Electron transport and redox reactions in carbon-based molecular electronic junctions

A unique molecular junction design is described, consisting of a molecular mono- or multilayer oriented between a conducting carbon substrate and a metallic top contact. The sp2 hybridized graphitic carbon substrate (pyrolyzed photoresist film, PPF) is flat on the scale of the molecular dimensions, and the molecular layer is bonded to the substrate via diazonium ion reduction to yield a strong, conjugated C-C bond. Molecular junctions were completed by electron-beam deposition of copper, titanium oxide, or aluminium oxide followed by a final conducting layer of gold. Vibrational spectroscopy and XPS of completed junctions showed minimal damage to the molecular layer by metal deposition, although some electron transfer to the molecular layer resulted in partial reduction in some cases. Device yield was high (>80%), and the standard deviations of junction electronic properties such as low voltage resistance were typically in the range of 10-20%. The resistance of PPF/molecule/Cu/Au junctions exhibited a strong dependence on the structure and thickness of the molecular layer, ranging from 0.13 ohms cm2 for a nitrobiphenyl monolayer, to 4.46 ohms cm2 for a biphenyl monolayer, and 160 ohms cm2 for a 4.3 nm thick nitrobiphenyl multilayer. Junctions containing titanium or aluminium oxide had dramatically lower conductance than their PPF/molecule/Cu counterparts, with aluminium oxide junctions exhibiting essentially insulating behavior. However, in situ Raman spectroscopy of PPF/nitroazobenzene/AlO(x)/Au junctions with partially transparent metal contacts revealed that redox reactions occurred under bias, with nitroazobenzene (NAB) reduction occurring when the PPF was biased negative relative to the Au. Similar redox reactions were observed in PPF/NAB/TiO(x)/Au molecular junctions, but they were accompanied by major effects on electronic behavior, such as rectification and persistent conductance switching. Such switching was evident following polarization of PPF/molecule/TiO2/Au junctions by positive or negative potential pulses, and the resulting conductance changes persisted for several minutes at room temperature. The "memory" effect implied by these observations is attributed to a combination of the molecular layer and the TiO2 properties, namely metastable "trapping" of electrons in the TiO2 when the Au is negatively biased.     

Electronic characteristics of fluorene/TiO2 molecular heterojunctions

The electronic properties of molecular junctions of the general type carbon/molecule/TiO2Au were examined as examples of "molecular heterojunctions" consisting of a molecular monolayer and a semiconducting oxide. Junctions containing fluorene bonded to pyrolyzed photoresist film (PPF) were compared to those containing Al2O3 instead of fluorene, and those with only the TiO2 layer. The responses to voltage sweep and pulse stimulation were strongly dependent on junction composition and temperature. A transient current response lasting a few milliseconds results from injection and trapping of electrons in the TiO2 layer, and occurred in all three junction types studied. Conduction in PPFTiO2Au junctions is consistent with space charge limited conduction at low voltage, then a sharp increase in current once the space charge fills all the traps. With fluorene present, there is a slower, persistent change in junction conductance which may be removed by a reverse polarity pulse. This "memory" effect is attributed to a redox process in the TiO2 which generates TiIII and/or TiII, which have much higher conductance than TiO2 due to the presence of conduction band electrons. The redox process amounts to "dynamic doping" of the TiO2 layer by the imposed electric field. The memory effect arises from a combination of the properties of the molecular and oxide layers, and is a special property of the molecular heterojunction configuration.     

