Formation of ordered self-assembled monolayers by adsorption of octylthiocyanates on Au(111)

Self-assembled monolayers (SAMs) were formed by the spontaneous adsorption of octythiocyanate (OTC) on Au(111) using both solution and ambient-pressure vapor deposition methods at room temperature and 50 degrees C. The surface structures and adsorption characteristics of the OTC SAMs on Au(111) were characterized by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). The STM observation showed that OTC SAMs formed in solution at room temperature have unique surface structures including the formation of ordered and disordered domains, vacancy islands, and structural defects. Moreover, we revealed for the first time that the adsorption of OTC on Au(111) in solution at 50 degrees C led to the formation of SAMs containing small ordered domains, whereas the SAMs formed by vapor deposition at 50 degrees C had long-range ordered domains, which can be described as (radical3 x 2 radical19)R5 degrees structures. XPS measurements of the peaks in the S 2p and N 1s regions for the OTC SAMs showed that vapor deposition is the more effective method as compared to solution deposition for obtaining high-quality SAMs by adsorption of OTC on gold. The results obtained will be very useful in understanding the SAM formation of organic thiocyanates on gold surfaces.     

Coverage-dependent Orientations of Dy@C82 Molecules on Au(111) Surface

The adsorption and molecular orientation of Dy@C82 isomer I on Au(111) has been investi-gated using ultrahigh-vacuum scanning tunneling microscopy at 80 K. At low coverages, the Dy@C82 molecules tend to grow along the step edges of Au(111), forming small clusters and molecular chains. Adsorption of Dy@C82 on the edges is dominated by the fullerene-substrate interaction and presents various molecular orientations. At higher coverages, the Dy@C82 is found to form ordered islands consisting of small domains of equally oriented molecules. The Dy@C82 molecules in the islands prefer the adsorption configurations with the major C2 axis being approximately parallel to the surface of the substrate. Three preferable orientations of the Dy@C82 molecules are found in a two-dimensional hexagonal close packed overlayer. These observations are attributed to the interplay of the fullerene-substrate interaction and dipole-dipole interaction between the metallofullerenes.     

Coverage effects and the nature of the metal-sulfur bond in S/Au(111): high-resolution photoemission and density-functional studies

The bonding of sulfur to surfaces of gold is an important subject in several areas of chemistry, physics, and materials science. Synchrotron-based high-resolution photoemission and first-principles density-functional (DF) slab calculations were used to study the interaction of sulfur with a well-defined Au(111) surface and polycrystalline gold. Our experimental and theoretical results show a complex behavior for the sulfur/Au(111) interface as a function of coverage and temperature. At small sulfur coverages, the adsorption of S on fcc hollow sites of the gold substrate is energetically more favorable than adsorption on bridge or a-top sites. Under these conditions, S behaves as a weak electron acceptor but substantially reduces the density-of-states that gold exhibits near the Fermi edge. As the sulfur coverage increases, there is a weakening of the Au-S bonds (with a simultaneous reduction in the Au --> S charge transfer and a modification in the S sp hybridization) that facilitates changes in adsorption site and eventually leads to S-S bonding. At sulfur coverages above 0.4 ML, S(2) and not atomic S is the more stable species on the gold surface. Formation of S(n)(n > 2) species occurs at sulfur coverages higher than a monolayer. Very similar trends were observed for the adsorption of sulfur on polycrystalline surfaces of gold. The S atoms bonded to Au(111) display a unique mobility/reactivity not seen on surfaces of early or late transition metals.     

In Situ dynamic monitoring of electrochemical oxidative adsorption and reductive desorption processes of a self-assembled monolayer of hexanethiol on a Au(111) surface in KOH ethanol solution by scanning tunneling microscopy

Electrochemical oxidative formation and reductive desorption processes of a self-assembled monolayer (SAM) of hexanethiol on a Au(111) surface in KOH ethanol solutions containing various concentrations of hexanethiol were investigated by in situ scanning tunneling microscopy in real time. The generation and disappearance of vacancy islands (VIs), corresponding to the formation and desorption of the SAM, respectively, were observed as anodic and cathodic current, respectively, flowed when the thiol concentration was higher than ca. 1 microM. When the VIs disappeared after the reductive desorption of the SAMs, the herringbone structure corresponding to the (radical3 x 23) structure of Au(111), was observed on the surface, indicating that a clean reconstructed surface was exposed even in the hexanethiol ethanol solution. During both oxidative adsorption and reductive desorption of the SAMs, the shape of the steps of the gold substrate changed drastically and the step lines became parallel to the 121 direction of the Au(111) surface, suggesting that gold atoms on the surface were extremely mobile during these processes. The coalescence of adjacent vacancy islands and growth of larger islands triangular in shape accompanied with the disappearance of nearby smaller islands were observed, confirming that the VIs grew according to the Ostward ripening model.     

