Molecular-scale investigation of tolane disulfide self-assembled monolayers on Au(111) using scanning tunneling microscopy

Molecular-scale surface structures of self-assembled monolayers (SAMs) formed by the spontaneous adsorption of tolane disulfides (TDS) on Au(111) in a 1 mM mixed solution of ethanol/N, N'-dimethylformamide (9:1) were examined using scanning tunneling microscopy (STM). The STM study revealed that TDS SAMs formed after a 24 h immersion at room temperature were composed of two-dimensional (2D) ordered phases with inhomogeneous surface morphologies and no clear domain boundaries. However, after 2 h immersion at 50 degrees C, uniform 2D ordered domains with clear domain boundaries were observed, which could be described as c(3 x square root of 3) structures with centered rectangular unit cell. Interestingly, a unique intermediate ordered phase with a low surface coverage was also observed. After a longer immersion for 24 h at 50 degrees C, only the uniform c(3 x square root of 3) domains were observed with a corrugation that may have reflected surface reconstruction of the Au(111) surfaces. From this study, we found that 2D ordered TDS SAMs with large and uniform domains on Au(111) can be obtained by controlling the solution temperature and immersion time.     

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.     

Quasi‐Epitaxial Growth of Magnetic Nanostructures on 4H‐Au Nanoribbons

Phase engineering of nanomaterials is an effective strategy to tune the physicochemical properties of nanomaterials for various promising applications. Herein, by using the 4H‐Au nanoribbons as templates, four novel magnetic nanostructures, namely 4H‐Au @ 14H‐Co nanobranches, 4H‐Au @ 14H‐Co nanoribbons, 4H‐Au @ 2H‐Co nanoribbons, and 4H‐Au @ 2H‐Ni nanoribbons, are synthesized based on the quasi‐epitaxial growth. Different from the conventional epitaxial growth of metal nanomaterials, the obtained Co and Ni nanostructures possess different crystal phases from the Au template. Due to the large lattice mismatch between Au and the grown metals (i.e., Co and Ni), ordered misfit dislocations are generated at the Co/Au and Ni/Au interfaces. Notably, a new super‐structure of Co is formed, denoted as 14H. Both 4H‐Au @ 14H‐Co nanobranches and nanoribbons are ferromagnetic at room temperature, showing similar Curie temperature. However, their magnetic behaviors exhibit distinct temperature dependence, resulting from the competition between spin and volume fluctuations as well as the unique geometry. This work paves the way to the templated synthesis of nanomaterials with unconventional crystal phases for the exploration of phase‐dependent properties.     

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.     

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.     

Chiral‐Selective Formation of 1D Polymers Based on Ullmann‐Type Coupling: The Role of the Metallic Substrate

The chiral‐selective formation of 1D polymers from a prochiral molecule, namely, 6,12‐dibromochrysene in dependence of the type of metal surface is demonstrated by a combined scanning tunneling microscopy and density functional theory study. Deposition of the chosen molecule on Au(111) held at room temperature leads to the formation of a 2D porous molecular network. Upon annealing at 200 °C, an achiral covalently linked polymer is formed on Au(111). On the other hand, a chiral Cu‐coordinated polymer is spontaneously formed upon deposition of the molecules on Cu(111) held at room temperature. Importantly, it is found that the chiral‐selectivity determines the possibility of obtaining graphene nanoribbons (GNRs). On Au(111), upon annealing at 350 °C or higher cyclo‐dehydrogenation occurs transforming the achiral polymer into a GNR. In contrast, the chiral coordination polymer on Cu(111) cannot be converted into a GNR.     

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.     

TEM investigation of self-organized PbSe quantum dots as a function of spacer layer thickness and growth temperature

PbSe quantum dot/PbEuTe superlattices were grown on PbTe/BaF₂(111) using molecular beam epitaxy. The spacer thickness was varied from 32.4 to 312 nm and the growth temperature was 335 or 380°C. Three different dot stacking sequences form with either vertical, face-centered cubic like or disordered stacking sequence along the [111] growth direction. The different stacking sequence can be controlled by the thickness of the spacer layer and the growth temperature. The dots are fully strained and the shape of the dots is either triangular pyramids or dome like depending on the spacer layer thickness. An analysis of the lateral and vertical correlation of the dots as well as the size and shape of the buried dots with respect to spacer thickness and growth temperature is presented.     