Conducting polymer memory devices based on dynamic doping

Molecular electronic junctions consisting of a 20 nm thick layer of polypyrrole (PPy) and 10 nm of TiO2 between conducting layers of carbon and gold were investigated as potential nonvolatile memory devices. By making the polymer layer much thinner than conventional polymer electronic devices, it is possible to dynamically oxidize and reduce the polypyrrole layer by an applied bias. When the electrode in contact with the PPy is biased positive, oxidation of the PPy occurs to yield a conducting polaron state. The junctions exhibit a large increase in conductance in response to the positive bias, which is reversed by a subsequent negatively biased pulse. Switching between the conducting and nonconducting state can occur for pulses at least as short as 10 micros, and the conducting state persists after a positive bias pulse for at least 1 week. The read/write/read/erase cycle may be repeated for at least 1700 cycles, although with an error rate of approximately 3% due mainly to an incomplete "erase" step. The speed and retention of the PPy/TiO2 junctions are far superior to those of the analogous fluorene/TiO2 devices lacking the polymer, and the conductance changes are absent if SiO2 is substituted for TiO2. The observations are consistent with "dynamic doping" of the solid-state polymer layer, with the possible involvement of adventitious mobile ions. Although the speed of the current polymer/TiO2 junctions is slower than commercial dynamic random access memory, their retention is approximately 5 orders of magnitude longer.     

In situ Raman spectroscopy of bias-induced structural changes in nitroazobenzene molecular electronic junctions

Carbon/nitroazobenzene (NAB)/titanium/gold molecular electronic junctions with active thicknesses of 7-8 nm were constructed having partially transparent Ti/Au top contacts, which permitted in situ monitoring of molecular structure with Raman spectroscopy for applied biases between +3 and -3 V. Deposition of the Ti/Au top contacts resulted in spectral changes similar to those accompanying NAB reduction in a conventional spectroelectrochemical experiment. Upon application of +3 V (carbon relative to Ti), the spectrum indicated reoxidation of the NAB reduction product, and this redox cycle could be repeated at least three times. When a voltage excursion to -2 or -3 V occurred, the spectra indicated irreversible loss of the nitro group, and a dramatic but reversible decrease in Raman intensity over the entire shift range examined. Negative applied voltage causes formation of reduced NAB and a high oxidation state of titanium, while positive voltage forms oxidized NAB and injects electrons into the titanium oxide layer. The spectral changes were correlated with current/voltage curves in order to probe the mechanism of rectification and conductance switching reported previously. Overall, the combination of spectroscopic and voltammetric results implies a conduction mechanism involving both NAB and titanium oxide, possibly mediated by the injection of carriers into the semiconducting titanium oxide, or by reduction of an insulating titanium oxide to a more conductive form.     

Strong effects of molecular structure on electron transport in carbon/molecule/copper electronic junctions

Carbon/molecule/copper molecular electronic junctions were fabricated by metal deposition of copper onto films of various thicknesses of fluorene (FL), biphenyl (BP), and nitrobiphenyl (NBP) covalently bonded to flat, graphitic carbon. A "crossed-wire" junction configuration provided high device yield and good junction reproducibility. Current/voltage characteristics were investigated for 69 junctions with various molecular structures and thicknesses and at several temperatures. The current/voltage curves for all cases studied were nearly symmetric, scan rate independent, repeatable at least thousands of cycles and exhibited negligible hysteresis. Junction conductance was strongly dependent on the dihedral angle between phenyl rings and on the nature of the molecule/copper "contact". Junctions made with NBP showed a decrease in conductivity of a factor of 1300 when the molecular layer thickness increased from 1.6 to 4.5 nm. The slope of ln(i) vs layer thickness for both BP and NBP was weakly dependent on applied voltage and ranged from 0.16 to 0.24 A(-1). These attenuation factors are similar to those observed for similar molecular layers on modified electrodes used to study electrochemical kinetics. All junctions studied showed weak temperature dependence in the range of approximately 325 to 214 K, implying activation barriers in the range of 0.06 to 0.15 eV. The carbon/molecule/copper junction structure provides a robust, reproducible platform for investigations of the dependence of electron transport in molecular junctions on both molecular structure and temperature. Furthermore, the results indicate that junction conductance is a strong function of molecular structure, rather than some artifact resulting from junction fabrication.     

