Electron transport across the alkanethiol self-assembled monolayer/Au(111) interface: role of the chemical anchor

Alkanethiol self-assembled monolayers (SAMs) on Au(111) are model systems for molecular electronics. We probe the role of the chemisorption bond on electron dynamics at the SAM/Au interface using time-resolved two-photon photoemission. Formation of the Au-S bond is evidenced by a localized sigma resonance, which broadens and shifts upward in energy when the lying-down chemisorbed molecules stand up. The localized chemisorption bond does not affect the electronic coupling between delocalized image resonances and the metal substrate. Instead, lifetimes of image resonances are decreased due to scattering with S atoms within the thiol or thiolate monolayer.     

The dynamics of noble metal atom penetration through methoxy-terminated alkanethiolate monolayers

We have studied the interaction of vapor-deposited Al, Cu, Ag, and Au atoms on a methoxy-terminated self-assembled monolayer (SAM) of HS(CH(2))(16)OCH(3) on polycrystalline Au[111]. Time-of-flight secondary ion mass spectrometry, infrared reflection spectroscopy, and X-ray photoelectron spectroscopy measurements at increasing coverages of metal show that for Cu and Ag deposition at all coverages the metal atoms continuously partition into competitive pathways: penetration through the SAM to the S/substrate interface and solvation-like interaction with the -OCH(3) terminal groups. Deposited Au atoms, however, undergo only continuous penetration, even at high coverages, leaving the SAM "floating" on the Au surface. These results contrast with earlier investigations of Al deposition on a methyl-terminated SAM where metal atom penetration to the Au/S interface ceases abruptly after a approximately 1:1 Al/Au layer has been attained. These observations are interpreted in terms of a thermally activated penetration mechanism involving dynamic formation of diffusion channels in the SAM via hopping of alkanethiolate-metal (RSM-) moieties across the surface. Using supporting quantum chemical calculations, we rationalized the results in terms of the relative heights of the hopping barriers, RSAl > RSAg, RSCu > RSAu, and the magnitudes of the metal-OCH(3) solvation energies.     

Interfacial electrostatics of self-assembled monolayers of alkane thiolates on Au(111): work function modification and molecular level alignments

We have isolated at T < 150 K a weakly adsorbed dimethyl disulfide (DMDS) layer on Au(111) and studied how the vibrational states, S core hole level shifts, valence band photoemission, and work function measurements evolve upon transforming this system into chemisorbed methylthiolate (MT) self-assembled monolayers (SAM) by heating above 200 K. By combining these observations with detailed theoretical electronic structure simulations, at the density functional level, we have been able to obtain a detailed picture of the electronic interactions at the interface between Au and adsorbed thiolates and disulfides. All of our measurements may be interpreted with a simple model where MT is bound to the Au surface with negligible charge transfer. Interfacial dipoles arising from Pauli repulsion between molecule and metal surface electrons are present for the weakly adsorbed DMDS layer but not for the chemisorbed species. Instead, for the chemisorbed species, interfacial dipoles are exclusively controlled by the molecular dipole, its interaction with the dipoles on neighboring molecules, and its orientation to the surface. The ramifications of these results for alignment of molecular levels and interfacial properties of this class of materials are discussed.     

Density Functional Theory Study of Pd Aggregation on a Pyridine-Terminated Self-Assembled Monolayer

By using density functional theory calculations, the initial steps towards Pd metal cluster formation on a pyridine-terminated self-assembled monolayer (SAM) consisting of 3-(4-(pyridine-4-yl)phenyl)propane-1-thiol on an Au(1 1 1) surface are investigated. Theoretical modelling allows the investigation of structural details of the SAM surface and the metal/SAM interface at the atomic level, which is essential for elucidating the nature of Pd–SAM and Pd–Pd interactions at the liquid/solid interface and gaining insight into the mechanism of metal nucleation in the initial stage of electrodeposition. The structural flexibility of SAM molecules was studied first and the most stable conformation was identified, planar molecules in a herringbone packing, as the model for Pd adsorption. Two binding sites are found for Pd atoms on the pyridine end group of the SAM. The strong interaction between Pd atoms and pyridines illustrates the importance of SAM functionalisation in the metal nucleation process. Consistent with an energetic driving force of approximately −0.3 eV per Pd atom towards Pd aggregation suggested by static calculations, a spontaneous Pd dimerisation is observed in ab initio molecular dynamic studies of the system. Nudged elastic band calculations suggest a potential route with a low energy barrier of 0.10 eV for the Pd atom diffusion and then dimerisation on top of the SAM layer.     

