Highly oriented pyrolitic graphite anomalous structures and fullerenes self-assembly

Scanning tunneling microscopy (STM) was used to look for unusual self-structures on highly oriented pyrolitic graphite (HOPG) that can mimic fullerenes assemblies. HOPG features that may be taken as C₆₀ molecular structures were found on this surface. The HOPG self-structures have been presented earlier as anomalies of the bare HOPG surface in the literature. The experimental results are in agreement with earlier STM reports on bare and modified HOPG.     

Imaging of ferroelectric vinylidene fluoride and trifluoroethylene copolymer films by scanning tunneling microscopy

In this paper, we reported the possibility to image non-conducting P(VDF-TrFE) copolymer films by STM. The films had the thickness of ∼25.0 nm and were spin-coated onto Au or graphite substrates. For films deposited on Au substrates, STM images showed grain structures of ∼100 nm, much larger than the grains of bare Au substrate. With increased scan rate, the film surface was damaged by STM tip and extreme protrusions and holes were observed. For films deposited on graphite substrates, we only obtained an image of very flat plane and could not observe the topography of the film surface. It seemed that the tip had pierced through the uppermost P(VDF-TrFE) layers and only imaged the layers nearest to the substrate. Asymmetrical current-voltage curves were observed from copolymer films deposited on HOPG. Experimental results were discussed.     

Formation of Gallium-induced nanostructures on single crystal HOPG surface

The room temperature growth of gallium atoms on the highly oriented pyrolytic graphite (HOPG) surface has been performed. The gallium atoms were deposited by thermal evaporation method in an ultra high vacuum system at a base pressure 5 × 10⁻¹⁰ torr. The X-ray photo electron spectroscopy (XPS) studies had been performed to confirm the presence of gallium atoms on HOPG surface. Scanning tunneling spectroscopy (STM) technique was employed to study the surface morphology of the clean HOPG surface and gallium covered HOPG surfaces which recognize the formation of gallium induced nanostructures. The deconvoluted XPS core level spectra of C (1s) and Ga (3d) demonstrate the possible interaction between substrate and the adsorbate atoms. The STM analysis revealed that the gallium deposition on HOPG led to significant change in the surface morphology. It was observed that the Ga atoms adsorbed as layer structure on HOPG surface for low coverage while quasi one-dimensional chain like nanostructure (1 ± 0.2 nm) has been formed for higher Ga coverage. The nanostructured surfaces induced by Ga deposition are found to be stable and could be used as a template for the growth of metallic nanostructures.     

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.     

二维磁结构的扫描隧道显微术研究

文章介绍了近年来利用扫描隧道显微术（STM）对表面和薄膜磁结构的研究进展。二维或表面磁结构可以通过在非磁性单晶上外延磁性单原子层薄膜形成，也可以在清洁的磁性单晶表面形成。利用磁性的STM针尖可以观测到原子分辨的表面磁结构。这将增进人们从纳米尺度对磁性的理解，并推动磁电子学的发展。     

BCx layers with honeycomb lattices on an NbB2(0001) surface

At elevated temperatures of 1000-1500 K, carbon (C) atoms that segregated to a surface and mixed with the boron (B) honeycomb lattice resulted in the formation of three different BC(x) layers as the topmost layers of NbB(2)(0001). Two of the layers were commensurate lattices: √7 × √7 and √3 × √3 structures; the third was incommensurate. The characteristic features of the √3 × √3 lattice with a honeycomb structure are discussed on the basis of the experimental data.     

Structural change of radiation defects in graphite crystals induced by STM probing

It was found that STM (scanning tunneling microscopy) images of defects in highly oriented pyrolytic graphite introduced by bombardment of 400 eV Ar⁺ ions in ultra-high vacuum exhibit substantial changes in the course of STM probing. Detailed examination of abrupt changes in the tunneling current measured at defect sites during voltage scans shows that the primary cause of the defect-image change was found to be neither the injected current nor the injected power but the absolute value of the voltage applied between the probe tip and the sample. We propose that an electric polarization induced force attracting the sample surface toward the probe tip widens the layer spacing of the graphite surface, leading to an acceleration of the lateral diffusion of interstitial atoms introduced by the ion irradiation, which results in a change in the defect structures and the accompanying electronic structures sensible in the STMimaging. Received: 14 June 2001 / Accepted: 7 September 2001 / Published online: 20 December 2001     

ATOMIC CHARGE SUPERPOSITION CALCULATIONS OF STM IMAGES OF 2D-ORDERED AMINO ACID ADSORBATES(Ⅱ)

In the preceding paper, we have successfully used the atomic charge superposition (ACS) method to calculate STM images of 2D-ordered structures of glycine molecules adsorbed on graphite (HOPG). In this work we focus on alanine/HOPG system. Firstly, we make a thorough searching for all of the possible 2D-ordered aggregation structures that can form linear chains or 2D nets of hydrogen bonds between the molecules and simultaneously satisfy the Van der Waal's radii of the condtituent atoms, just like in the case of 3D crystal of the molecules. Secondly, in order to interpret the experimental images, we use the ACS method to calculate STM images of the possible structures. It turns out that many of the experimental images can be interpreted satisfactorily with their calculated counterparts. This result further exhibits the great potential of using STM to study organic and biological molecules.     