Water adsorption, desorption, and clustering on FeO(111)

The adsorption of water on FeO(111) is investigated using temperature programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRAS). Well-ordered 2 ML thick FeO(111) films are grown epitaxially on a Pt(111) substrate. Water adsorbs molecularly on FeO(111) and desorbs with a well resolved monolayer peak. IRAS measurements as a function of coverage are performed for water deposited at 30 and 135 K. For all coverages (0.2 ML and greater), the adsorbed water exhibits significant hydrogen bonding. Differences in IRAS spectra for water adsorbed at 30 and 135 K are subtle but suggest that water adsorbed at 135 K is well ordered. Monolayer nitrogen TPD spectra from water covered FeO(111) surfaces are used to investigate the clustering of the water as a function of deposition or annealing temperature. Temperature dependent water overlayer structures result from differences in water diffusion rates on bare FeO(111) and on water adsorbed on FeO(111). Features in the nitrogen TPD spectra allow the monolayer wetting and 2-dimensional (2D) ordering of water on FeO(111) to be followed. Voids in a partially disordered first water layer exist for water deposited below 120 K and ordered 2D islands are found when depositing water above 120 K.     

Solvent effects on the adsorption and self-organization of Mn12 on Au(111)

A sulfur-containing single molecule magnet, [Mn12O12(O2CC6H4SCH3)16(H2O)4], was assembled from solution on a Au(111) surface affording both submonolayer and monolayer coverages. The adsorbate morphology and the degree of coverage were inspected by scanning tunneling microscopy (STM), while X-ray photoelectron spectroscopy (XPS) allowed the determination of the chemical nature of the adsorbate on a qualitative and quantitative basis. The properties of the adsorbates were found to be strongly dependent on the solvent used to dissolve the magnetic complex. In particular, systems prepared from tetrahydrofuran solutions gave arrays of isolated and partially ordered clusters on the gold substrate, while samples prepared from dichloromethane exhibited a homogeneous monolayer coverage of the whole Au(111) surface. These findings are relevant to the optimization of magnetic addressing of single molecule magnets on surfaces.     

Alkanethiol/Au(111) self-assembled monolayers contain gold adatoms: scanning tunneling microscopy before and after reaction with atomic hydrogen

Alkanethiol self-assembled monolayers on Au(111) are widely studied, yet the exact nature of the sulfur-gold bond is still debated. Recent studies suggest that Au(111) is significantly reconstructed, with alkanethiol molecules binding to gold adatoms on the surface. These adatoms are observed using scanning tunneling microscopy before and after removing the organic monolayer with an atomic hydrogen beam. Upon monolayer removal, changes in the gold substrate are seen in the formation of bright, triangularly shaped islands, decreasing size of surface vacancy islands, and faceting of terrace edges. A 0.143 +/- 0.033 increase in gold coverage after monolayer removal shows that there is one additional gold adatom for every two octanethiol molecules on the surface.     

Preparation and structural characterization of RuS2 nanoislands on Au(111)

Among all the transition metal sulfides, ruthenium sulfide (RuS2) has been shown to be the most active catalyst for the hydrodesulfuriztion processes. Using X-ray photoemission spectroscopy (XPS) and scanning tunneling microscopy (STM), we have found a novel approach for the preparation of RuS2 nanoislands on an Au(111) substrate. Chemical vapor deposition of Ru3(CO)12 leads to metallic Ru nanoclusters on the gold substrate. Although sulfidation has not been observed on extended Ru (0001) surface, Ru nanoclusters react with S2, forming ruthenium sulfide. While the majority of the sulfide is in the form of nanosized clusters that aggregate into clustered islands, a small fraction of the sulfide is seen as flat islands. When Ru3(CO)12 was deposited on a sulfur-modified gold substrate at elevated temperature, flat islands of ruthenium sulfide are formed exclusively. The flat islands are single-layer RuS2 nanocrystals with a (111) surface termination which exhibits an ordered array of sulfur vacancies. On such RuS2 (111) surfaces, excess sulfur is stable at low temperature and induces surface reconstruction, and desorbs at high temperature. The RuS2(111)/Au system provides an excellent model system for ruthenium sulfide catalysts.     