Structure and Electron Transport at Metal Atomic Junctions Doped with Dichloroethylene

We have investigated the structure and electron transport at dichloroethylene-doped metal atomic junctions at low temperatures (20 K) in ultra-high vacuum, using Fe, Ni, Pd, Cu, Ag, and Au. The metal atomic junctions were fabricated using the mechanically controllable break junction technique. After introducing the dichloroethylene (DCE), the conductance behavior of Fe, Ni, and Pd junctions was considerably changed, whereas little change was observed for Cu, Ag, and Au. For the Pd and Cu junctions, a clear peak was observed in their conductance histograms, showing that the single-molecule junction was selectively formed. To investigate the structure of the metal atomic junctions further, their plateau lengths were analyzed. The length analysis revealed that the Au atomic wire was elongated, and the metal atomic wires were formed for the other transition metals: those that do not normally form metal atomic wires without DCE doping, as DCE adsorption stabilized the metal atomic states. There is a strong interaction between DCE and the metals, where DCE supports the formation of the metal atomic wire for Fe, Ni, and Pd.     

基于电化学方法研究以铜和银为电极的对苯二甲酸单分子结电导

利用基于电化学跳跃接触的扫描隧道显微镜裂结法(ECSTM-BJ), 通过现场形成金属电极, 对以Cu和Ag为电极的对苯二甲酸单分子结电导进行了测量. 研究结果表明: 利用该方法对所有数据直接线性统计即可得到很好结果; 两种电极下都存在两套高和低电导值, 其中以Cu为电极的单分子结电导高低值分别为11.5和4.0 nS, 而以Ag为电极的单分子结电导分别为10.3和3.8 nS, 高值都约为低值的3倍, 且以Cu为电极的单分子结电导要略大于以Ag为电极的电导, 可归结于电极和分子的耦合不同造成的. 与同样条件下测量得到的烷基链羧酸单分子结电导只存在一套值相比,对苯二甲酸表现出两套电导值, 反应了分子内主链对分子结电导的影响.     

Electron-beam evaporated silicon as a top contact for molecular electronic device fabrication

This paper discusses the electronic properties of molecular devices made using covalently bonded molecular layers on carbon surfaces with evaporated silicon top contacts. The Cu "top contact" of previously reported carbon/molecule/Cu devices was replaced with e-beam deposited Si in order to avoid Cu oxidation or electromigration, and provide further insight into electron transport mechanisms. The fabrication and characterization of the devices is detailed, including a spectroscopic assessment of the molecular layer integrity after top contact deposition. The electronic, optical, and structural properties of the evaporated Si films are assessed in order to determine the optical gap, work function, and film structure, and show that the electron beam evaporated Si films are amorphous and have suitable conductivity for molecular junction fabrication. The electronic characteristics of Si top contact molecular junctions made using different molecular layer structures and thicknesses are used to evaluate electron transport in these devices. Finally, carbon/molecule/silicon devices are compared to analogous carbon/molecule/metal junctions and the possible factors that control the conductance of molecular devices with differing contact materials are discussed.     

Molecular conductance switch-on of single ruthenium complex molecules

Thiol-tethered Ru(II) terpyridine complexes were synthesized for a voltage-driven molecular switch and used to understand the switch-on mechanism of the molecular switches of single metal complexes in the solid-state molecular junction in a vacuum. Molecularly resolved scanning tunneling microscopy (STM) images revealed well-defined single Ru(II) complexes isolated in the highly ordered dielectric monolayer. When a negative sample-bias was applied, the threshold voltage to the high conductance state in the molecular junctions of the Ru(II) complex was consistent with the electronic energy gap between the Fermi level of the gold substrate and the lowest ligand-centered redox state of the metal complex molecule. As an active redox center leading to conductance switching in the molecule, the lowest ligand-centered redox state of Ru(II) complexes was suggested to trap an electron injected from the gold substrate. Our suggestions for a single-molecule switch-on mechanism in the solid state can provide guidance in a design that improves the charge-trapping efficiency of the ligands with different metal substrates.     