Lateral diffusion of thiol ligands on the surface of au nanoparticles: an electron paramagnetic resonance study

The lateral mobility of the thiolate ligands on the surface of Au nanoparticles was probed by EPR spectroscopy. This was achieved by using bisnitroxide ligands, which contained a disulfide group (to ensure attachment to the Au surface) and a cleavable ester bridge connecting the two spin-labeled branches of the molecule. Upon adsorption of these ligands on the surface of Au nanoparticles, the two spin-labeled branches were held next to each other by the ester bridge as evidenced by the spin-spin interactions. Cleavage of the bridge removed the link that kept the branches together. CW and pulsed EPR (DEER) experiments showed that the average distance between the adjacent thiolate branches on the Au nanoparticle surface only marginally increased after cleaving the bridge and thermal treatment. This implies that the lateral diffusion of thiolate ligands on the nanoparticle surface is very slow at room temperature and takes hours even at elevated temperatures (90 degrees C). The changes in the distance distribution observed at high temperature are likely due to ligands hopping between the nanoparticles rather than diffusing on the particle surface.     

Octithiophene on Cu(III) and Au(III): formation and electronic structure of molecular chains and films

Adsorption and electronic structure of octithiophene (8T) molecules on Cu(III) and Au(III) surfaces are investigated using scanning tunneling microscopy (STM) and spectroscopy (STS) at room temperature. We find a large difference in adsorption behavior of 8T molecules on the two surfaces. At the initial stage of adsorption, 8T molecules are stabilized in the form of molecular chain on a terrace of Cu(III), whereas neither such chain structure nor isolated 8T molecules have been observed on a terrace of Au(III). By increasing the amount of adsorbed molecules, a disordered monolayer film is formed on Cu(III) while a well-ordered monolayer film is formed on Au(III). From the spectroscopic investigations using bias-dependent STM images and STS spectra and by comparing the data with theoretical calculations, it is found that the electronic property of 8T molecules in the molecular chain on Cu(III) is different from that of a free-standing 8T molecule while that in the monolayer film on Au(III) keeps original character of the free-standing 8T molecule. The present study shows that adsorption of 8T molecules on Cu(III) results in a formation of adsorption-induced states near the Fermi level.     

Stability of electric characteristics of Au films on Si(111)5.55 × 5.55-Cu surface exposed to oxygen

Dependence of the surface electric conductivity of the layered Au/Si(111)5.55 × 5.55-Cu structure on the thickness of Au film and exposure in oxygen has been studied using low-energy electron diffraction, Auger electron spectroscopy, and four-point-probe conductivity measurements. The samples were obtained by depositing Au (1–5 monolayers, ML) in vacuum at room temperature onto preliminary prepared Si(111)5.55 × 5.55-Cu surface, after which the structure was kept in oxygen (to a total exposure varied within 0–14000 L) at room temperature. It is established that the increasing oxygen exposure of both the initial and Si(111)5.55 × 5.55-Cu surface and that coated with gold to 1–3 ML leads to a significant decrease in the surface conductivity of samples. In contrast, the conductivity of samples coated with more than 3 ML of gold remains almost unchanged, which is explained by the fact that a continuous Au film is formed in this case on the Si(111)5.55 × 5.55-Cu surface.     

Interactions of NO2 with sewage sludge based composite adsorbents

Interactions of NO2 present in most air were analyzed at room temperature on composite sewage sludge-derived adsorbents. They consist of carbonaceous and inorganic phases with the majority of the latter. The adsorption capacity was evaluated using the dynamic breakthrough experiments. The materials before and after NO2 exposure were characterized using adsorption of nitrogen, thermal analysis and FTIR. The results showed differences in the surface activities of sludge-derived materials towards immobilization and reduction of nitric dioxide. Nitrates and nitrite are the main products of surface reactions. This is linked to the presence of active oxides and hydroxides, which are formed when the surface is exposed to water. The highest activity of the sample pyrolyzed at 650 degrees C is owing to the high content of those species formed as a result of decomposition of inorganic salts (likely chlorides, sulfates and phosphates) during thermal treatment. When sludge is pyrolyzed at 950 degrees C those oxides are engaged in stable mineral phases formed in solid-state reactions, which limits the surface activity towards NO2 retention. The reactivity of the high temperature pyrolyzed samples can be linked to the physical adsorption of water. In a water film nitrous and nitric acid can be formed and they can further react with inorganic and carbonaceous phases to the limited extent.     

