Unique ordered domains of biphenylthiol self-assembled monolayers on Au(111)

The surface structure and adsorption conditions of biphenylthiol (BPT) self-assembled monolayers (SAMs) on Au(111) were examined using scanning tunneling microscopy (STM) and X-ray photoelectron microscopy (XPS). STM imaging revealed that the structural order of BPT SAMs formed in a 0.01 mM ethanol solution at 60 degrees C decreases with increasing immersion time. Interestingly, BPT SAMs formed after 30 min have unique ordered domains containing well-ordered (square root of 3 x square root of 3)R30 degrees structures and bright rows that are connected by small aggregated domains with a periodicity of approximately 10 angstroms, results that have never been observed for other thiol SAM systems. Distances between the bright rows were 20-35 angstroms. The bright small domains contained five or six BPT molecules each, which may have originated from differences in the adsorption orientations of biphenyl groups that were induced by localized interactions between them. XPS measurements for BPT SAMs on Au(111) showed the two sulfur peaks at 161.2 and 162.2 eV, implying the formation of chemisorbed monolayers. Our results are anticipated to be useful for understanding the formation and structure of BPT SAMs on gold surfaces.     

Immobilization of methylene blue on self-assembled iodine monolayers on gold

The immobilization of methylene blue (MB) on iodine-covered Au(111) is studied by electrochemical techniques, scanning tunneling microscopy (STM), Auger Electron Spectroscopy (AES), and Raman spectroscopy. Results show that MB species are efficiently adsorbed on the square root of 3 x square root of 3 R30 degrees I lattice on Au(111). The electrochemical behavior of the adsorbed MB molecules is reversible, indicating a relatively fast electron transfer from the Au(111) surface to the immobilized MB species through the iodine layer. STM images with molecular resolution are consistent with adsorption of MB dimers on a square root of 3 x square root of 3 R30 degrees I lattice placed atop of the Au(111) substrate. Results are compared to those obtained for MB immobilized on Au(111) covered by S(n) (n = 3-8) surface structures.     

An alkyl spacer effect on the structure of 4-fluorobenzenethiol and 4-fluorobenzenemethanethiol self-assembled monolayers on Au(111)

Self-assembled monolayers (SAMs) formed by the adsorption of 4-fluorobenzenethiol (4-FBT) and 4-fluorobenzenemethanethiol (4-FBMT) on Au(111) were examined by scanning tunneling microscopy (STM) to understand the effect of a flexible methylene spacer between the sulfur head-group and phenyl group and the effect of solution temperature on the formation and structure of the SAMs. Although the adsorption of 4-FBT on Au(111) at room temperature for 24 h generated only disordered phase SAMs containing gold adatom islands, 4-FBT at 75 degrees C for 2 h formed mixed SAMs: disordered phases and ordered (2 x 12√(2))R10 degrees superlattice with a rectangular unit cell containing six adsorbed molecules. On the other hand, SAMs formed from 4-FBMT, with a methylene spacer, at room temperature for 24 h on Au(111) had irregularly ordered phases containing uniformly distributed VIs with lateral dimensions of 2-5 nm; SAMs formed from 4-FBMT at 75 degrees C for 2 h were composed of slightly improved ordered phases and larger VIs with lateral dimensions of 5-12 nm as a result of Ostwald ripening. From this study, we found that the methylene spacer plays an important role in controlling the structure of SAMs formed from p-substituted fluorinated aromatic thiols.     

Germanium adsorption on Ag(111): an AES-LEED and STM study

The adsorption of germanium on Ag(111) has been investigated using Scanning Tunneling Microscopy, Auger Electron Spectroscopy and Low Energy Electron Diffraction. From the shape of the Auger peak-to-peak versus time curves, we deduce that at room temperature the growth mode is nearly layer-by-layer at least for the first two layers. In the sub-monolayer range, the growth starts by the formation of a (mean square root of 3 x mean square root of 3)R30 degrees surface superstructure which is complete at 1/3 monolayer coverage. Beyond this coverage a rectangular c(mean square root of 3 x 7) superstructure is observed. STM images reveal that this last reconstruction is formed by an ordered arrangement of self-assembled Ge tetramers giving rise to a surprising undulation of the surface.     

