In-situ STM studies of electrochemical underpotential deposition of Pb on Au(111)

A modified scanning tunnelling microscope (STM) has been used to observe in-situ deposition and stripping of an electrochemical film. With STM tip and sample immersed in an acid electrolyte, single atomic steps on Au(111) have been imaged during the deposition and stripping of a monolayer-thick, underpotential deposit (UPD) of Pb. Integration of the electrochemical current passed during the film deposition and evidence from the STM images themselves confirm monolayer coverage. Our images show enhanced film growth at step edges and defect sites. Observations of single plating and stripping cycles indicate that the Au substrate returns unaltered. Except for atomic resolution images of Au(111), which we have not yet achieved in an electrolyte, all types of Au surface features seen in air are reproduced under the electrolytic solution. The modifications made to our STM in order to perform in-situ electrochemical experiments are described.     

Imaging of hydrogen-induced Si(111) surface with the scanning tunnelling microscope

We have directly observed the hydrogen-induced changes of the Si(111)7times7 surface using a scanning tunnelling microscope (STM). The 7times7 reconstructed atomic structure was formed on a clean surface of Si(111). But when the clean surface was dosed with typically 1–2 L [1 L (Langmuir) = 1·33 times 10^?4 Pa. sec] hydrogen, the 7 times 7 image was gradually smeared out and then a 1 times 1 unreconstructed pattern appeared. After dosing with 5–10 L hydrogen, the STM image exhibited a new long-periodic structure together with the 1times1 structure underneath. These experimental results may be ascribed to the chemisorption of hydrogen atoms on clean Si surfaces.     

Well-ordered structure of methylene blue monolayers on Au(111) surface: electrochemical scanning tunneling microscopy studies

Well-ordered structure of methylene blue (MB) monolayers on Au(111) surface has been successfully obtained by controlling the substrate potential. Electrochemical scanning tunneling microscopy (ECSTM) examined the monolayers of MB on Au(111) in 0.1 M HClO(4) and showed long-range ordered, interweaved arrays of MB with quadratic symmetry on the substrate in the potential range of double-layer charging. High-resolution ECSTM image further revealed the details of the MB monolayers structure of c(5 x 5 radical 3)rect and the flat-lying orientation of ad-molecules. The dependence of molecular organization on the substrate potential and the formation mechanism of well-ordered structure on Au(111) surface were investigated in detail. The obtained well-ordered structure at the interface between a metal and an aqueous electrolyte might possibly be used as high-density device for signal memory and templates for the advanced nanopatterning of surfaces.     

Electric field-induced changes of W(110) and W(111) tips

Using field emission and scanning electron microscopy we have studied the influence of strong electric fields on the thermally induced growth behaviour of field emission tips. For smaller fields (i.e. smaller than needed for a satisfactory field emission image) we observe an enlargement of low-index faces, which for higher fields develops into a building-up of micro-structures and roughening on the initially spherical part of the tip surface. In an intermediate state only the region near the (111) directions contributes to the field emission pattern. For the highest fields employed the results indicate the growth of local protrusions preferentially near (100) faces. Our results show that in scanning tunnelling microscopy W(111) tips should be superior to the commonly used W(110) tips.     

Oriented immobilization of Pseudomonas putida putidaredoxin at a gold (111)–buffer interface: a real time scanning tunnelling microscopy study

A scanning tunnelling microscopy study of adsorption of wild‐type Pseudomonas putida putidaredoxin at a gold (111)–buffer interface has been made in real time. Reversible adsorption has been observed reflecting weak interaction of the wild‐type protein with a gold (111) electrode. A genetically engineered mutant, C73S‐D58C, which contains a surface thiol, has been used for ‘immobilization’ and ‘orientated adsorption’ on the gold surface. The implication of such orientated immobilization in development of a bio‐electrode surface has been predicted.     

