Photon emission from adsorbed C60 molecules with sub-nanometer lateral resolution

We present the first experimental demonstration of spatially resolved photon emission of individual molecules on a surface. A scanning tunneling microscope (STM) was used as a local electron source to excite photon emission from hexagonal arrays of C₆₀ molecules on Au(110) surfaces. Specifically, we show that in maps of photon emission intensities, C₆₀ fullerenes appear as arrays of individual light emitters 4 Å in diameter and separated by 10 Å. Comparison with simultaneously recorded STM images reveals, that most intense emission is detected when the STM tip is centered above a molecule. The results demonstrate the highest spatial resolution of light emission to date using a scanning probe technique.     

The structural and electronic properties of silicon nanoribbons on Ag(110): A first principles study

We have investigated the structures of silicon nanoribbons on Ag(110) using first principles calculations. The armchair silicon nanoribbons (ASiNRs) and zigzag silicon nanoribbons (ZSiNRs) with different widths are analyzed. The formation energy study shows that the ASiNRs with the width of 16 Å are the most stable structures. These ASiNRs have the structural parameters same as experimental ones. The simulated scanning tunneling microscope (STM) images of these ASiNRs also agree well with the experimental results. Thus, these ASiNRs are supposed to be the nanoribbons grown in experiment. The electronic structures shows that the ASiNRs are metallic, which is in agreement with the experiments.     

Barrier height imaging of Si(1 1 1)3 × 1-Ag reconstructed surfaces

We investigated the bias voltage polarity dependence of atomically resolved barrier height (BH) images on Si(1 1 1)3 × 1-Ag surfaces. The BH images were very similar to scanning tunneling microscopy (STM) images in both the empty and filled states. This similarity strongly supports the interpretation that the BH image reflects the vertical decay rate of the surface local density of states (LDOS). Differences in contrast and protrusion shapes between BH and STM images were observed. We attributed these differences to the geometric contribution to the STM image and to the improved spatial resolution of the BH image due to the lock-in technique.     

Atomic structure of the carbon induced Si(0 0 1)-c(4 × 4) surface

The atomic and electronic structures of the Si(0 0 1)-c(4 × 4) surface have been studied by scanning tunneling microscopy (STM) and density functional theory (DFT). To explain the experimental bias dependent STM observations, a modified mixed ad-dimer reconstruction model is introduced. The model involves three tilted Si dimers and a carbon atom incorporated into the third subsurface layer per c(4 × 4) unit cell. The calculated STM images show a close resemblance to the experimental ones.     

Hydrogen-induced metallization on Ge(1 1 1) c(2 × 8)

We have studied hydrogen adsorption on the Ge(1 1 1) c(2 × 8) surface using scanning tunneling microscopy (STM) and angle-resolved photoelectron spectroscopy (ARPES). We find that atomic hydrogen preferentially adsorbs on rest atom sites. The neighbouring adatoms appear higher in STM images, which clearly indicates a charge transfer from the rest atom states to the adatom states. The surface states near the Fermi-level have been followed by ARPES as function of H exposure. Initially, there is strong emission from the rest atom states but no emission at the Fermi-level which confirms the semiconducting character of the c(2 × 8) surface. With increasing H exposure a structure develops in the close vicinity of the Fermi-level. The energy position clearly indicates a metallic character of the H-adsorbed surface. Since the only change in the STM images is the increased brightness of the adatoms neighbouring a H-terminated rest atom, we identify the emission at the Fermi-level with these adatom states.     

Organic superconductors revisited

The surfaces of a ten years aged crystal and a freshly prepared κ-(BEDT-TTF)₂Cu(NCS)₂ crystal were compared by scanning tunneling microscopy (STM). The molecularly-resolved STM images of the bc plane of the crystals agree with each other and with the electronic contrast obtained by new density functional theory (DFT) based simulations. Even after ten years STM images of the molecular stacking of BEDT-TTF display a variation in brightness at the positions of different molecules. We attribute this symmetry breaking concerning the brightness in the STM images of the otherwise equivalent BEDT-TTF dimers to the electronic states of a relaxed surface.     