Dynamics of the interaction of vapor-deposited copper with alkanethiolate monolayers: bond insertion, complexation, and penetration pathways

We have investigated the interaction of vapor-deposited copper with -CH3, -OH, -OCH3, -COOH, and -CO2CH3 terminated alkanethiolate self-assembled monolayers (SAMs) adsorbed on polycrystalline Au using time-of-flight secondary ion mass spectrometry and density functional theory calculations. For -OH, -COOH, and -CO2CH3 terminated SAMs measurements indicate that for all copper coverages there is a competition between Cu atom bond insertion into C-O bonds, stabilization at the SAM/vacuum interface, and penetration to the Au/S interface. In contrast, on a -OCH3 terminated SAM Cu only weakly interacts with the methoxy group and penetrates to the Au substrate, while for a -CH3 terminated SAM deposited copper only penetrates to the Au/S interface. The insertion of copper into C-O terminal group bonds is an activated process. We estimate that the barriers for Cu insertion are 55 +/- 5 kJ mol(-1) for the ester, 50 +/- 5 kJ mol(-1) for the acid, and 55 +/- 5 kJ mol(-1) for the hydroxyl terminated SAMs. The activation barrier for the copper insertion is much higher for the -OCH3 SAM. Copper atoms with energies lower than the activation barrier partition between complexation (weak interaction) with the terminal groups and penetration through the monolayer to the Au/S interface. Weakly stabilized copper atoms at the SAM/vacuum interface slowly penetrate through the monolayer. In contrast to the case of Al deposition, C-O bond insertion is favored over C=O, C-H, and C-C bond insertion.     

不同受限状态下链硫醇的非线性光学响应

以和频(SFG)振动光谱技术探测了正十二硫醇(DDT)在不同受限状态下的分子振动信号,包括金属基底上的自组装单层(SAM)分子,放置在二氧化硅基底上的表面DDT化的金纳米粒子以及金纳米粒子的甲苯溶液.在三种状态下都探测到了来自于DDT分子的振动光谱,振动光谱的区别提供了在不同受限态下DDT分子的结构信息.在金属基底上DDT分子排列规整,放置在二氧化硅基底上的金纳米粒子表面的DDT分子具有一定的柔性,在空气-甲苯溶液界面金纳米粒子表面的DDT分子高度无序.此外,光谱实验显示,金纳米粒子表面的分子振动信号产生了局域场增强的效应,相对于金基底上的自组装单层分子而言,增强系数为102-103,取决于光谱的偏振组合.     

A Colloidal Au Monolayer Modulates the Conformation and Orientation of a Protein at the Electrode/Solution Interface

The orientation and conformation of adsorbed cytochrome c (cyt c) at the interface between an electrode modified with colloidal Au and a solution were studied by electrochemical, spectroscopic, and spectroelectrochemical techniques. The results indicate that the colloidal Au monolayer formed via preformation of an organic self‐assembled monolayer (SAM) can increase the electronic coupling between the SAM and cyt c in the same manner as bifunctional molecular bridges, one functional group of which is bound to the electrode surface while the other interacts with the protein surface. The approach of cyt c to the modified electrode/solution interface can be assisted by strong interactions of the intrinsic charge of colloidal particles with cyt c, while the heme pocket remains almost unchanged due to the screening effect of the negatively charged field created by the intrinsic charge. The conformational changes of cyt c induced by its adsorption at a bare glassy carbon electrode/solution interface and the effect of the electric field on the ligation state of the heme can be avoided at the colloidal‐Au‐modified electrode/solution interface. Finally, a possible model for the adsorption orientation of cyt c at the colloidal‐Au‐modified electrode/solution interface is proposed.     