Effect of Asymmetric Anchoring Groups on Electronic Transport in Hybrid Metal/Molecule/Graphene Single Molecule Junctions

A combined experimental and theoretical study on molecular junctions with asymmetry in both the electrode type and in the anchoring group type is presented. A scanning tunnelling microscope is used to create the “asymmetric” Au-S-(CH₂)n-COOH-graphene molecular junctions and determine their conductance. The measurements are combined with electron transport calculations based on density functional theory (DFT) to analyze the electrical conductance and its length attenuation factor from a series of junctions of different molecular length (n). These results show an unexpected trend with a rather high conductance and a smaller attenuation factor for the Au-S-(CH₂)_n-COOH-graphene configuration compared to the equivalent junction with the “symmetrical” COOH contacting using the HOOC-(CH₂)_n-COOH series. Owing to the effect of the graphene electrode, the attenuation factor is also smaller than the one obtained for Au/Au electrodes. These results are interpreted through the relative molecule/electrode couplings and molecular level alignments as determined with DFT calculations. In an asymmetric junction, the electrical current flows through the less resistive conductance channel, similarly to what is observed in the macroscopic regime.     

Static investigation of adsorption and hetero‐diffusion of copper,silver, and gold adatoms on the (111) surface

In this work, we have used the static molecular simulations combined with an interatomic potential derived from the embedded‐atom method to study the adsorption and hetero‐diffusion on the (111) surface of Cu, Ag, and Au adatoms by using LAMMPS code. The investigation is performed for six heterogeneous systems such as Ag/Au(111), Ag/Cu(111), Au/Ag(111), Au/Cu(111), Cu/Ag(111), and Cu/Au(111). First, we have investigated the relaxation trends and the bond lengths of the atoms in the systems. The calculation results show that, the top layer spacing between the first and second layers of the Au(111), Ag(111), and Cu(111) substrates is contracted. This contraction is found to be more important in the Au(111) substrate. On the other hand, the strong reduction of the binding length is found in Au/Cu(111) for the different adsorption sites. In addition, the binding, adsorption, and static activation energies for all studied systems were examined. The results indicated that the binding and adsorption energies reached their maximum values in the Au/Cu(111) and Au/Ag(111) systems, respectively. Moreover, the static activation barriers for hopping diffusion on the (111) surfaces are found to be low compared with those found in the (100) and (110) surfaces. Therefore, our calculations showed that the difference in energy between the hcp and fcc sites on the (111) surfaces is very small. Copyright © 2017 John Wiley & Sons, Ltd.     

Preparation of highly uniform Ag/TiO2 and Au/TiO2 supported nanoparticle catalysts by photodeposition

Photodeposition of Ag nanoparticles on commercial TiO2 particles and nanoparticles was performed in order to provide direct visualization of the spatial distribution of photoactive sites on sub-micrometer-scale and nanoscale TiO2 particle surfaces and to create materials for potential catalytic applications. HRTEM (high-resolution transmission electron microscopy) and HAADF-STEM (high-angle annular dark-field scanning transmission electron microscopy) were used to characterize these materials. The size and spatial distributions of the Ag nanoparticles on the commercial TiO2 were not uniform; the concentration of Ag was higher on grain boundaries and at the edges of these submicrometer particles. In the case of TiO2 nanoparticles, the size distribution of the Ag nanoparticles deposited was relatively uniform and independent of irradiation time and photon energy. The amount of Ag deposited on TiO2 nanoparticles was at least 6 times higher than that on the commercial samples for comparable irradiation conditions. Compared to the case of Ag photodeposition, the difference in the amount of Au photodeposited on TiO2 particles and nanoparticles was even greater, especially at low precursor concentrations. Photodeposition on TiO2 nanoparticles is suggested as a potential method for the preparation of Au/TiO2 catalysts, as loadings in excess of 10 wt % of uniform 1 nm metal particles were achieved in this work.     