Adsorption structure of germanium on the Ru(0 0 0 1) surface

Coverage-dependent adsorption energy of the Ge/Ru(0 0 0 1) growth system and the geometrical distortions of the most stable adsorption structure are investigated through first-principles calculations within density functional theory. A local minimum in adsorption energy is found to be at a Ge coverage of 1/7 monolayer with a Ru(0 0 0 1)- symmetry. Based on this stale superstructure, the scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) images are simulated by means of surface local-density of states (LDOS). The results are consistent well with the STM measurements on the phase for Ge overlayer on Ru(0 0 0 1). From this stimulation, the relations between the STM images and the lattice distortion are also clarified.     

The effects of nonequilibrium charge distribution in scanning tunneling spectroscopy of semiconductors

Results are presented from a low-temperature scanning tunneling microscopy (STM) investigation of III-V semiconductor surfaces cleaved in situ along a (110) plane. The STM topographic images reveal the presence of surface charge structures. The possibility of their observation depends on the charge state of the apex of the STM tip. Peaks are also observed in the local tunneling conductivity spectra. The energy position of these peaks and the energy position of the edges of the band gap change with distance from the defect. A theoretical model is proposed which demonstrates that the experimental scanning tunneling spectroscopy (STS) data can be explained by effects due to a nonequilibrium electron distribution in the contact area, which gives rise to localized charges. In this model the on-site Coulomb repulsion of localized charges and their interaction with semiconductor electrons are treated self-consistently. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 4, 299–304 (25 August 1998)     

Quasi-one-dimensional structures on the Si(1 1 1) surface induced by Ba adsorption

Ba-induced quasi-one-dimensional reconstructions of the Si(1 1 1) surface have been investigated by low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). While the 3 × ‘2’ surface shows double-periodicity along the stripes in STM images consistent with half-order streaks observed in LEED patterns, no sign of the double-periodicity along the chain direction was detected for the 5 × 1 surface. The 5× stripes in STM images show internal structures with multiple rows. The two rows comprising the boundaries of a 5× stripe in the filled-state STM image are found to have 3a × √3/2 spacing across the stripe. The observation of the successive 3× and 2× spacings between the boundary rows supports a structural model proposed for the Ba-induced 5 × 1 Si reconstruction composed of honeycomb chains and Seiwatz chains. The highest coverage 2 × 8 surface does not reveal a quasi-1D row structure in STM images.     

Two-dimensional self-assembly of esters with different configurations at the liquid-solid interface

Self-assembled monolayers of hexadecyl palmitate (HP) and 3,3′-thiodipropionic acid di-n-octadecyl ester (TADE) physisorbed on highly oriented pyrolytic graphite (HOPG) are investigated using scanning tunneling microscope (STM) and computer simulation. Both molecules form alkane-like linear shapes to maximize the interactions with substrate when they adsorb on HOPG surface. The HP molecules self-assemble into lamellae with the chain-trough angle of 48°, which is the result of a shifting 3/2 units from the adjacent molecule in a lamella. Based on the simulation insights combined with STM images, we confirm that a perpendicular orientation appears in which the HP molecular backbone is rotated 90° with respect to the substrate such that the carbonyl points away from the HOPG surface. TADE molecules form three kinds of configurations with chain-trough angles of 90°, 72° and 60° by shifting 0, 1/2 and 1 units from their adjacent molecules, respectively. The bright stripes in STM images reveal the electron density distribution of the part between two ester groups. The energy differences of three TADE adsorption configurations by molecular mechanics (MM) simulation are used to explain the structural coexistence phenomenon. It is also shown that lattice match between alkyl chain of molecules and HOPG substrate could change molecular conformation upon self-assembly.     