Scanning tunnelling microscopy studies of heteroepitaxy: CaF2 on Si(111)

We apply scanning tunnelling microscopy and tunnelling spectroscopy to study the initial stages of CaF₂ epitaxy on Si(111)-(7×7) for a range of deposition temperatures. We find that deposition at surface temperatures <700°C leads to CaF₂ clustering. At temperatures between 750 and 800°C two new structures, a 2×3 and a (√3 X √3***)R30°, are observed. Tunnelling spectra and topographs obtained at different energies allow us to measure interface band gaps, and determine the valence state of Ca bonded directly to silicon and the valence state of Ca in the second layer. More importantly, we demonstrate that STM can be used to image thick insulating layers of CaF₂ by tunnelling into the conduction band of the films. One of our goals in this study has been to test the ability of STM to image insulating multilayers. It is generally believed that STM cannot be applied to insulators. We find, however, that despite the large band gap of ～12 eV, the CaF₂ conduction band is accessible, and that insulating films can be imaged by STM.     

Adlayer structure of octa-alkoxy-substituted copper(II) phthalocyanine on Au(111) by electrochemical scanning tunneling microscopy

Electrochemical scanning tunneling microscopy (ECSTM) has been used to examine the adlayer of octa-alkoxy-substituted copper(II) phthalocyanines (CuPc(OC(8)H(17))(8)) on Au(111) in 0.1 M HClO(4), where the molecular adlayer was prepared by spontaneous adsorption from a benzene solution containing this molecule. Topography STM scans revealed long-range ordered, interweaved arrays of CuPc(OC(8)H(17))(8) with coexistent rectangular and hexagonal symmetries. High-quality STM molecular resolution yielded the internal molecular structure and the orientation of CuPc(OC(8)H(17))(8) admolecules. These STM results could shed insight into the method of generating ordered molecular assemblies of phthalocyanine molecules with long-chained substitutes on metal surface.     

Comparison of LEED and STM measurements of vicinal Si(111)

LEED beam-profile and STM measurements have been used in combination to study the ordering of stepped Si(111) surfaces misoriented by 4° toward the [***211] direction. LEED measurements show that ordering of the surface steps is dependent on the thermal history of the sample, but give little clue about the reasons. An initial cleaning at 1250°C followed by slow cooling is required to obtain a well-ordered step structure. STM measurements show that cleaning at a lower temperature (850°C) results in a surface containing highly disordered patches which are possibly correlated with residual carbon. These disordered regions evidently inhibit step order. STM images of rapidly quenched surfaces show a very different sort of disorder consisting of long wavelength (5–10 nm) corrugations of rms vertical amplitude 2 nm.     

Tribological Properties of Self-Assembled Monolayers and Their Substrates Under Various Humid Environments

Using friction force microscopy (FFM) under controlled environments, we have systematically investigated the humidity effect on the frictional properties of two important classes of self-assembled monolayers (SAMs), i.e., N-octadecyltrimethoxysilane (OTE, CH₃(CH₂)₁₇Si(OCH₃)₃) on SiO₂(OTE/SiO₂), and N-alkanethiols on Au(111), together with their respective substrates. Experimental results show that both OTE and alkylthiol SAMs can decrease the friction force between a Si₃N₄ atomic force microscope (AFM) tip and substrates. The nearly humidity-independent friction of the two kinds of SAMs indicates that these SAMs are ideal lubricants in applications of micro-electro-mechanical systems (MEMS) under different environments. The humidity dependence—as the humidity increases, the friction first increases and then decreases—of the two substrates, SiO₂ and Au(111), can be explained by the adsorption of water. The decrease in the friction at high humidity is attributed to the low viscosity in the multilayers of water, while the increase in the friction at low humidity can be explained by the high viscosity between the water monolayer and the surfaces (AFM tip and sample), possibly due to the confinement effects. The effect of modification of the AFM tip with alkanethiol molecules on the humidity dependence of Au(111) friction has also been investigated.     

Unique domain structure of pi-conjugated tolanethioacetate self-assembled monolayers on Au(111)

Surface structures of tolanethioacetate (TTA) self-assembled monolayers (SAMs) on Au(111), formed in a 0.5mM N,N'-dimethylformamide (DMF) solution, were investigated as a function of solution temperature by scanning tunneling microscopy (STM). The STM study revealed that thioacetyl-terminated TTA molecules on Au(111) did not form ordered SAMs at room temperature and 80 degrees C, whereas the adsorption of TTA molecules on Au(111) at a solution temperature of 50 degrees C led to the formation of two mixed phases: a disordered phase and a unique ordered phase, consisting rod-like domains, which can be described as a ( radical6x radical13)15 degrees superstructure. From this study, it was demonstrated that solution temperature is a key factor controlling the two-dimensional SAM structure of TTA molecules.     

