Effect of functional group (fluorine) of aromatic thiols on electron transfer at the molecule-metal interface

Electron transfer at the molecule-metal interface of self-assembled monolayers of 1,1';4',1'-terphenyl-4'-thiol (BBB) and its partially fluorinated counterpart (BFF: p-thiophenyl-nonafluorobiphenyl) on Au(111) is investigated by core-hole clock spectroscopy. Ultrafast electron transfer at the BBB/Au(111) interface in the low-femtosecond regime (on the same time scale as the C 1s core-hole lifetime, approximately 6 fs) was observed. In contrast, for BFF/Au(111), the interface electron transfer was forbidden during the core-hole decay. This strongly suggests that fluorination of phenyl rings significantly enhances the localization of the excited electrons in the LUMO.     

Ultrafast electron transfer from oligo(p-phenylene-ethynylene)thiol to gold

The electron transfer dynamics of oligo(p-phenylene-ethynylene) (OPE) SAM on Au(111) was studied by resonant photoemission spectroscopy. The ultrafast electron transfer from OPE molecules to Au substrate was clearly observed. The time scale for this charge transfer is much less than 6 fs, the core-hole lifetime for C 1s. This strongly suggests that there is an intense interfacial electronic coupling between OPE molecules and the Au substrate.     

Configuration-dependent interface charge transfer at a molecule-metal junction

The role of the molecule-metal interface is a key issue in molecular electronics. Interface charge transfer processes for 4-fluorobenzenethiol monolayers with different molecular orientations on Au(111) were studied by resonant photoemission spectroscopy. The electrons excited into the LUMO or LUMO+1 are strongly localized for the molecules standing up on Au(111). In contrast, an ultrafast charge transfer process was observed for the molecules lying down on Au(111). This configuration-dependent ultrafast electron transfer is dominated by an adiabatic mechanism and directly reflects the delocalization of the molecular orbitals for molecules lying down on Au(111). Theoretical calculations confirm that the molecular orbitals indeed experience a localization-delocalization transition resulting from hybridization between the molecular orbitals and metal surface. Such an orientation-dependent transition could be harnessed in molecular devices that switch via charge transfer when the molecular orientation is made to change.     

Al2O3/Au(111)反相催化剂在CO氧化反应中界面作用的理论研究

氧化物负载的金催化剂具有温和条件下优异的CO催化氧化活性。实验与理论计算表明,金与氧化物两相界面在催化反应过程中具有重要地位。反相催化剂提供了全新的角度以探究界面的重要地位。本文以Au（111）表面负载Al₂O₃团簇为反相催化剂模型,基于密度泛函理论,对催化剂模型的构型、界面性质以及O₂、CO的吸附与氧化进行了理论计算与研究。理论计算表明：电荷的迁移增强了Al₂O₃小团簇在Au（111）表面的附着,在催化剂金表面与氧化铝的两相界面位置,Au原子与Al原子的协同作用使得氧分子易于在界面位置吸附,并因此高度活化。对催化CO氧化反应路径,分别计算了缔合机理和解离机理不同路径,从活化能分析表明缔合机理比解离机理更可能发生。本文的工作揭示了反相催化剂催化CO氧化的活性本质,表明两相界面在金催化CO氧化中具有重要作用。     

Ultra-thin PTCDA layers studied by optical spectroscopies

3,4,9,10-Perylenetetracarboxylic dianhydride (PTCDA) was deposited using organic molecular beam deposition (OMBD) onto various substrates, i.e. mica(0001), Au(111) layers on mica, and Se-passivated GaAs(100). Layer thicknesses were from 2 to 30 nm. Reflectance and transmittance measurements were performed in order to identify PTCDA absorption features and find suitable laser wavelengths for subsequent Raman investigations. Despite the low thicknesses the Raman spectra reveal strong scattering by the molecular vibrational modes, in particular above 1200 cm^–1. Frequency shifts of various modes in the layers from their values in PTCDA source material may indicate the influence of the substrates. Similar shifts were also observed in infrared spectra of the same materials. Received: 5 August 1998 / Received: 25 October 1998 / Accepted: 26 October 1998     

