide band gap materials.

Ni nanocrystals on HOPG(0001): A scanning tunnelling microscope study.

The growth mode of small Ni clusters evaporated in UHV on HOPG has been investigated by scanning tunnelling microscopy. The size, the size distribution, and the shape of the clusters have been evaluated for different evaporation conditions and annealing temperatures. The total coverage of the surface strongly depends on the evaporation rate and time, whereas the influence of these parameters is low on the cluster size. Subsequent stepwise annealing has been performed. This results in a reduction of the total amount of the Ni clusters accompanied by a decreasing in the overall coverage of the surface. The diameter of the clusters appears to be less influenced by the annealing than is their height. Besides this, the cluster shape is strongly influenced, changing to a quasi-hexagonal geometry after the first annealing step, indicating single-crystal formation. Finally, a reproducible methodology for picking up individual clusters is reported [1].

Production of extended single-layer graphene.

Graphene has attracted an enormous amount of interest recently because of its unique electronic, optical, mechanical, and other properties. We report a promising method for producing single-layer graphene fully covering an entire substrate at low temperature. Single-layer graphene sheets have been synthesized on a whole 2 cm ×2 cm nickel (Ni) film deposited on a highly oriented pyrolytic graphite (HOPG) substrate by heating the Ni/HOPG in a vacuum. The carbon atoms forming our graphene are diffused from the graphite substrate through the nickel template. Our results demonstrate how to control the amount of carbon atoms for graphene formation to yield graphene films with a fine controlled thickness and crystal structure. Our method represents a significant step toward the scalable synthesis of high-quality graphene films with predefined thickness and toward realizing the unique properties of graphene films.

Phase Manipulation between c(4 x 2) and p(2 x 2) on the Si(100) surface at 4.2 K.

Phase manipulation between c(4x2) and p(2x2) on the Si(100) surface has been demonstrated at 4.2 K for the first time using a low-temperature scanning tunneling microscope. We have discovered that it is possible to change the c(4x2) surface into the p(2x2) surface, artificially, through a flip-flop motion of the buckling dimers by using a sample bias voltage control. Also, scanning at a negative bias voltage or applying a pulse voltage can restore the c(4x2) surface. The STM images as a function of bias voltage and tunneling current reveal the interesting dynamics of the buckling dimers on the long debated surface. Our results will show that energetic tunneling electrons are most likely responsible for the observed phase transition from c(4x2) to p(2x2).

Novel local density of state mapping technique for low-dimensional systems.

A novel local density of state (LDOS) probing method for low-dimensional electron systems is proposed. By applying a two-dimensional fast Fourier transform to a real-space image obtained by scanning tunneling microscopy (STM), visualization of a complementary image in k-space can be realized. Especially, low-dimensional Fermi contours can be extracted by applying the k-space imaging to real-space images containing sufficient LDOS information around the Fermi level. To realize a more enhanced LDOS visualization in both spaces, we have proposed the use of special materials for STM tips, which have relatively large LDOSs at the Fermi level. To demonstrate this idea, several kinds of STM tips (Ag, Au, W and Nb) with different types of LDOSs were developed. An Au(111)-(22 x square root(3)) reconstructed surface, where Shockley surface-state electrons form a nearly free electron gas, was selected as a test sample for the LDOS extraction. Visualization of standing waves in the surface LDOS modulated by herringbone reconstruction was attempted using the various types of STM tips. Significant effects of the LDOSs of the STM tips were clarified.