Importance of the Anchor Group Position (Para versus Meta) in Tetraphenylmethane Tripods: Synthesis and Self‐Assembly Features

The efficient synthesis of tripodal platforms based on tetraphenylmethane with three acetyl‐protected thiol groups in either meta or para positions relative to the central sp³ carbon for deposition on Au (111) surfaces is reported. These platforms are intended to provide a vertical arrangement of the substituent in position 4 of the perpendicular phenyl ring and an electronic coupling to the gold substrate. The self‐assembly features of both derivatives are analyzed on Au (111) surfaces by low‐temperature ultra‐high‐vacuum STM, high‐resolution X‐ray photoelectron spectroscopy, near‐edge X‐ray absorption fine structure spectroscopy, and reductive voltammetric desorption studies. These experiments indicated that the meta derivative forms a well‐ordered monolayer, with most of the anchoring groups bound to the surface, whereas the para derivative forms a multilayer film with physically adsorbed adlayers on the chemisorbed para monolayer. Single‐molecule conductance values for both tripodal platforms are obtained through an STM break junction experiment.     

The structure, growth and reactivity of electrodeposited Ru/Au(111) surfaces

In order to elucidate electronic effects on the oxidation of CO on small Ru clusters, we investigated this reaction on well defined Ru/Au(111) model systems via parallel in-situ STM studies of the structure and electrochemical deposition of Ru on Au(111) in H₂SO₄ solution and cyclic voltammetry of CO monolayer oxidation on these surfaces. The Ru deposit consists of nanoscale islands, which coalesce with increasing coverage. The Ru saturation coverage depends on the deposition potential, resulting in Ru submonolayer (>0.1 V), (defective) monolayer (≥−0.1 V), and multilayer films (<−0.1 V). At potentials >0.6 V irreversible formation of Ru oxide/hydroxide species is observed, which can be partly reduced in the range 0.4 to 0.0 V. CO stripping commences at ≈0.1 V and occurs over a broad potential range. From the stripping charge a local CO coverage on the Ru monolayer islands of 0.7 ML was estimated. The observed influence of the morphology of the Ru deposit on the CO stripping voltammetry is explained by (local) variations in the CO adsorption energy due to electronic modifications of the Ru film.     

Investigation of the Adsorption and Self Assembly of Isocyanide Derivatives on Au（111） Surface

The adsorption and self-assembly of isocyanide derivatives on Au（111） surface were investigated by density functional theory （DFF） and molecular dynamics simulation. The calculation for phenyl isocyanide by DFT was based on cluster and slab models. The self-assembled monolayers of 2-isocyanoazulene and 1,3-diethoxycarbony 1- 2-isocyanoazulene on Au（111） were simulated using Au-C force field parameters developed by us. It was found that the top site was the most preferred position, and the isocyanoazulene and its derivatives could form the ordered face to edge self-assembled monolayer on gold surface indeed, and the molecules stood on the gold surface vertically.     

Pb deposition on I-coated Au(111). UHV-EC and EC-STM studies

This article concerns the growth of an atomic layer of Pb on the Au(111)( radical3 x radical3)R30 degrees -I structure. The importance of this study lies in the use of Pb underpotential deposition (UPD) as a sacrificial layer in surface-limited redox replacement (SLRR). SLRR reactions are being applied in the formation of metal nanofilms via electrochemical atomic layer deposition (ALD). Pb UPD is a surface-limited reaction, and if it is placed in a solution of ions of a more noble metal, redox replacement can occur, but limited by the amount of Pb present. Pb UPD is a candidate for use as a sacrificial layer for replacement by any more noble element. It has been used by this group for both Cu and Pt nanofilm formation using electrochemical ALD. The I atom layer was intended to facilitate electrochemical annealing during nanofilm growth. Two distinctly different Pb atomic layer structures are reported, studied using in situ scanning tunneling microscopy (STM) with an electrochemical flow cell and ultrahigh vacuum surface analysis combined directly with electrochemical reactions (UHV-EC). Starting with the initial Au(111)( radical3 x radical3)R30 degrees -I, 1/3 monolayer of I on the Au(111) surface, Pb deposition began at approximately 0.1 V. The first Pb UPD structure was observed just below -0.2 V and displayed a (2 x radical3)-rect unit cell, for a structure composed of 1/4 monolayer each of Pb and I. The I atoms fit in Pb 4-fold sites, on the Au(111) surface. The structure was present in domains rotated by 120 degrees. Deposition to -0.4 V resulted in complete loss of the I atoms and formation of a Pb monolayer on the Au(111), which produced a Moiré pattern, due to the Pb and Au lattice mismatch. These structures represent two well-defined starting points for the growth of nanofilms of other more noble elements. It is apparent from these studies that the adsorption of I- on Pb is weak, and it will rinse away. If Pb is used as a sacrificial metal in an electrochemical ALD cycle and adsorbed I atoms are employed for electrochemical annealing, I atoms will need to be applied each cycle.     