Electron tunneling from a metallic TS2 layer underneath an ultra-thin MS layer with semiconducting properties for misfit-layer compounds

The effects of electron tunneling from the underlying TS₂ (H) layer on the scanning tunneling microscopy (STM) images of the uppermost MS (Q) layer have been studied for the misfit-layer compounds which are represented by the chemical formula {(MS)_1+x}_m{TS₂}_n. Systematic STM observations have been carried out under ultra-high vacuum (UHV) conditions for the 1Q/1H, 1.5Q/1H and 2Q/1H types of misfit-layer compounds. As Q layer thickness increases from about 6 to 12 Å while going from the 1Q/1H type to the 2Q/1H type, pseudo-tetragonal arrays of bright spots as expected from the atomic arrangement of a Q layer are observed more easily and more distinctly. It is found that tunneling electrons from the underlying H layer play an important role on the STM observations of the 1Q/1H and 1.5Q/1H types of compounds. Fast Fourier transform (FFT) analyses give clear evidences for electron tunneling from the underlying H layer and scattering by surface atoms of the uppermost Q layer and a mutual modulation structure peculiar to the compounds.     

Growth morphology of ultra-thin Ni films on Pd(1 0 0)

A series of thin Ni films, with thicknesses between 0.2 ML to 13 ML, were deposited on a Pd(1 0 0) substrate (a = 3.89 Å) at room temperature (RT). The growth morphology was investigated using scanning tunneling microscopy (STM). STM images indicate the existence of three different growth modes as a function of increasing coverage. Up to 6.5 ML, the films grow pseudomorphically, consistent with a face-centered tetragonal (fct) structure. From 6.5 ML to 10.5 ML a new apparent interlayer distance of 1.0 ± 0.1 Å is established. The new structure is accompanied by the appearance of an arrangement of filaments on the top layer surface. These filaments are presumably related to a strain relief mechanism of the fct films. Finally above 10.5 ML the Ni films recover the face-centered cubic (fcc) lattice constants. The filaments evolve, as a function of coverage, to form a net-like structure over the whole surface.     

Direct measurement of electron transport features in cytochrome c via V–I characteristics of STM currents

The morphology of and electron tunneling through single and cluster cytochrome c molecules deposited on self-assembled dodecanthiol monolayer film on a gold substrate have been studied experimentally using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy. STM images of a single cytochrome c molecule revealed a globular structure with a diameter of 4 nm and height of 1.5 nm. A spectroscopic study obtained by recording tunneling current–bias voltage (V–I) curves revealed that the STM current increases stepwise at asymmetric threshold sample bias voltages of +100 mV and –200 mV.     

Observation of coexistence of 1D and 2D nanostructures in cobalt dipyrromethene trimer complexes adsorbed on a graphite surface

We report the direct observation of 1D and 2D nanostructures of cobalt dipyrromethene trimer complexes adsorbed on a highly oriented pyrolytic graphite surface using scanning tunneling microscopy (STM). STM images showed two types of ordered structures coexisting on the surface: long 1D molecular chains isolated on the terraces, and 2D hexagonal patterns confined by a 1D chain and/or a graphite step edge. These 1D and 2D structures are attributed to ‘edge-on’ and ‘face-on’ complex alignments on the surface, respectively. In both configurations, substrate-mediated molecule-molecule interactions may play a significant role in stabilizing the nanostructures.     

Photoemission and scanning tunneling experiments with small particles on solid surfaces

The fascination of research with nanometersized objects in contact with a macroscopic surface will be illustrated by two examples: mass-selected supported transition-metal clusters and C₆₀ molecules on metallic single-crystal substrates. The preparation, mass-selection and deposition of the small particles will be described in some detail. The main experimental techniques involved in the characterization of their electronic and structural properties are photoelectron spectroscopy and scanning tunneling methods. For the transition-metal clusters the evolution of the valence band with cluster size reveals a trend to metal formation. When the tip of a Scanning Tunneling Microscope (STM) is placed above individual C₆₀ molecules intense light emission is observed. The diameter of this emission spot is approximately 4 Å. This observation indicates the possibility of an optical spectroscopic analysis on the scale of individual molecules.     