Electrochemical metal deposition on top of an organic monolayer

Electrochemical deposition of metals (platinum or gold) only on top of an organothiolate, 1,4-benzenedimethanethiol (BDMT) or hexanedithiol (HDT), self-assembled monolayer (SAM) on a Au(111) substrate was achieved by electrochemical reduction of PtCl(4)(2-) or AuCl(4)(-) ion, which was preadsorbed on one free thiol end group of the dithiol SAM formed on a Au surface, in a metal-ion-free sulfuric acid solution at potentials more negative than the reduction potential of the metal ion. Angle-resolved X-ray photoelectron spectroscopy (AR-XPS) measurement after the reduction of preadsorbed PtCl(4)(2-) ion on BDMT/Au(111) electrode showed the presence of Pt not underneath but on top of the BDMT SAM. After a negative potential scan of the Pt/BDMT/Au(111) electrode to -1.30 V in 0.1 M KOH solution, a typical cyclic voltammogram of a clean Au(111) electrode was obtained, showing that the BDMT SAM with a Pt layer was reductively desorbed. These results proved that a Pt-BDMT SAM-Au substrate sandwich structure without a short circuit between the two metals was successfully constructed by this technique. Furthermore, a decanethiol (DT) monolayer was constructed on a Au layer, which was formed by the reduction of preadsorbed AuCl(4)(-) ion on HDT/Au(111) electrode. The formation of DT/Au/HDT/Au(111) structure was confirmed as two cathodic peaks corresponding to reductive desorption of DT from Au on top of the HDT/Au(111) at -0.97 V and that of Au/ HDT from Au(111) at -1.12 V were observed when potential was scanned negatively to -1.35 V.     

Self-assembly of an octanethiol monolayer on a gold-stepped surface

We investigate the influence of the native staircase nanostructure of a Au(111) vicinal surface upon the self-assembly of alkylthiols. Through a comparison with standard alkylthiol SAMs deposited on Au(111) flat surfaces, we show that on the vicinal surface the octanethiol monolayer (OT SAM) reproduces the nanopatterned staircase structure, giving rise to a new kind of molecular layer self-ordered on the nanometer scale. The SAM's structure is determined by UHV STM and PM-IRRAS measurements and exhibits a specific behavior relative to the nanostructured substrate. The differences from the film grown on Au(111) are attributed to the influence of step edges on the molecular packing, leading to a specific 2D crystallographic order through the step edges.     

Interaction between benzenedithiolate and gold: classical force field for chemical bonding

We have constructed a group of classical potentials based on ab initio density-functional theory (DFT) calculations to describe the chemical bonding between benzenedithiolate (BDT) molecule and gold atoms, including bond stretching, bond angle bending, and dihedral angle torsion involved at the interface between the molecule and gold clusters. Three DFT functionals, local-density approximation (LDA), PBE0, and X3LYP, have been implemented to calculate single point energies (SPE) for a large number of molecular configurations of BDT-1, 2 Au complexes. The three DFT methods yield similar bonding curves. The variations of atomic charges from Mulliken population analysis within the molecule/metal complex versus different molecular configurations have been investigated in detail. We found that, except for bonded atoms in BDT-1, 2 Au complexes, the Mulliken partial charges of other atoms in BDT are quite stable, which significantly reduces the uncertainty in partial charge selections in classical molecular simulations. Molecular-dynamics (MD) simulations are performed to investigate the structure of BDT self-assembled monolayer (SAM) and the adsorption geometry of S adatoms on Au (111) surface. We found that the bond-stretching potential is the most dominant part in chemical bonding. Whereas the local bonding geometry of BDT molecular configuration may depend on the DFT functional used, the global packing structure of BDT SAM is quite independent of DFT functional, even though the uncertainty of some force-field parameters for chemical bonding can be as large as approximately 100%. This indicates that the intermolecular interactions play a dominant role in determining the BDT SAMs global packing structure.     

Mechanical stabilization effect of water on a membrane-like system

The penetration resistance of a prototypical model-membrane system (HS-(CH2)11-OH self-assembled monolayer (SAM) on Au(111)) to the tip of an atomic force microscope (AFM) is investigated in the presence of different solvents. The compressibility (i.e., height vs tip load) of the HS-(CH2)11-OH SAM is studied differentially, with respect to a reference structure. The reference consists of hydrophobic alkylthiol molecules (HS-(CH2)17-CH3) embedded as nanosized patches into the hydrophilic SAM by nanografting, an AFM-assisted nanolithography technique. We find that the penetration resistance of the hydrophilic SAM depends on the nature of the solvent and is much higher in the presence of water than in 2-butanol. In contrast, no solvent-dependent effect is observed in the case of hydrophobic SAMs. We argue that the mechanical resistance of the hydroxyl-terminated SAM is a consequence of the structural order of the solvent-SAM interface, as suggested by our molecular dynamics simulations. The simulations show that in the presence of 2-butanol the polar head groups of the HS-(CH2)11-OH SAM, which bind only weakly to the solvent molecules, try to bind to each other, disrupting the local order at the interface. On the contrary, in the presence of water the polar head groups bind preferentially to the solvent that, in turn, mediates the release of the surface strain, leading to a more ordered interface. We suggest that the mechanical stabilization effect induced by water may be responsible for the stability of even more complex, real membrane systems.     