Atomic Friction Modulation on the Reconstructed Au(111) Surface

Friction between a nanoscale tip and a reconstructed Au(111) surface is investigated both by atomic force microscopy (AFM) and molecular statics calculations. Lateral force AFM images exhibit atomic lattice stick–slip behavior with a superstructure corresponding to the herringbone reconstruction pattern. However, the superstructure contrast is not primarily due to variations in the local frictional dissipation (which corresponds to the local width of the friction loop). Rather, the contrast occurs primarily because the local centerline position of the friction loop is periodically shifted from its usual value of zero. Qualitatively, similar behavior is reproduced in atomistic simulations of an AFM tip sliding on the reconstructed Au(111) substrate. In both simulations and experiments, this centerline modulation effect is not observed on unreconstructed surfaces. Similarly, using a topographically flat surface as a hypothetical control system, the simulations show that the centerline modulation is not caused by variations in the reconstructed surface’s topography. Rather, we attribute it to the long-range variation of the local average value of the tip-sample interaction potential that arises from the surface reconstruction. In other words, surface atoms located at unfavorable sites, i.e., in the transition between face-centered-cubic (FCC) and hexagonal-close-packed (HCP) regions, have a higher surface free energy. This leads to a varying conservative force which locally shifts the centerline position of the friction force. This demonstrates that stick–slip behavior in AFM can serve as a rather sensitive probe of the local energetics of surface atoms, with an attainable lateral spatial resolution of a few nanometers.     

Self‐assembled monolayers of DNA on cysteamine modified Au(111) surface: Atomic force microscopy study

The λ‐DNA molecules self‐assemble on cysteamine‐modified gold (111) surface to form flat‐lying self‐assembled monolayers (SAMs). The formation kinetics of such DNA SAMs is studied by atomic force microscopy (AFM). AFM results show that DNA molecules do not arrange themselves on cysteamine‐modified gold (111) surface into a well‐ordered monolayer. It is also found that the surface density of DNA monolayer does not increase as the DNA concentration increases. The high temperature of DNA solution and the immersing in ultrapure water produce some obvious DNA bundles. Whereas divalent cations in DNA solution result in the formation of more compact DNA films. The obtained information may be useful for practical application of the DNA films and further theoretical studies. Microsc. Res. Tech., 2009. © 2009 Wiley‐Liss, Inc.     

Acetonitrile (CH3CN) and methyl isocyanide(CH3NC)adsorption on Pt(111) surface: a DFT study

The adsorption of CH3CN and CH3NC on the Pt(111)surface at the 1/4 monolayer(ML)coverage has been carried out at the level of density functional theory for understanding hydrogenation processes of nitriles.The most favored adsorption structure for CH3CN is the C-N bond almost parallel to the surface with the C-N bond interaction with adjacent surface Pt atoms.For CH3NC,the most stable configuration is the CH3NC locates at the face center cubic(fcc)site with the C-atom bonded to three Pt atoms.In addition,the HCN and HNC adsorption has been computed,and the adsorption pattern is nearly similar to the CH3CN and CH3NC,respectively.The adsorbed molecules rehybridize on the surface,becoming non-linear with a bent C-C-N or C-N-C angle.Furthermore,the binding mechanism of these molecules on the Pt(111)surface is also analyzed.     

TEM and AES investigations of surface-diffusion-induced aging processes in thin Au films on Ag(111)

Surface-diffusion-induced aging processes have been observed in epitaxial Au films on Ag(111) which were prepared by vapour deposition at 30°C and subsequently annealed at temperatures between 100 and 210°C. In discontinuous Au films (thickness<5 monolayers) at temperatures below 170°C overlayers of Ag substrate material are created on top of the Au films, whereas at temperatures above 170°C the film and substrate materials are intermixed in the surface region. Continuous Au films, however, are completely levelled during annealing. The growth-induced surface roughness disappears, and perfectly flat surfaces develop exhibiting only some 2D islands or pits. The results obtained for the Au-Ag system are expected to be applicable to other systems, too.     