Ultra-thin PTCDA layers studied by optical spectroscopies

3,4,9,10-Perylenetetracarboxylic dianhydride (PTCDA) was deposited using organic molecular beam deposition (OMBD) onto various substrates, i.e. mica(0001), Au(111) layers on mica, and Se-passivated GaAs(100). Layer thicknesses were from 2 to 30 nm. Reflectance and transmittance measurements were performed in order to identify PTCDA absorption features and find suitable laser wavelengths for subsequent Raman investigations. Despite the low thicknesses the Raman spectra reveal strong scattering by the molecular vibrational modes, in particular above 1200 cm^–1. Frequency shifts of various modes in the layers from their values in PTCDA source material may indicate the influence of the substrates. Similar shifts were also observed in infrared spectra of the same materials. Received: 5 August 1998 / Received: 25 October 1998 / Accepted: 26 October 1998     

Luminescence from 3,4,9,10-perylenetetracarboxylic dianhydride on Ag(111) surface excited by tunneling electrons in scanning tunneling microscopy

The electronic excitations induced with tunneling electrons into adlayers of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) on Ag(111) have been investigated by in situ fluorescence spectroscopy in scanning tunneling microscopy (STM). A minute area of the surface is excited by an electron tunneling process in STM. Fluorescence spectra strongly depend on the coverage of PTCDA on Ag(111). The adsorption of the first PTCDA layer quenches the intrinsic surface plasmon originated from the clean Ag(111). When the second layer is formed, fluorescence spectra are dominated by the signals from PTCDA, which are interpreted as the radiative decay from the manifold of first singlet excited state (S(1)) of adsorbed PTCDA. The fluorescence of PTCDA is independent of the bias polarity. In addition, the fluorescence excitation spectrum agrees with that by optical excitation. Both results indicate that S(1) is directly excited by the inelastic impact scattering of electrons tunneling within the PTCDA adlayer.     

The mechanism of emerging catalytic activity of gold nano-clusters on rutile TiO2(110) in CO oxidation reaction

This paper reveals the fact that the O adatoms (O(ad)) adsorbed on the 5-fold Ti rows of rutile TiO(2)(110) react with CO to form CO(2) at room temperature and the oxidation reaction is pronouncedly enhanced by Au nano-clusters deposited on the above O-rich TiO(2)(110) surfaces. The optimum activity is obtained for 2D clusters with a lateral size of ～1.5 nm and two-atomic layer height corresponding to ～50 Au atoms∕cluster. This strong activity emerging is attributed to an electronic charge transfer from Au clusters to O-rich TiO(2)(110) supports observed clearly by work function measurement, which results in an interface dipole. The interface dipoles lower the potential barrier for dissociative O(2) adsorption on the surface and also enhance the reaction of CO with the O(ad) atoms to form CO(2) owing to the electric field of the interface dipoles, which generate an attractive force upon polar CO molecules and thus prolong the duration time on the Au nano-clusters. This electric field is screened by the valence electrons of Au clusters except near the perimeter interfaces, thereby the activity is diminished for three-dimensional clusters with a larger size.     

Experimental and DFT studies of gold nanoparticles supported on MgO(111) nano-sheets and their catalytic activity

A wet chemical preparation of MgO with the (111) facet as the primary surface has recently been reported and with alternating layers of oxygen anions and magnesium cations, this material shows unique chemical and physical properties. The potential to utilize the MgO(111) surface for the immobilization of metal particles is intriguing because the surface itself offers a very different environment for the metal particle with an all oxygen interface, as opposed to the typical (100) facet that possesses alternating oxygen anion and magnesium cation sites on the surface. Gold nanoparticles have demonstrated a broad range of interesting catalytic properties, but are often susceptible to aggregation at high temperatures and are very sensitive to substrate effects. Here, we investigate gold-supported on MgO(111) nanosheets as a catalyst system for the aerobic oxidation of benzyl alcohol. Gold nanoparticles deposited on MgO(111) show an increased level of activity in the solvent-free benzyl alcohol aerobic oxidation as compared to gold nanoparticles deposited on a typical MgO aerogel. TEM studies reveal that the gold nanoparticles have a hemispherical shape while sitting on the main surface of MgO(111) nanosheets, with a large Au-MgO interface. Given that the gold nanoparticles deposited on the two types of MgO have similar size, and that the two types of unmodified MgO show almost the same activities in the blank reaction, we infer that the high activity of Au/MgO(111) is due to the properties of the (111) support and/or those of the gold-support interface. To understand the binding of Au on low-index MgO surfaces and the charge distribution at the surface of the support, we have performed density functional theory (DFT) calculations on all low-index MgO substrates (with and without gold), using a model Au(10) cluster. Due to similar lattice constants of Au(111) and MgO(111) planes, the Au cluster retains its structural integrity and binds strongly on MgO(111) with either oxygen or magnesium termination. Furthermore, we have found that for the (001) and (110) substrates the charges of the ions in the top surface layer have similar values as in bulk MgO, but that on (111) surfaces these charges are significantly different. This difference in surface charge determines the direction of the electronic transfer upon adsorption of gold, such transfer occurring so as to restore the bulk MgO charge values. Using the results from theoretical calculations, we provide an explanation of our observations of increased catalytic activity in the case of the Au/MgO(111) system.     