Au-MgB2-Au纳米结点的负微分电阻效应

运用密度泛函理论结合非平衡格林函数的方法对MgB2直线原子链与两半无限Au（100）电极构成纳米结点的电子输运特性进行了第一性原理计算．在模拟Au-MgB2-Au纳米结点的拉伸过程中,计算了结点在不同距离下的结合能与电导．结果发现结点的Au-B键长为1．90A,B-Mg键长为2．22A时,结合能最大,结构最稳定,此时结点平衡电导为0．51G0（G0=2e^0／h）．通过计算投影态密度发现电子通过结点时主要是通过B、Mg原子的px和py电子轨道形成的π键进行传输的．在-1．5～1．5V的电压范围内,结点的电流-电压近似为线性关系,表现出类似金属的导电性质,而当正负电压高于15V时,电流对称性逐渐减小,即存在负微分电阻效应,从不同电压下透射谱的变化对负微分电阻现象进行了分析与讨论．     

复合半导体负载金属材料光催化性能研究

CO₂和烃类光催化直接合成烃类氧化物在合成化学、碳资源利用和环境保护等方面均有重大意义。用溶胶-凝胶和浸渍-还原相结合的方法制得M/V₂O₅-TiO₂(M=Pd、Cu、Ni和Ag)光催化剂。利用XRD、TPR、IR、TPD、UV-Vis DRS和光反应器等技术研究了负载金属复合半导体的物相结构、吸附性能、光吸收性能和光催化反应性能。结果表明：金属负载在复合半导体上延迟了TiO₂由锐钛矿向金红石相的转化,增强了V与载体TiO₂的相互作用,使TiO₂光吸收限发生蓝移,对可见光部分的吸收明显增加,拓宽了催化剂的光响应范围;材料吸光性能强弱顺序Pd/V₂O₅-TiO₂ >Cu/V₂O₅-TiO₂ >Ag/V₂O₅-TiO₂>Ni/V₂O₅-TiO₂;材料的吸附性能及反应物的吸附态是反应发生的关键,CO₂在Ag/V₂O₅-TiO₂表面无法形成卧式吸附态,没有目的产物甲基丙烯酸(MAA)生成,光量子效率低;光吸收性能较好的Pd/V₂O₅-TiO₂对CO₂吸附能力过强,卧式吸附态脱附温度高,光催化效率不高;Cu/V₂O₅-TiO₂对CO₂吸附能力适中,CO₂与C₃H₆脱附温度较接近,实现了“光-表面-热”的协同作用,光量子效率最高,达15.1%。     

CO adsorption on pure and binary-alloy gold clusters: a quantum chemical study

We performed density-functional theory analysis of nondissociative CO adsorption on 22 binary Au-alloy (Au(n)M(m)) clusters: n=0-3, m=0-3, and m+n=2 (dimers) or 3 (trimers), M=Cu/Ag/Pd/Pt. We report basis-set superposition error corrections to adsorption energies and include both internal energy of adsorption (DeltaU(ads)) and Gibbs free energy of adsorption (DeltaG(ads)) at standard conditions (298.15 K and 1 atm). We found onefold (atop) CO binding on all the clusters except Pd2 (twofold/bridged), Pt2 (twofold/bridged), and Pd3 (threefold). In agreement with the experimental results, we found that CO adsorption is thermodynamically favorable on pure Au/Cu clusters but not on pure Ag clusters and also observed the following adsorption affinity trend: Pd>Pt>Au>Cu>Ag. For alloy dimers we found the following patterns: Au2>M Au>M2 (M=Ag/Cu) and M2>M Au>Au2 (M=Pd/Pt). Alloying Ag/Cu dimers with (more reactive) Au enhanced adsorption and the opposite effect was observed for PdPt dimers. The Ag-Au, Cu-Au, and Pd-Au trimers followed the trends observed on dimers: Au3>M Au2>M2Au>M3 (M=Ag/Cu) and Pd3>Pd2Au>PdAu2>Au3. Interestingly, Pt-Au trimers reacted differently and alloying with Au systematically increased the adsorption affinity: PtAu2>Pt2Au>Pt3>Au3. A strikingly different behavior of Pt is also manifested by the triplet spin state and onefold (atop) binding in Pt3-CO which is in contradiction with the singlet spin state and threefold binding in Pd3-CO. We found a linear correlation between CO binding energy (BE) and elongation of the CO bond. For Ag-Au and Cu-Au clusters, the increase in CO BE (and elongation of the C-O bond which is probably due to the back donation) is accompanied by the decrease in the cluster-CO distance suggesting that the donation (from 5sigma highest occupied molecular orbital in CO to cluster lowest unoccupied molecular orbital) mechanism also contributes to the BE. For Pd-Au clusters, the cluster-CO distance (and CO bond length) increases with increase in the BE, suggesting that the donation mechanism may not be important for those clusters. No clear trend was observed for Pt-Au clusters.     