The effect of fluorination on the surface chemistry of alkyl ethers on Cu(111)

By using small fluorinated ethers as models for perfluoropolyalkylether (PFPAE) lubricants, we have been able to determine the effect of fluorination on the bonding of the alkyl ethers adsorbed on the Cu(111) surface. The desorption energies have been determined by using temperature programmed desorption (TPD). The model compounds studied were dioxolane , diethyl ether ((CH₃CH₂)₂O), dimethoxymethane ((CH₃O)₂CH₂), dimethyl ether ((CH₃)₂O) and their perfluorinated analogues. All of the molecules studied adsorb molecularly and reversibly on the Cu(111) surface exhibiting first-order desorption kinetics. Upon fluorination of the alkyl ethers, the adsorbate-metal bond was weakened by 14 to 8 kcal/mol. The intermolecular interaction parameters for the hydrogenated ethers indicated repulsive adsorbate-adsorbate interactions, while the fluorinated ethers have attractive adsorbate-adsorbate interactions.     

Initial steps in the surface chemistry of vapor phase lubrication by organophosphorus compounds

The surface chemistry of trimethylphosphite (CH₃O)₃P has been studied on Cu(111) and Ni(111) surfaces in order to model the initial steps in the reactions of vapor phase lubrication by organophosphorus compounds. The initial reactions involve scission of the P–O bonds to deposit methoxy groups (CH₃O_(ad)) on the surfaces. On the Cu(111) surface the formation of CH₃O_(ad) species occurs only after oxidation of the surface. The CH₃O_(ad) groups on Cu(111) decompose by β‐hydride elimination to produce formaldehyde (O=CH₂) and adsorbed hydrogen. CH₃O_(ad) groups are formed from (CH₃O)₃P on the clean Ni(111) surface and decompose by complete dehydrogenation to CO and adsorbed hydrogen atoms. This chemistry is very similar to that observed for CH₃OH on these surfaces. These results suggest that alkoxides are important intermediates in the decomposition of vapor phase lubricants on metal surfaces. This revised version was published online in July 2006 with corrections to the Cover Date.     

Upper-bound anisotropic yield locus calculations assuming 111-pencil glide

Deformation by 111-pencil glide has been analyzed by an upper-bound model which combines a least-shear analysis and Piehler's maximum virtual work analysis. The least-shear analysis gives exact solutions if three 111 slip systems are active, while the maximum work analysis provides solutions for the case of four active slip systems. Independent checks are used to determine which solution method is appropriate.Computer calculations using this model have been made to determine; (1) the orientation dependence of the Taylor factor for axisymmetric deformation; (2) the yield loci for textured materials having [100], [110] and [111] sheet metals and rotational symmetry; (3) the isotropic yield locus for randomly oriented materials; and (4) flow stresses along critical loading paths for various assumed textures with rotational symmetry. The latter calculations indicate that anisotropic yield loci of textured bcc metals with rotational symmetry are much better approximated by σ_x^a + σ_y^a + R¦σ_x − σ_y¦^a = (R + 1)Y^a where R is the strain ratio and Y is the tensile yield strength with an exponent a = 6 rather than with a = 2 as postulated by Hill. It is not known how well upper-bound calculations like these represent actual yielding behavior.     

Mono- and multiatomic steps with constant periodicity as observed by STM in vicinal Au(111) surfaces

Scanning tunnelling microscopy images of a vicinal Au(111) surface obtained in UHV are presented. Arrays of mono- and multiatomic steps along the [011] direction are seen with a peculiarly constant periodicity. The steps, exposing (100) facets, have a height ranging from one to seven atoms while the terrace width of eight atoms remains constant.     

Investigation of intrinsic crystalline Si(111) and amorphous silicon surfaces in air with STM

Crystalline (111) and amorphous silicon surfaces have been studied by scanning tunnelling microscopy. An orientated, reproducible, corrugated structure has been observed on Si(111) surfaces. The voltage dependence of the corrugation amplitude may be attributable to surface states. The surfaces of amorphous silicon thin films show some reproducible structure in the range of a few tens of ångströms, observable only when the applied voltage between the tip and sample is between ?1·3 and +0·4V.     

In situ,atomic scale observation of electrode topography and reactions

The topographical changes occurring on a Au(111) electrode during simple electrochemical reactions have been followed with an STM capable of operating in situ, i.e. in the electrochemical environment, and of yielding atomic scale resolution. Changes in the surface structure induced by adsorption and desorption of Cl^? ions could be observed and the effects of subjecting the sample to an oxidation-reduction cycle could be monitored.