Scanning tunneling microscopy study of pinning-induced vortex lattice distortion in ion-irradiated NbSe2

We observe vortex pinning in 2.2 GeV Au-ion irradiated NbSe₂ by scanning tunneling microscopy (STM) at 3K. The ion irradiation generates columnar defects which act as pinning sites. At various external magnetic fields the vortex arrangement is clearly resolved but shows strong distortion. The location of individual defects is extracted from STM data and compared to the vortex arrangement.     

Time-resolved current response of a nanosecond laser pulse illuminated STM tip

Time-resolved dependence of the transient current through a ns laser pulse illuminated scanning tunneling microscope (STM) tip/sample gap in tunneling mode and out of tunneling range is presented. A self-designed fast STM-preamplifier (bandwidth 35 MHz) allows one to resolve the fine structure of the transient signal as well as the observation of some effects that are undetectable by using conventional low-band preamplifiers. The dependence of the threshold laser pulse intensity, which corresponds to the beginning of electron emission from tip (in non-tunneling mode), as a function of the tip/sample distance was investigated. At tip/sample distances from tunnel contact up to approximately 1 μm a linear dependence is found. This behavior is in good agreement with the theory for field enhancement in a STM tip/sample system. In tunneling mode a ns (fast component) as well as a μs (slow component) current response was found as a result of the laser pulse illumination. These data suggest the tip bending to be an important factor in clarifying the thermal/mechanical mechanism of laser-assisted surface nanomodification. Received: 4 May 1998 / Accepted: 29 January 1999 / Published online: 28 April 1999     

Ordered arrays of myoglobin adsorbed on the surfactant modified surface by scanning tunneling microscopy

Myoglobin molecules were deposited on a surfactant sodium dodecyl sulfate modified HOPG surface and imaged in air with a high resolution scanning tunneling microscope (STM) for the first time. STM images exhibit not only ordered arrays of the surfactant molecules but also regular two-dimensional arrays of myoglobin molecules. From STM images, the myoglobin molecule can be described as an ellipsoid-shaped pattern for the tertiary structure. In this study the dimensions of a myoglobin molecule were determined approximately as 43.0 × 36.2 × 8 ų, which are in good agreement with the known data from X-ray analysis, except for the height of a molecule which cannot be estimated from STM.     

Mismatch dislocations caused by preferential sputtering of a platinum-nickel alloy surface

Preferential sputtering and recoil mixing of a Pt₂₅Ni₇₅(111) single crystal surface leads to platinum enrichment in the upper monolayers, thereby increasing the lattice constant in these layers. This results in subsurface lattice mismatch dislocations, which have been studied by scanning tunneling microscopy. While the subsurface dislocations are only visible as shallow ditches in STM topographs, the Burgers vectors of the dislocation system can be determined by means of atomically resolved images of dislocations reaching the surface. A comparison with simulations of lattice relaxation using embedded-atom potentials shows good agreement with STM data and further allows the determination of the thickness of the Pt enrichment. We have estimated the Pt concentration in these layers from the dislocation density and studied the annealing behaviour of the surface.     

Model calculations of STM imaging and manipulation of oxygen on Pt(111)

We study tip-adsorbate–substrate interactions in scanning tunneling microscopy (STM) manipulation and imaging, and the influence of impurities on the images. Thence, we perform molecular dynamics simulations and calculate qualitative STM images for oxygen on Pt(1 1 1) surface. The adsorption site of the oxygen molecule is found to be in accordance with ab initio calculations. The calculated STM image has a good resemblance to the experimental ones. The contamination of the tip by oxygen or water alters the STM image strongly. Molecular dynamics simulations on manipulations of oxygen on the surface reveal several mechanisms of how molecular oxygen can be either produced or decomposed with STM tip. Finally, we find out that transfer of oxygen from the surface to an STM tip is not very probable.