Two-dimensional pentacene:3,4,9,10-perylenetetracarboxylic dianhydride supramolecular chiral networks on Ag(111)

Self-assembly of the binary molecular system of pentacene and 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) on Ag(111) has been investigated by low-temperature scanning tunneling microscopy, molecular dynamics (MD), and density functional theory (DFT) calculations. Well-ordered two-dimensional (2D) pentacene:PTCDA supramolecular chiral networks are observed to form on Ag(111). The 2D chiral network formation is controlled by the strong interfacial interaction between adsorbed molecules and the underlying Ag(111), as revealed by MD and DFT calculations. The registry effect locks the adsorbed pentacene and PTCDA molecules into specific adsorption sites due to the corrugation of the potential energy surface. The 2D supramolecular networks are further constrained through the directional CO...H-C multiple intermolecular hydrogen bonding between the anhydride groups of PTCDA and the peripheral aromatic hydrogen atoms of the neighboring pentacene molecules.     

Structure and bonding of large aromatic molecules on noble metal surfaces: The example of PTCDA

Recent efforts to understand the interaction of large aromatic molecules with metal surfaces are discussed. We focus exclusively on work involving the model molecule 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) and the noble metal surfaces of Cu, Ag, and Au. Using this material system as an example, salient features of the (chemical) bond between an extended π-conjugated electron system and a metallic substrate are illustrated. Interface structures are a valuable indicator of the metal–molecule interaction strength. Consistent with the trend observed for small molecule adsorption, they indicate that the interaction strength of PTCDA with the metal substrate decreases in the order Cu–Ag–Au. The interfaces of PTCDA with the Au(1 1 1) and Ag(1 1 1) surfaces have been studied in particular detail. The interaction of Au(1 1 1) with PTCDA is weak, leading to point-on-line coincidence between the lattices of the substrate and the molecular overlayer. Experimental results on this surface are generally consistent with a predominantly physisorptive bonding of PTCDA. The situation is different on Ag surfaces, and in particular on Ag(1 1 1), where clear signs of PTCDA chemisorption are observed in many ensemble averaging and single molecule spectroscopies. Issues of electronic and geometric structure as well as electron–vibron interaction, and their relation to the chemical molecule–substrate interaction, are discussed in detail.     

Fabrication of surface-supported low-dimensional polyimide networks

Interest in thermal and chemical stability of surface-supported organic networks has stimulated recent attempts to covalently interlink adsorbed molecular species into extended nanostructures. We show, using low-temperature scanning tunneling microscopy, that imidization of anhydrides and amines adsorbed on Au(111) can be thermally initiated under controlled ultrahigh vacuum conditions. Using two types of amine-functionalized polyphenyl molecules together with the organic semiconductor PTCDA, monolayer thick linear polymeric strands and a porous polymeric network with nanoscale dimensions are obtained.     

Charging energy and barrier height of pentacene on Au(111): a local-orbital hybrid-functional density functional theory approach

We analyze the pentacene/Au(111) interface by means of density functional theory (DFT) calculations using a new hybrid functional; in our approach we introduce, in a local-orbital formulation of DFT, a hybrid exchange potential, and combine it with a calculation of the molecule charging energy to properly describe the transport energy gap of pentacene on Au(111). Van der Waals forces are taken into account to obtain the adsorption geometry. Interface dipole potentials are also calculated; it is shown that the metal/pentacene energy level alignment is determined by the potential induced by the charge transfer between the metal surface and the organic material, as described by the induced density of interface states model. Our results compare well with the experimental data.     