pH-dependent adsorption of Au nanoparticles on chemically modified Si3N4 MEMS devices

Microelectromechanical systems (MEMS) are devices that represent the integration of mechanical and electrical components in the micrometer regime. Self-assembled monolayers (SAMs) can be used to functionalise the surface of MEMS resonators in order to fabricate chemically specific mass sensing devices. The work carried out in this article uses atomic force microscopy (AFM) and X-ray photoemission spectroscopy (XPS) data to investigate the pH-dependent adsorption of citrate-passivated Au nanoparticles to amino-terminated Si₃N₄ surfaces. AFM, XPS and mass adsorption experiments, using ‘flap’ type resonators, show that the maximum adsorption of nanoparticles takes place at pH = 5. The mass adsorption data, obtained using amino functionalised ‘flap’ type MEMS resonators, shows maximum adsorption of the Au nanoparticles at pH = 5 which is in agreement with the AFM and XPS data, which demonstrates the potential of such a device as a pH responsive nanoparticle detector.     

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.     

Cyano‐Functionalized Triarylamines on Au(111): Competing Intermolecular versus Molecule/Substrate Interactions

The self‐assembly of cyano‐substituted triarylamine derivatives on Au(111) is studied with scanning tunneling microscopy and density functional theory calculations. Two different phases, each stabilized by at least two different cyano bonding motifs are observed. In the first phase, each molecule is involved in dipolar coupling and hydrogen bonding, while in the second phase, dipolar coupling, hydrogen bonding and metal‐ligand interactions are present. Interestingly, the metal–ligand bond is already observed for deposition of the molecules with the sample kept at room temperature leaving the herringbone reconstruction unaffected. It is proposed that for establishing this bond, the Au atoms are slightly displaced out of the surface to bind to the cyano ligands. Despite the intact herringbone reconstruction, the Au substrate is found to considerably interact with the cyano ligands affecting the conformation and adsorption geometry, as well as leading to correlation effects on the molecular orientation.     

Interface dipole formation of different ZnPcCl(8) phases on Ag(111) observed by Kelvin probe force microscopy

Recently, we investigated the adsorption of octachloro zinc phthalocyanine (ZnPcCl(8)) on Ag(111) by scanning tunneling microscopy. Compared to the standard phthalocyanine, halogenated phthalocyanine molecules show a much more complex binding behavior, which results in the formation of three different structural phases. These phases follow from the ordering process with the formation of 8, 4 and 0 intermolecular hydrogen-halogen bonds (Abel et al 2006 ChemPhysChem?7 82). In the present work we investigate these phases by Kelvin probe force microscopy in order to quantitatively deduce the electric interface barrier of the first monolayer. Our measurements reveal that the binding behavior does not only affect the structural ordering but also the interface dipole formation, which leads to different work functions. The fact that we observe interface barriers of opposite signs between ordered and disordered molecular layers underlines the importance of exactly knowing the molecular arrangement at the interface when assembling organic molecule devices.     

Stripe domain analysis of alkanethiol and alkynethiol monolayers self-assembled on the surfaces of gold grains

The self-assembled monolayers (SAMs) of alkanethiols such as 1-dodecanethiol (DDT) on the surface of polycrystalline gold grain on quartz crystal microbalance (QCM) at room temperature and alkynethiols such as phenylethynyl thiol (PET) on the surface of Au(111)/mica under − 65 °C have been fabricated. A multimode scanning probe microscope (SPM) investigation for the first time reveals the formation of stripe domain of DDT SAMs together with roundish domain. This feature was not caused by an annealing treatment but might be induced by coexistence of a few different facets and reconstruction of the surface on the grain. The stripe domain of PET SAMs could also be found on the surface of the grain, which was within the substrate of the gold/mica. It shows that the feature of the stripe domain for organothiol monolayers self-assembled on gold grain surfaces possesses a certain generality. Furthermore, the arrangement of organothiol stripe domain can be well understood from the interpretation of the relationship between the stripe width and width direction, molecule interval distance, molecule length and tilt angles of the thiols.     