不同受限状态下链硫醇的非线性光学响应

以和频(SFG)振动光谱技术探测了正十二硫醇(DDT)在不同受限状态下的分子振动信号, 包括金属基底上的自组装单层(SAM)分子, 放置在二氧化硅基底上的表面DDT化的金纳米粒子以及金纳米粒子的甲苯溶液. 在三种状态下都探测到了来自于DDT分子的振动光谱, 振动光谱的区别提供了在不同受限态下DDT分子的结构信息. 在金属基底上DDT分子排列规整, 放置在二氧化硅基底上的金纳米粒子表面的DDT分子具有一定的柔性, 在空气-甲苯溶液界面金纳米粒子表面的DDT分子高度无序. 此外, 光谱实验显示, 金纳米粒子表面的分子振动信号产生了局域场增强的效应, 相对于金基底上的自组装单层分子而言, 增强系数为10²-10³, 取决于光谱的偏振组合.     

Using image resonances to probe molecular conduction at the n-heptane/Au(111) interface

The binding energies and lifetimes of the n=1 image resonance on Au(111) are measured as a function of n-heptane layer thickness by femtosecond time-resolved two-photon photoemission (TR-2PPE) spectroscopy. The lifetime of the image resonance dramatically increases from approximately 4 fs on clean Au(111) to 1.6 ps with three layers of n-heptane. Because the image resonance is above the L1 band edge of Au, this increase in lifetime is attributed to the tunneling barrier presented by the sigma-sigma* band gap of the n-heptane film. We use the one-dimensional dielectric continuum model (DCM) to approximate the surface potential and to determine the binding energies and the lifetimes of the image resonances. The exact solution of the DCM potential is determined in two ways: the first by wave-packet propagation and the second by using a tight-binding Green's function approach. The first approach allows band-edge effects to be treated. The latter approach is particularly useful in illustrating the similarity between TR-2PPE and conductance measurements.     

Surface/interface electronic structure in C(60) anchored aminothiolate self-assembled monolayer: an approach to molecular electronics

Electronic structure in self-assembled monolayers (SAMs) of C(60) anchored 11-amino-1-undecane thiol (C(60)-11-AUT) on Au(111) was studied by means of ultraviolet photoelectron spectroscopy and hybrid density functional theory calculations. Valence band features of the molecular conformation revealed the interface electronic structure to be dominated by sigma(S-Au), localized at the thiolate anchor to Au. Formation of a localized covalent bond as a result of hybridization between N P(z) orbital of -NH(2) group of the thiolate SAM and the pi level of C(60) resulted in a symmetry change from I(h) in C(60) to C1 in C(60)-11-AUT SAM. Appearance of low, but finite amplitude surface electronic states of bonded C(60), much beyond the Fermi level, ruled out Au-C(60) end group contact. The band gap E(g) of the SAM, determined to be 2.7 eV, was drastically reduced from the insulating alkanethiol SAMs ( approximately 8.0 eV) and fell intermediate between the C(60) ground state (N electrons, 1.6 eV) and C(60) solid (N+/-1 electrons, 3.7 eV).     

Toward molecular electronic circuitry: selective deposition of metals on patterned self-assembled monolayer surfaces

We have developed a simple, robust method by which to construct complex two-dimensional structures based on controlling interfacial chemistry. Our approach is to employ UV-photopatterning and the reaction of vapor-deposited metals with self-assembled monolayers. To demonstrate the method, we have selectively vapor-deposited Mg on a patterned -CH3/-COOH-terminated alkanethiolate surface. The deposited metal penetrates through the -CH3 SAM to the Au/S interface while reacting with and accumulating on top of the -COOH SAM. This work has important applications in molecular/organic electronics, sensing, and other technologies. Our method has many advantages: it is extensible to many different materials, easily parallelized, affords precise nanoscale placement, and is fully compatible with photolithography.     