Electrochemical methods for the preparation of gold-coated TiO2 nanoparticles with variable coverages

We report here the first electrochemical methods to prepare elemental Au0-coated TiO2 nanoparticles with controllable coverages. First, Au substrates were cycled in a deoxygenated aqueous solution containing 0.1 N HCl and 1 mM TiO2 nanoparticles from -0.28 to +1.22 V versus Ag/AgCl at 500 mV/s with different numbers of scans. The durations at the cathodic and anodic vertexes were 10 and 5 s, respectively. After this process, positively charged Au-coated TiO2 nanoparticles were formed in the solutions. Then a cathodic overpotential of 0.6 V from the open circuit potential of ca. 0.82 V versus Ag/AgCl was applied under sonication to synthesize elemental Au0-coated TiO2 nanoparticles. The coverage of Au shells in the elemental Au-coated TiO2 nanoparticles is varied from 10% to 95% by increasing the number of scans from 10 to 50 in preparing the positively charged Au-coated TiO2 nanoparticles. The extremely high coverage of 95% in this study is notable, as compared with other methods to prepare Au-coated TiO2 nanoparticles.     

Role of micro-structure and interfacial properties in the higher photocatalytic activity of TiO2-supported nanogold for methanol-assisted visible-light-induced splitting of water

This paper deals with the textural, microstructural and interfacial properties of Au/TiO(2) nanocomposites, in relation to their photocatalytic activity for splitting of water. TiO(2) samples of two different morphologies were employed for dispersing different cocatalysts, such as: Au, Pt, Ag or Cu, for the sake of comparison. The samples were characterized using powder XRD, XPS, UV-visible, thermoluminescence, SEM, HRTEM and SAED techniques. Compared to other metal/TiO(2) photocatalysts, Au/TiO(2) with an optimum gold loading of 1 wt% was found to exhibit considerably higher activity for visible light induced production of H(2) from splitting water in the presence of methanol. Further, the sol-gel prepared TiO(2) (s.TiO(2)), having spherical grains of 10-15 nm size, displayed better photoactivity than a Degussa P25 catalyst. The electron microscopy investigations on s.TiO(2) revealed significant heterogeneity in grain morphology of individual TiO(2) particles, exposure of the lattice planes, metal dispersion, and the interfacial metal/TiO(2) contacts. The gold particles were found to be in a better dispersed state. O(2) TPD experiments revealed that the gold nanoparticles and Au/TiO(2) interfaces may serve as distinct binding sites for adsorbate molecules. At the same time, our thermoluminescence measurements provide an insight into Au-induced new defect states that may facilitate the semiconductor-to-metal charge transfer transition. In conclusion, the superior photocatalytic activity of Au/TiO(2) may relate to the grain morphology of TiO(2), dispersion of gold particles, and the peculiar architecture of metal/oxide heterojunctions; giving rise in turn to augmented adsorption of reactant molecules and their interaction with the photo-generated e(-)/h(+) pair. The role played by methanol as a sacrificial reagent in photocatalytic splitting of water is discussed.     