Surface‐Confined Electropolymerization of Methylene Blue on Gold Electrodes

We report on the electrochemical behaviour and electropolymerization of self‐assembled monolayers (SAMs) of methylene blue (MB) on gold electrodes. The SAMs of MB on gold electrodes were prepared by immersing the substrates into a solution of 1.0 mM MB in absolute ethanol for different times at room temperature. Cyclic voltammetry experiments exhibited that reductive desorption of MB monolayer takes place at three different potentials on polycrystalline gold electrodes, while reductive desorption of MB monolayer consists of only one peak on single crystal Au(111) substrates. Calculated charge densities for different immersion times indicated that optimal immersion time for self‐assembly of MB is 96 h. Electropolymerization of SAMs of MB on gold electrode was achieved by applying 0.95 V for 1 s in 0.1 M borate buffer solution (pH: 9.0). It was observed that poly(MB) monolayers are highly stable in acidic media. ATR‐FTIR and UV‐vis spectra exhibited differences between monomer and polymer monolayers, which are attributed to surface‐confined electropolymerization. STM image of poly(MB) monolayer on Au(111) substrate revealed a surface that is covered by well‐ordered, collateral nanowires with an average size of 3 nm.     

Two-dimensional Molecular Phase Transition of Alkylated-TDPB on Au(111) and Cu(111) Surfaces

The derivatives of aromatic cores bearing alkyl chains with different lengths are of potential interest in on-surface chemistry, and thus have been widely investigated both at liquid-solid interfaces and in vacuum. Here, we report on the structural evaluation of self-assembled 1,3,5-tri(4-dodecylphenyl)benzene(TDPB) molecules with increased molecular coverages on both Au(111) and Cu(111) surfaces. As observed on Au(111), rhombic and herringbone structures emerge successively depending on surface coverage. In the case of Cu(111), the same process of phase conversion is also observed, but with two distinct structures. In comparison, the self-assembled structures on Au(111) surface are packed more densely than that on Cu(111) surface under the same preparation conditions. This may fundamentally result from the higher adsorption energy of TDPB molecules on Cu(111), restricting their adjustment to optimize a thermodynamically favorable molecular packing.     

Platinum nanofilm formation by EC-ALE via redox replacement of UPD copper: studies using in-situ scanning tunneling microscopy

The growth of Pt nanofilms on well-defined Au(111) electrode surfaces, using electrochemical atomic layer epitaxy (EC-ALE), is described here. EC-ALE is a deposition method based on surface-limited reactions. This report describes the first use of surface-limited redox replacement reactions (SLR(3)) in an EC-ALE cycle to form atomically ordered metal nanofilms. The SLR(3) consisted of the underpotential deposition (UPD) of a copper atomic layer, subsequently replaced by Pt at open circuit, in a Pt cation solution. This SLR(3) was then used a cycle, repeated to grow thicker Pt films. Deposits were studied using a combination of electrochemistry (EC), in-situ scanning tunneling microscopy (STM) using an electrochemical flow cell, and ultrahigh vacuum (UHV) surface studies combined with electrochemistry (UHV-EC). A single redox replacement of upd Cu from a PtCl(4)(2-) solution yielded an incomplete monolayer, though no preferential deposition was observed at step edges. Use of an iodine adlayer, as a surfactant, facilitated the growth of uniformed films. In-situ STM images revealed ordered Au(111)-(square root 3 x square root 3)R30 degrees-iodine structure, with areas partially distorted by Pt nanoislands. After the second application, an ordered Moiré pattern was observed with a spacing consistent with the lattice mismatch between a Pt monolayer and the Au(111) substrate. After application of three or more cycles, a new adlattice, a (3 x 3)-iodine structure, was observed, previously observed for I atoms adsorbed on Pt(111). In addition, five atom adsorbed Pt-I complexes randomly decorated the surface and showed some mobility. These pinwheels, planar PtI(4) complexes, and the ordered (3 x 3)-iodine layer all appeared stable during rinsing with blank solution, free of I(-) and the Pt complex (PtCl(4)(2-)).     