STM/nc-AFM investigation of (n×6) reconstructed GaAs(0 0 1) surface

We have investigated the n×6 reconstructed GaAs(0 0 1) surface with scanning tunneling and non-contact atomic force microscopy techniques (STM/nc-AFM). For the first time atomically resolved nc-AFM images of that surface are shown. The images confirm the presence of rows of arsenic dimers in the topmost layer as predicted by the current model of n×6 reconstructed surface. However, in contrast to previous reports we found that postulated As dimer sites are not fully occupied. Moreover, the images suggest that ×6 symmetry is present on the surface even in absence of the dimers. We show that due to probing of different surface properties nc-AFM and STM are complementary tools for complex surfaces investigation.     

STM analysis of triosmium carbonyl cluster adsorption at HOPG

The study of metallic carbonyl clusters as precursors in tailoring the heterogeneous metal catalysts has been of great importance. The catalytic nature of the adsorbed clusters in thin film form depends on the chemical properties of the substrate used. The metal-support interaction will determine various properties such as the surface morphology, adsorption features and the structural orientations. We report a scanning tunneling microscopy (STM) study of an osmium carbonyl cluster (Os₃(CO)₁₁(NCCH₃)) adsorbed on highly oriented pyrolytic graphite (HOPG). STM measurements showed that the osmium carbonyl cluster interacts with HOPG in such a way that it adsorbs on the basal plane showing regular lattice structure, whereas the axial planes of the HOPG surface shows no ordered structure. The regular cluster lattice structure of the carbonyl cluster on the basal plane of the graphite has lattice parameters of a=1.4 nm and b=1.5 nm. We believe that the regular orientation of the cluster indicates a monolayer adsorption of the cluster on the graphite basal planes. Scanning tunneling spectroscopy (STS) measurements also indicated an insulating behavior for the cluster molecules on HOPG, with a significant energy gap value of ca. 300 mV. The cluster interaction at the active sites, i.e. axial planes of the graphite, was also observed by in situ STM measurements.     

Self-assembled monolayers of radical molecules physisorbed on HOPG(0 0 0 1) substrate studied by scanning tunnelling microscopy and electron paramagnetic resonance techniques

In this paper, we present a combined STM and EPR study on the adsorption and self-organization of monolayers formed from 2-(14-Carboxytetradecyl)-2-ethyl-4,4-dimethyl-3-oxazolidinyloxy (16DS) and 4′,4′-Dimethylspiro(5α-cholestane-3,2′-oxazolidin)-3′-yloxy (CSL) adsorbed on a highly oriented pyrolitic graphite HOPG(0 0 0 1) substrate. Both 16DS and CSL molecules are persistent free radicals containing a paramagnetic doxyl group. The STM measurements of 16DS on HOPG(0 0 0 1) were performed at the liquid-solid interface while the studies of CSL on HOPG(0 0 0 1) were carried out under ultrahigh vacuum conditions. It was found that the 16DS molecules on the HOPG(0 0 0 1) surface form a highly-ordered monolayer with a domain structure. The high-resolution STM images show structural details of 16DS molecules on HOPG(0 0 0 1) revealing the paramagnetic doxyl group. In contrast, CSL molecules on HOPG(0 0 0 1) form a well-ordered monolayer without domain structure. The EPR results indicate that both compounds deposited on HOPG(0 0 0 1) substrate are not reduced and retain their paramagnetic character. We believe that the molecular systems described can be used in single spin detection experiments using an electron spin noise-scanning tunnelling microscopy (ESN-STM) technique. In particular, the possibility of obtaining contrast spin signals from the paramagnetic and diamagnetic parts of molecules increases the significance of our results.     

Unambiguous interpretation of atomically resolved force microscopy images of an insulator

The (111) surface of CaF2 was imaged with dynamic mode scanning force microscopy and modeled using atomistic simulation. Both experiment and theory showed a clear triangular contrast pattern in images, and theory demonstrated that the contrast pattern is due to the interaction of a positive electrostatic potential tip with fluorine ions in the two topmost surface layers. We find a good agreement of position and relative height of scan line features between theory and experiment and thus establish for the first time an unambiguous identification of sublattices of an insulator imaged by force microscopy.     

Contrast reversal and shape changes of atomic adsorbates measured with scanning tunneling microscopy

Systematic, quantitative comparisons between scanning tunneling microscopy (STM) experiments and first principles simulations of O(2 x 2)/Ru(0001) have been performed. The shape of the atomic adsorbates in the images depends strongly on the tunneling resistance and changes reversibly from circular (high resistance) to triangular (low resistance). In addition, after adsorption of oxygen on the STM tip we observe a contrast reversal on the surface, confirmed by extensive numerical simulations.     