STM study of Au adsorption on Si(111)-7 x 7 surface: voltage and temperature dependence

We presented the scanning tunneling microscopy (STM) results on the study of Au adsorption at Si(111)-7 x 7 reconstructed surface. The voltage-dependent STM measurements indicated that there are at least three kinds of Au clusters and two types of single Au atoms adsorption on Si(111)-7 x 7 surface with Au coverage of about 0.2 monolayer. After the Au adsorbed Si surface was annealed at about 250 degrees C, the adsorbed Au clusters would diffuse into the Si substrate, and consequently create surface defects on the Si substrate. Sequentially annealed the sample at about 500 degrees C, the diffused Au would emerge out again and form larger 3-dimension Au clusters at the Si surface.     

Zinc porphyrin-driven assembly of gold nanofingers

Nanofingers of gold covered by porphyrins are prepared by a combination of atomic manipulation and surface self-organization. A submonolayer of zinc(II) 5,10,15,20-tetrakis(4-tert-butylphenyl)-porphyrin (ZnTBPP) axially ligated to a self-assembled monolayer of 4-aminothiophenol (4-ATP) on Au(111) is prepared and studied using a combination of ultrahigh vacuum techniques. Under the electric field produced by the STM tip, the relatively weakly bound Au surface atoms along the discommensuration lines become mobile due to the strong bond to 4-ATP, while the tendency of the porphyrins towards self-assembly result in a collective motion of gold clusters. The clusters diffuse onto the surface following well-defined pathways along the [112] direction and then reach the step edges where they assembled, thus forming nanofingers. First-principles density functional theory calculations demonstrate the reduction of the binding energies between the surface gold clusters and the substrate induced by adsorption of thiols. Scanning tunneling microscopy images show assemblies across three adjacent discommensuration lines of the Au(111)-(22 x square root 3) reconstruction, which collectively diffuse along these lines to form islands nucleated at step edges.     

Reconstructed structures of nanosized co islands on Ag/Ge(111) mean square root of 3 x mean square root of 3 surfaces

Structural evolution of Co/Ag/Ge(111) at high temperatures was studied by using scanning tunneling microscopy and low energy electron diffraction. The mean square root of 3 x mean square root of 3-Ag layer between the substrate Ge( 11) and Co adatoms can avoid the formation of Co-Ge compounds below 800 K. The Co atoms nucleate to form islands where mean square root of 13 x mean square root of 13 or 2 x 2 reconstructions were observed after annealing between 373 K and 737 K. The mean square root of 13 x mean square root of 13 structure with mirror symmetry relative to [-211], [11-2], and [1-21] axes was observed for 1-2 layer Co islands. Co islands with over 2 layers appear 2 x 2 structure. All reconstruction structures of the nano-sized Co islands and substrate Ag/Ge(111) mean square root of 3 x mean square root of 3 surface were analyzed using the atomic hard sphere model. The bright protrusions of these reconstructions all sit in the centers of Ag or Ge trimers, which were predicted to have maximum binding energy.     

In-situ examination of the selective etching of an alkanethiol monolayer covered Au{111} surface

An examination of the selective etching mechanism of a 1-alkanethiol self-assembled monolayer (SAM) covered Au{111} surface using in-situ atomic force microscopy (AFM) and molecular resolution scanning tunnelling microscopy (STM) is presented. The monolayer self-assembles on a smooth Au{111} surface and typically contains nanoscale non-uniformities such as pinholes, domain boundaries and monatomic depressions. During etching in a ferri/ferrocyanide water-based etchant, selective and preferential etching occurs at SAM covered Au(111) terrace and step edges where a lower SAM packing density is observed, resulting in triangular islands being relieved. The triangular islands are commensurate with the Au(111) lattice with their long edges parallel to its [11¯0] direction. Thus, SAM etching is selective and preferential attack is localized to defects and step edges at sites of high molecular density contrast.     

Metal-free phthalocyanine (H2Pc) molecule adsorbed on the Au(111) surface: formation of a wide domain along a single lattice direction

Using low-temperature scanning tunneling microscopy (STM), we observed the bonding configuration of the metal-free phthalocyanine (H₂Pc) molecule adsorbed on the Au(111) surface. A local lattice formation started from a quasi-square lattice aligned to the close-packed directions of the Au(111) surface. Although we expected the lattice alignment to be equally distributed along the three crystallographically equivalent directions, the domain aligned normal to the ridge of the herringbone structure was missing in the STM images. We attribute this effect to the uniaxial contraction of the reconstructed Au(111) surface that can account for the formation of a large lattice domain along a single crystallographical direction.     