Atomic‐Level Elucidation of the Initial Stages of Self‐Assembled Monolayer Metallization and Nanoparticle Formation

The development of high‐performance molecular electronics and nanotech applications requires deep understanding of atomic level structural, electronic, and magnetic properties of electrode/molecular interfaces. Recent electrochemical experiments on self‐assembled monolayers (SAMs) have identified highly practical means to generate nanoparticles and metal monolayers suspended above substrate surfaces through SAM metallizations. A rational basis why this process is even possible is not yet well‐understood. To clarify the initial stages of interface formation during SAM metallization, we used first‐principles spin‐polarized density functional theory (DFT) calculations to study Pd diffusion on top of 4‐mercaptopyridine (4MP) SAMs on Au(111). After distinguishing potential‐energy surfaces (PESs) for different spin configurations for transition metal atoms on the SAM, we find adatom diffusion is not possible over the clean 4MP–SAM surface. Pre‐adsorption of transition‐metal atoms, however, facilitates atomic diffusion that appears to explain multiple reports on experimentally observed island and monolayer formation on top of SAMs. Furthermore, these diffusions most likely occur by moving across low‐lying and intersecting PESs of different spin states, opening the possibility of magnetic control over these systems. Vertical diffusion processes were also investigated, and the electrolyte was found to play a key role in preventing metal permeation through the SAM to the substrate.     

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of self-assembled monolayers of ruthenium complexes on gold

Self-assembled monolayers (SAMs) of three ruthenium complexes, [Ru(L)(2)](PF(6))(2), [Ru(L)(tpyPO(3))](PF(6))(2), and [Ru(L18)(tpyPO(3))](PF(6))(2), were prepared on evaporated gold films on glass or stainless steel plates; where L = 2, 6-bis(benzimidazoyl)pyridine, tpyPO(3) = 2,6-bis(2,2':6', 2"-terpyridyl)pyridine phosphanate, and L18 = 2, 6-bis(N-octadecylbenzimidazoyl)pyridine. Structures of these SAM complexes were studied by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). The SAMs were either prepared by direct binding of Ru-complexes to Au films by alkanethiol or by the multilayer method. In the multilayer method 1,4-thiobutylphosphate was used to form a base layer on an Au film, and the base layer was then chemically bridged to the Ru-complexes by zirconium phosphate. MALDI-TOFMS of SAM1, that had been prepared by direct binding of [Ru(L)(2)](PF(6))(2) to the Au film by an octanethiol group, showed cleavage at the S-Au linkages and elimination of the counter anion to yield a molecular ion and its dimeric ion. On the other hand, SAM2 and SAM3, which had been prepared by bridging Ru-complexes [Ru(L)(tpyPO(3))](PF(6))(2) or [Ru(L18)(tpyPO(3))](PF(6))(2) to the base layers with zirconium phosphate, showed dissociation from the base layers and elimination of the counter anion to give ions of the Ru complex molecules and their fragmentation ions. No molecular ion containing the base layer resulting from the S-Au bond cleavage was observed. Copyright 2000 John Wiley & Sons, Ltd.     

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.     

Ballistic electron emission microscopy studies of Au/molecule/n-GaAs diodes

We present nanometer-scale resolution, ballistic electron emission microscopy (BEEM) studies of Au/octanedithiol/n-GaAs (001) diodes. The presence of the molecule dramatically increases the BEEM threshold voltage and displays an unusual transport signature as compared to reference Au/GaAs diodes. Furthermore, BEEM images indicate laterally inhomogeneous interfacial structure. We present calculations that address the role of the molecular layer at the interface. Our results indicate that spatially resolved measurements add new insight to studies using conventional spatial-averaging techniques.     

Polarized near-edge x-ray-absorption fine structure spectroscopy of C60-functionalized 11-amino-1-undecane thiol self-assembled monolayer: molecular orientation and evidence for C60 aggregation

Near-edge x-ray-absorption fine structure (NEXAFS) spectroscopy was adopted to probe the unoccupied electronic states of C60 anchored onto an organized assembly of 11-amino-1-undecane thiol on Au(111). The polarization dependence of the intensity of pi* resonance associated with C60 pi network revealed the self-assembled monolayer (SAM) system to be oriented with an average molecular tilt angle of 57 degrees with respect to the surface normal. Invoking the absence of solid-state band dispersion effects and in comparison to solid C60 and /or 1-ML C60/Au(111), the electronic structure of the resulting assembly was found dominated by spectral position shift and linewidth and intensity changes of the lowest unoccupied molecular orbital (LUMO), LUMO+1, and LUMO+2 orbitals. The latter implied hybridization between N Pz of -NH2 group of thiolate SAM and pi levels of C60, resulting in a nucleophilic addition with a change in the symmetry of C60 from Ih to C1 in the SAM. Occurrence of a new feature at 285.3 eV in the NEXAFS spectrum, assigned previously to pi* graphitic LUMO, signified the formation of aggregated clusters, (C60)n of C60 monomer. Low tunneling current scanning tunneling microscopy confirmed them to be spherical and stable aggregates with n approximately 5.