Room and high-temperature scanning tunnelling microscopy and spectroscopy (HT-STM/STS) investigations of surface nanomodifications created on the TiO2(1 1 0) surface

High-temperature scanning tunnelling microscopy, scanning tunnelling spectroscopy and current imaging tunnelling spectroscopy (HT-STM/STS/CITS) were used to study the topographic and electronic structures changes due to surface modifications of the TiO₂(1 1 0) surface caused by the STM tip. In situ high-temperature STM results showed that the created modifications were stable even at elevated temperatures. The STS/CITS results showed the presence of energy gap below the Fermi level on the untreated regions. The disappearance of energy gap below the Fermi level on the modifications created by the tip was observed. It is assumed that the presence of the tip can change the chemical stoichiometry of the surface from TiO_2−x towards Ti₂O₃.     

石墨上纳米尺度金岛的形成

用扫描隧道显微镜研究了真空蒸镀在高定向热解石墨上金岛的形成和形状．随着蒸镀量的增加及时间的推移，金原子在表面通过扩散而逐渐合并成越来越大的原子团，以至岛，甚至岛群．虽然几个纳米大小的原子团仍十分可动，但在蒸镀量大于20单层时的岛或岛群已十分稳定．研究发现，同一蒸镀量下，各个金岛具有非常接近的宽度和高度，用薄膜成核的圆柱状模型计算岛的宽度与高度之比表明，金岛非常接近热力学平衡状态．这些形状各异的通过生长而自组装形成的纳米尺度金岛可用来进行介观物理的研究 关键词：     

FOURIER ANALYSIS OF TEMPORAL AND SPATIAL OSCILLATIONS OF TUNNELING CURRENT IN SCANNING TUNNELING MICROSCOPY

Partially oxidized Si(111) surfaces and surfaces of highly oriented pyrolytic graphite (HOPG) were studied by two different ultrahigh vacuum scanning tunneling microscope (UHV-STM) systems and by an STM system working under ambient conditions, respectively. The STM current images of partially oxidized Si(111) surfaces and HOPG surfaces were analyzed by one/two-dimensional fast Fourier transformation (1D-FFT/2D-FFT). The phenomenon of temporal oscillations of tunneling current on the partially oxidized Si(111) surfaces was detected with both UHV-STM systems. Temporal as well as spatial oscillations of tunneling current appeared in highly resolved STM current images of the Si(111) surfaces simultaneously, but both kinds of oscillations could be discriminated according to their different influence on the 2D-FFT spectra of the current images, while varying the scanning range and rate. On clean HOPG surfaces only spatial oscillations of tunneling current induced by the surface structure were observed.     

Formation of Two-Dimensional AgTe Monolayer Atomic Crystal on Ag(111) Substrate

We report on the formation of two-dimensional monolayer AgTe crystal on Ag(111) substrates. The samples are prepared in ultrahigh vacuum by deposition of Te on Ag(111) followed by annealing. Using a scanning tunneling microscope(STM) and low electron energy diffraction(LEED), we investigate the atomic structure of the samples.The STM images and the LEED pattern show that monolayer AgTe crystal is formed on Ag(111). Four kinds of atomic structures of AgTe and Ag(111) are observed:(i) flat honeycomb structure,(ii) bulked honeycomb,(iii)stripe structure,(iv) hexagonal structure. The structural analysis indicates that the formation of the different atomic structures is due to the lattice mismatch and relief of the intrinsic strain in the AgTe layer. Our results provide a simple and convenient method to produce monolayer AgTe atomic crystal on Ag(111) and a template for study of novel physical properties and for future quantum devices.     

外电场下STM钨针尖电子结构的理论研究

采用离散变分局域密度泛函方法，研究了外电场对钨(111)面针尖电子结构的影响.详细计算和分析了在不同偏压和距离条件下，钨针尖的隧道激活轨道和电荷分布.研究结果表明：隧道激活轨道中针尖原子的成分对外偏压的极性、大小以及针尖与样品之间的距离都较敏感.与过去理论计算结果不同，钨针尖原子的5d_z²轨道对隧道激活轨道有一定贡献，但并不是最主要的.在加正偏压时对隧道激活轨道贡献最大的为5d_xz和5d_yz轨道，而在加负偏压时则为包括 关键词：     

Distance-dependent STM-study of the W(110)/C-R(15×3) surface

The W(110)/C-R(15×3) reconstructed surface has been studied by STM at variable tip-surface separation controlled by the tunneling gap resistance. A pronounced dependence of the STM image contrast as a function of tip height has been observed which is explained by the suppression of higher Fourier components, i.e. small wavelength features, with increasing tip height and an additional spatial dependence of the decay length of the surface wavefunction. As an important implication of our study we have found that STM images of non-trivial surface structures can depend critically on the tunneling gap resistance.     

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.