MgB2 Superconducting Tips for Scanning Tunneling Microscopy Study

We report a simple method for the fabrication of reproducible, clean, and stable MgB₂ superconducting tips. The quality of these tips has been verified by imaging the surface of a thin Au(111) film sample, using a low temperature scanning tunneling microscopy (STM). Using the MgB₂ superconducting tip, high-quality semiatomically resolved STM surface images of the thin Au(111) film sample have been observed, which unambiguously indicates that the fabrication of relatively superconducting MgB₂, suitable for use as STM tips, is feasible.     

MgB2 Superconducting Tips for Scanning Tunneling Microscopy Study

We report a simple method for the fabrication of reproducible, clean, and stable MgB₂ superconducting tips. The quality of these tips has been verified by imaging the surface of a thin Au(111) film sample, using a low temperature scanning tunneling microscopy (STM). Using the MgB₂ superconducting tip, high-quality semiatomically resolved STM surface images of the thin Au(111) film sample have been observed, which unambiguously indicates that the fabrication of relatively superconducting MgB₂, suitable for use as STM tips, is feasible.     

Metal-free phthalocyanine (H2Pc) molecule adsorbed on the Au(111) surface: formation of a wide domain along a single lattice direction

Abstract

Using low-temperature scanning tunneling microscopy (STM), we observed the bonding configuration of the metal-free phthalocyanine (H₂Pc) molecule adsorbed on the Au(111) surface. A local lattice formation started from a quasi-square lattice aligned to the close-packed directions of the Au(111) surface. Although we expected the lattice alignment to be equally distributed along the three crystallographically equivalent directions, the domain aligned normal to the ridge of the herringbone structure was missing in the STM images. We attribute this effect to the uniaxial contraction of the reconstructed Au(111) surface that can account for the formation of a large lattice domain along a single crystallographical direction.     

Long-range order induced by cobalt porphyrin adsorption on aminothiophenol-functionalized Au(111): the influence of the induced dipole

Porphyrins are useful in materials science for optical, photoelectrochemical and chemical sensor applications. Solid films of oriented porphyrins on gold can be realized through a simple procedure and without synthesizing thiol-derivatized porphyrins. In order to immobilize the porphyrin rings on the surface, we prepared a 4-aminothiophenol (4-ATP) self-assembled monolayer (SAM) on gold(111) followed by axial legation, in situ, of cobalt(II) 5,10,15,20-tetrakis(4-tert-butylphenyl)-porphyrin (CoTBPP). Ultrahigh vacuum (UHV) Scanning Tunneling Microscopy (STM) studies performed on the SAMs revealed the Au(111) herringbone structure reconstruction, probably due to adsorption/desorption processes of molecules. STM images and Scanning Tunneling Spectroscopy (STS) measurements clearly showed that the immobilization of molecules also induced an electronic perturbation on the gold surface. This effect is ascribed to the presence of oriented molecular dipole layers between the metal and the organic material.     

The adsorption of Ni on the Mo(111) crystal face

STM, LEED, AES, TDS and Δ? measurements were performed to investigate the adsorption of Ni on the molybdenum (111) surface. The adsorption energy of Ni atoms on the Mo(111) surface was determined. At 300 K the layer-by-layer growth mechanism was observed. No faceting of the Mo(111) surface was observed after the annealing. Annealing leads to the adsorbate agglomeration and formation of Ni islands in the shape of pyramids.     

Direct evidence of arsenic(III)-carbonate complexes obtained using electrochemical scanning tunneling microscopy

Electrochemical scanning tunneling microscopy (ECSTM), ion chromatography (IC), and electrospray ionization-mass spectrometry/mass spectrometry were applied to investigate the interactions between arsenite [As(III)] and carbonate and arsenate [As(V)] and carbonate. The chemical species in the single and binary component solutions of As(III), As(V), and carbonate were attached to a Au(111) surface and then imaged in a 0.1 M NaClO4 solution at the molecular level by ECSTM. The molecules formed highly ordered adlayers on the Au(111) surface. High-resolution STM images revealed the orientation and packing arrangement of the molecular adlayers. Matching the STM images with the molecular models constructed using the Hyperchem software package indicated that As(III) formed two types of complexes with carbonate, including As(OH)2CO3- and As(OH)3(HCO3-)2. No complexes were formed between As(V) and carbonate. IC chromatograms of the solutions revealed the emergence of the new peak only in the aged As(III)-carbonate solution. MS spectra showed the presence of a new peak at m/z 187 in the aged As(III)-carbonate solution. The results obtained with the three independent methods confirmed the formation of As(OH)2CO3-. The results also indicated that As(OH)3 could be associated with HCO3- through a hydrogen bond. The knowledge of the formation of the As(III) and carbonate complexes will improve the understanding of As(III) mobility in the environment and removal of As(III) in water treatment systems.     