Length-dependent transport in molecular junctions based on SAMs of alkanethiols and alkanedithiols: effect of metal work function and applied bias on tunneling efficiency and contact resistance

Nanoscopic tunnel junctions were formed by contacting Au-, Pt-, or Ag-coated atomic force microscopy (AFM) tips to self-assembled monolayers (SAMs) of alkanethiol or alkanedithiol molecules on polycrystalline Au, Pt, or Ag substrates. Current-voltage traces exhibited sigmoidal behavior and an exponential attenuation with molecular length, characteristic of nonresonant tunneling. The length-dependent decay parameter, beta, was found to be approximately 1.1 per carbon atom (C(-1)) or 0.88 A(-)(1) and was independent of applied bias (over a voltage range of +/-1.5 V) and electrode work function. In contrast, the contact resistance, R(0), extrapolated from resistance versus molecular length plots showed a notable decrease with both applied bias and increasing electrode work function. The doubly bound alkanedithiol junctions were observed to have a contact resistance approximately 1 to 2 orders of magnitude lower than the singly bound alkanethiol junctions. However, both alkanethiol and dithiol junctions exhibited the same length dependence (beta value). The resistance versus length data were also used to calculate transmission values for each type of contact (e.g., Au-S-C, Au/CH(3), etc.) and the transmission per C-C bond (T(C)(-)()(C)).     

The role of the organic layer functionalization in the formation of silicon/organic layer/metal junctions with coinage metals

The design of silicon/alkyl layer/metal junctions for the formation of optimal top metal contacts requires knowledge of the mechanistic and energetic aspects of the interactions of metal atoms with the modified surface. This involves (a) the interaction of the metal with the terminal groups of the organic layer, (b) the diffusion of metal atoms through the organic layer and (c) the reactions of metal atoms with the silicon surface atoms. The diffusion through the monolayer and the metal catalyzed breakage of Si-C bonds must be avoided to obtain high quality junctions. In this work, we performed a comprehensive density functional theory investigation to identify the reaction pathways of all these processes. In the absence of a reactive terminal group, gold atoms may penetrate through a compact alkyl monolayer on Si(111) with no energy barrier. However, the presence of thiol terminal groups introduces a high energy barrier which blocks the diffusion of metals into the monolayer. The diffusion barriers increase in the order Ag < Au < Cu and correlate with the stability of metal-thiolate complexes whereas the barriers for the formation of metal silicides increase in the order Cu < Au < Ag in correlation with the increasing metallic radii. The reactivity of gold clusters with functionalized Si(111) surfaces was also investigated. Metal silicide formation can only be avoided by a compact monolayer terminated by a reactive functional group. The mechanistic and energetic picture obtained in this work contributes to understanding of the factors that influence the quality of top metal contacts during the formation of silicon/organic layer/metal junctions.     

Ag/Au Mixed Sites Promote Oxidative Coupling of Methanol on the Alloy Surface

Nanoporous gold, a dilute alloy of Ag in Au, activates molecular oxygen and promotes the oxygen‐assisted catalytic coupling of methanol. Because this trace amount of Ag inherent to nanoporous gold has been proposed as the source of oxygen activation, a thin film Ag/Au alloy surface was studied as a model system for probing the origin of this reactivity. Thin alloy layers of Ag_xAu_1?x, with 0.15≤x≤0.40, were examined for dioxygen activation and methanol self‐coupling. These alloy surfaces recombine atomic oxygen at different temperatures depending on the alloy composition. Total conversion of methanol to selective oxidation products, that is, formaldehyde and methyl formate, was achieved at low initial oxygen coverage and at low temperature. Reaction channels for methyl formate formation occurred on both Au and Au/Ag mixed sites with a ratio, as was predicted from the local 2‐dimensional composition.