Deposition of tetracene on GaSe passivated Si(111)

The growth of tetracene on GaSe half-sheet passivated Si(111) is investigated under ultrahigh vacuum (UHV) using low-energy electron diffraction (LEED) and photoelectron spectroscopy (PS). A highly ordered thin-film growth was observed in the initial stages of the deposition process. All proposed structures form a coincidence lattice with the underlying substrate, due to the influence of the molecule-substrate interactions and are built up by either flat lying tetracene molecules at low coverage or tilted molecules at higher coverages. Photoelectron spectroscopy (XPS/UPS) shows that the deposited tetracene molecules induce band bending in the silicon substrate. No band bending was observed in the tetracene film, and an interface dipole potential of 0.45 eV was measured between the GaSe passivated Si(111) surface and the tetracene film.     

Sb在Au单晶电极上结构敏感吸附行为的比较

本文研究比较Sb(III)在Au(111)和Au(100)电极上的不可逆吸附与还原和Sb的欠电位沉积行为及其相互影响.现场扫描隧道显微镜和循环伏安法测试结果表明,基底表面结构不仅影响阴离子的吸附行为和Sb的吸附结构,而且还影响其自身结构的稳定性.在Au(111)表面,致密无序膜的SbO+不可逆吸附层还原后基本保持原有的无序结构;而在Au(100)表面,由于SO42-的共吸附,不可逆吸附物种还原后形成(2×2)有序结构.在Au(111)表面上,Sb的欠电位沉积伴随显著的合金化,且因表面有序结构的破坏而形成沟道状二维结构;但对Au(100)表面,由于其晶格和尺寸与稳定的AuSb2合金之(100)面有较好的匹配性,使Au与Sb得以形成有序的表面化合物,从而避免了欠电位沉积过程中的表面合金化问题,进一步体现基底结构的敏感性和重要性.     

Oriented organic islands and one-dimensional chains on a Au(111) surface fabricated by electrodeposition: an STM study

Organic islands and oriented one-dimensional (1D) chains are fabricated on a Au(111) surface by electrodeposition. The cyclic voltammograms (CVs) of Au(111) in solutions containing nitrobenzene and picric acid show an electrochemical reaction in a negative potential region, which results in irreversible reductive deposition. The deposition process is monitored by in situ electrochemical scanning tunneling microscopy (ECSTM). At the double layer potential region, for example, nitrobenzene molecules form a well-defined adlayer in a (square root(3) x square root(3)) structure. With potential shifting negative to the reductive region, nitrobenzene is reduced to hydroxyaminobenzene. Organic islands were formed first and then aggregated into ordered 1D chains. The formation of these organic islands and 1D chains is completely potential-dependent. Intriguingly, the so-prepared islands and 1D chains are well-oriented along the reconstructed lines of the underlying Au(111) substrate and stable under ambient conditions even if the sample was removed from electrolyte solution. The results reported here provide a simple and effective method to fabricate oriented organic nanodots and nanowires on a solid surface by an electrochemical technique.     

Halogen-substituted thiophenol molecules on Cu(111)

Para-halosubstituted thiophenols (X-TPs, where X is Br, Cl, or F) form ordered islands and monolayers on Cu(111) at temperatures as low as 81 K. At incomplete coverages, all X-TPs adsorb with the dehydrogenated thiol group attached to the substrate and the substituted ring inclined toward the surface, as verified experimentally and theoretically. The structure of ordered islands has a pronounced dependence on the nature of the halogen substituent: while unsubstituted TP and pentafluoro-TP molecules do not self-assemble into extended ordered patterns at 81 K, X-TP molecules form a range of different structures which depend both on the size and electronegativity of the substituent, as well as on the coverage.     

Structural evolution of perfluoro-pentacene films on Ag(111): transition from 2D to 3D growth

The structural evolution and thermal stability of perfluoro-pentacene (PF-PEN) thin films on Ag(111) have been studied by means of low-temperature scanning tunnelling microscopy (STM), low-energy electron diffraction (LEED), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and thermal desorption spectroscopy (TDS). Well-defined monolayer films can be prepared by utilizing the different adsorption energy of mono- and multilayer films and selectively desorbing multilayers upon careful heating at 380 K, whereas at temperatures above 400 K, a dissociation occurs. In the first monolayer, the molecules adopt a planar adsorption geometry and form a well-ordered commensurate (6 × 3) superstructure where molecules are uniformly oriented with their long axis along the <110> azimuth. This molecular orientation is also maintained in the second layer, where molecules exhibit a staggered packing motif, whereas further deposition leads to the formation of isolated, tall islands. Moreover, on smooth silver surfaces with extended terraces, growth of PF-PEN onto beforehand prepared long-range ordered monolayer films at elevated temperature leads to needle-like islands that are uniformly aligned at substrate steps along <110> azimuth directions.