Fabrication and AFM investigation of the temperature-dependent surface morphology of Au (100) single crystal ultramicroelectrodes

A previously reported method for preparation of gold (111) single-crystal utramicroelectrodes (scumes) has been used to fabricate gold (100) scumes with effective diameters from 20 to 50 microm. Cyclic voltammograms for these ultramicroelectrodes obtained in perchloric acid show similar features to gold (100) single-crystal electrodes of more conventional sizes, but with differences that are a result of different surface preparation methods used before the measurement. The gold crystals used to prepare Au (100) scumes were grown at room temperature so that the cyclic voltammetric characteristics reflect the unique properties of a room temperature-ordered surface. The AFM images of the (100) facets of these crystals are also presented. The effects of annealing Au (100) at 800 degrees C for a short time were studied both electrochemically and using AFM and are discussed with respect to the data obtained for crystals grown at room temperature.     

Interfacial reaction between Au and Sn films electroplated for LED bumps

Au-20 wt% Sn eutectic solder is used as bumps in flip chip package of power LED (Light Emitting Diode) due to its excellent properties. The Au/Sn dual-layer films were fabricated on Si wafer by pulse electroplating of Au and Sn sequentially, and the solid?Csolid interfacial reaction during aging and the eutectic reaction during reflow soldering were investigated in the present work. After storage at room temperature for 1 week, three phases of AuSn, AuSn₂ and AuSn₄ were sequentially formed at the Au/Sn (10 ??m/10 ??m) interface, and the thickness of this reaction region was about 5 ??m. Firstly, AuSn₄ was formed at the Au/Sn interface, and then AuSn and AuSn₂ were formed at the Au/AuSn₄ interface. After aging at 150 °C for 5 and 10 h, a similar layered structure of AuSn/AuSn₂/AuSn₄ was also observed. Due to the faster diffusion of Au to Sn layer, all the Sn elements were consumed after aging at 150 °C for 15 h and AuSn₄ layer gradually transformed into AuSn and AuSn₂ layers. For the specimen of Au/Sn (9 ??m/6 ??m) films on Si chip, a bamboo-shoot-like microstructure of Au₅Sn/AuSn/AuSn₂ was formed in the reaction region after reflowed at 280 °C for 10 s; while a typical two-phase (Au₅Sn and AuSn) eutectic microstructure was formed after reflowed at 280 °C for 60 s.     

Alkyl chain conformation of octadecylsilane stationary phases by Raman spectroscopy. 1. Temperature dependence

Raman spectroscopy is used for the first time to probe the effect of temperature on the conformational order of polymeric and monomeric octadecylsilane stationary phases. Spectral data in the ν(C-C) and ν(C-H) regions are interpreted in terms of alkyl chain conformational state and its dependence on temperature. In contrast to the liquidlike disordered state characteristic of these stationary phases at room temperature, at liquid N(2) temperatures, the alkyl chains exist in a more ordered state with a residual level of gauche conformational defects. Systematic studies between -15 and 95 °C reveal more subtle changes in conformational order as ascertained from empirical spectral indicators including the intensity ratios I[ν(a)(CH(2))]/I[ν(s)(CH(2))] and I[ν(C-C)(T)]/I[ν(C-C)(G)]. Plots of these ratios as a function of temperature reveal two distinct regimes of behavior. By extrapolating the linear regions of these plots, a surface "phase transition" temperature of ～20 °C for both surface-confined octadecylsilane stationary phases is estimated that represents subtle changes in alkyl chain conformational order from a more ordered phase to a slightly more disordered phase. The similarity in behavior between the polymeric and monomeric octadecylsilane stationary phases is interpreted as evidence for similar interchain spacing of the alkylsilanes on these silica surfaces.