Quasi-collective motion of nanoscale metal strings in metal surfaces

Mass transport processes on metal surfaces play a key role in epitaxial growth and coarsening processes. They are usually described in terms of independent, statistical diffusion and attachment/detachment of individual metal adatoms or vacancies. Here we present high-speed scanning tunnelling microscopy (video-STM) observations of the dynamic behaviour of five-atom-wide, hexagonally ordered strings of Au atoms embedded in the square lattice of the Au(100)-(1x1) surface that reveal quasi-collective lateral motion of these strings perpendicular to as well as along the string direction. The perpendicular motion can be ascribed to small atomic displacements in the strings induced by propagating kinks, which also provides a mechanism for the exchange of Au atoms between the two string ends, required for motion in string direction. In addition, quasi-one-dimensional transport of Au adatoms along the string boundaries may contribute to the latter phenomenon according to density functional calculations.     

Effect of functional groups on the crystallization of ferric oxides/oxyhydroxides in suspension environment

This paper investigated the effects of five kinds of Au surfaces terminated with and without functional groups on the crystallization of ferric oxides/oxyhydroxides in the suspension condition. Self-assembled monolayers (SAMs) were used to create hydroxyl (--OH), carboxyl (--COOH), amine (--NH₂) and methyl (--CH₃) functionalized surfaces, which proved to be of the same surface density. The immersion time of substrates in the Fe(OH)₃ suspension was divided into two time portions. During the first period of 2 h, few ferric oxide/oxyhydroxide was deposited except that ?-Fe₂O₃ was detected on--NH₂ surface. Crystallization for 10 h evidenced more kinds of iron compounds on the functional surfaces. Goethite and maghemite were noticed on four functional surfaces, and maghemite also grew on Au surface. Deposition of ?-Fe₂O₃ was found on--OH surface, while the growth of orthorhombic and hexagon FeOOH were indicated on--NH₂ surface. Considering the wide existence of iron compounds in nature, our investigation is a precedent work to the study of iron biomineralization in the suspension area.     

STM investigation of substitute effect on oligothiophene adlayer at Au(111) substrate

Molecular adlayers of a series of oligothiophenes with carboxylic groups and alkyl substitutes, DTDA, TTDA, QTDA, and PTDA, are investigated by STM at Au(111) surface. The effect of molecular structure including alkyl chain and thiophene backbone on the adlayer structure is revealed. DTDA and TTDA with two and three thiophene rings, self-assembled into highly ordered long-range two dimensional structures via hydrogen bondings, while QTDA with four thiophene rings formed short-range ordered structure with hexagonal symmetry. PTDA with five thiophene rings showed disordered pattern due to its strong molecule-substrate interaction. The results are compared with those on HOPG surface, showing that the molecule-substrate interaction plays an important role in the adlayer formation of these oligothiophenes.     

Unusual diffusivity and clustering of alkali metals on the Si(111)-7x7 surface

In this paper I review our recent experimental and theoretical works on the behaviors of submonolayer alkali metals (Li, Na, K, Cs) on the Si(111)-7x7 surface. The important aspects in the experimental preparation are discussed. While Li forms clusters even at the initial coverage, all other alkali metals (Na, K, Cs) form two-dimensional (2D) gases at room temperature and low coverage, due to their unusual high diffusivity on the surface. At higher coverage, cluster formation is observed, but with very different behaviors for Na, K, and Cs. Issues relative to the phase transition with increasing coverage are discussed: (1) the mechanism for the 2D gas formation; (2) the effect of 2D gas formation on STM observations; (3) The effect of structure on the charge transfer from alkali metals to the surface; (4) the exchange of alkali metal atoms with the Si adatoms during the cluster formation.     

Cerium oxide layers on Pt(111): a scanning tunneling microscopy study

Ultrathin epitaxial layers of cerium oxide were prepared by oxidation of layers of an ordered Pt–Ce surface alloy on top of a Pt(111) single crystal. They consist of low-dimensional CeO₂ islands. Atomically resolved scanning tunnel microscopy (STM) images indicate a surface structure of the fluorite-type CeO₂(111) 1×1 phase and the presence of surface defects.