Tuning the hole injection barrier at the organic/metal interface with self-assembled functionalized aromatic thiols

Self-assembled functionalized aromatic thiols (oligophenylenes composed of building blocks of dimethoxy-substituted phenylenes, perfluoro-substituted phenylenes, and a terminal thiol group) were used to tune the hole injection barrier (Delta(h)) of copper(II) phthalocyanine (CuPc) on Au(111). Synchrotron-based high-resolution photoemission spectroscopy study reveals a significant reduction of Delta(h) by as much as 0.75 eV from Delta(h) = 0.9 eV for CuPc/Au(111) to Delta(h) = 0.15 eV for CuPc/BOF/Au(111), where BOF represents 4-pentafluorophenyl-1-(p-thiophenyl)-2,5-dimethoxybenzene. The delocalized pi orbitals of these functionalized aromatic thiols greatly facilitate effective charge transfer (hole or electron) across the SAM interface as compared to alkanethiols, hence making this novel interface modification scheme a simple and effective way to tune the hole injection barrier. This method has potential applications in molecular electronics, organic light-emitting diodes (OLED), organic field-effect transistors (OFETs), and organic solar cells.     

Charge transfer interactions of a Ru(II) dye complex and related ligand molecules adsorbed on Au(111)

The interaction of the dye molecule, N3 (cis-bis(isothiocyanato)bis(2,2(')-bipyridyl-4,4(')-dicarboxylato)-ruthenium(II)), and related ligand molecules with a Au(111) surface has been studied using synchrotron radiation-based electron spectroscopy. Resonant photoemission spectroscopy (RPES) and autoionization of the adsorbed molecules have been used to probe the coupling between the molecules and the substrate. Evidence of charge transfer from the states near the Fermi level of the gold substrate into the lowest unoccupied molecular orbital (LUMO) of the molecules is found in the monolayer RPES spectra of both isonicotinic acid and bi-isonicotinic acid (a ligand of N3), but not for the N3 molecule itself. Calibrated x-ray absorption spectroscopy and valence band spectra of the monolayers reveals that the LUMO crosses the Fermi level of the surface in all cases, showing that charge transfer is energetically possible both from and to the molecule. A core-hole clock analysis of the resonant photoemission reveals a charge transfer time of around 4 fs from the LUMO of the N3 dye molecule to the surface. The lack of charge transfer in the opposite direction is understood in terms of the lack of spatial overlap between the π?-orbitals in the aromatic rings of the bi-isonicotinic acid ligands of N3 and the gold surface.     

Probing the buried C60/Au(111) interface with atoms

To characterize the C(60)/Au(111) interface, we send Au atoms "diving" through the C(60) layer and observe their behavior at the interface. Our observations show that the interfacial diffusion of gold atoms and the nucleation of small Au islands at the interface are strongly dependent on the local C(60)-Au(111) bonding which varies from one domain to another. The contrast-disordered domain consisting of a large fraction of molecules bonded to Au vacancies has a special structure at the interface allowing Au atoms to be inserted beneath the bright-looking molecules while the dim molecules present a much stronger resistance to the diffusing Au atoms. This leads to the formation of isolated Au islands with discrete sizes, with the smallest island just about 1 nm across.     

Characterization of organic overlayers on well-defined substrates

Proceeding from some remarks on the importance of organic/inorganic interfaces and of the controlled growth of thin organic films for both, basic research and present or future applications it is shown that surface sensitive methods like NEXAFS, XPS, ARUPS, and TPD can nicely be applied for studying various model systems. These systems range from perylene single crystals, over perylene and PTCDA layers on Si(111), PTCDA on Ag(111), HCOOH on Ni(111) to adsorption and polymerization of thiophene on a Ag(111) surface. Selected data are shown, and some results are briefly discussed.     

Geometric and Electronic Behavior of C60 on PTCDA Hydrogen Bonded Network

Self-assembled supramolecular networks are promising spacer layer for electronic decoupling from the metal substrate.However,the mechanism behind of how the intrinsic electronic structure of spacer layers affects the adsorbate is still unclear.Here a hydrogen bonded network composed of n-type semiconducting molecules 3,4,9,10-perylene-tetracarboxylic-dianhydride(PTCDA)is prepared under ultra-high vacuum to serve as a spacer layer for functional organics C60 on Au(111).The geometric and electronic information of C60 was investigated by scanning tunneling microscopy and scanning tunneling spectroscopy(STM/STS)at 5 K.Effective decoupling from the metal surface yields an energy gap of 3.67 eV for C602nd,merely considering the HOMO-LUMO peak separation.The broadening of resonance peaks in STS measurements however indicates unneglected interlayer interactions in this hetero-organic system.Moreover,we scrutinize the nucleation sites of C60 on PTCDA layer and attribute this to the decreased diffusion capability on a less dense molecular arrangement possessing inhomogeneous spatial distribution of unoccupied molecular orbitals.