Self-assembled monolayers of alkanethiols on Au(111): surface structures, defects and dynamics

The surface structures, defects and dynamics of self-assembled monolayers (SAMs) on Au(111) are reviewed. In the case of the well-known c(4 x 2) and radical 3 x radical 3 R30 degrees surface structures, the present discussion is centered on the determination of the adsorption sites. A more complex scenario emerges for the striped phases, where a variety of surface structures that depends on surface coverage are described. Recently reported surface structures at non-saturation coverage show the richness of the self-assembly process. The study of surface dynamics sheds light on the relative stability of some of these surface structures. Typical defects at the alkanethiol monolayer are shown and discussed in relation to SAMs applications.     

Conformation and dynamics of arylthiol self-assembled monolayers on Au(111)

We report a computational investigation of the conformation and the dynamics of self-assembled monolayers (SAMs) of a set of aromatic thiols arranged in the ( radical3 x radical3)-R30 degrees packing ratio on a Au(111) surface using molecular dynamics (MD) simulations. It was found that the molecular conformations were better defined for the arylthiol with two phenyl groups as compared to those with a single phenyl group and that the chemical structure of the head and tail groups had a considerable influence on the system geometry. In line with the density functional theory (DFT) calculations of small thiol molecules, we found for the SAMs that the face-centered cubic (fcc) site on the Au(111) surface was the most preferred, followed by the hexagonal close-packed (hcp) site, while the bridge position showed the characteristics of a local energy maximum. The dynamics of thiol head groups on these three Au sites was found to govern the overall dynamics of SAMs as measured by the mean square displacement. We also report that both the conformation and the dynamics on the studied time scale were driven by the SAM formation energy.     

Rectangular (3 x 2 square root of 3) superlattice of a dodecanethiol self-assembled monolayer on Au(111) observed by ultra-high-vacuum scanning tunneling microscopy

A rectangular (3 x 2 radical3) surface lattice for long-term-annealed dodecanethiol self-assembled monolayers on Au(111) is observed by ultra-high-vacuum scanning tunneling microscopy. The new lattice has the same density and a unit cell of the same size as the well-known c(4 x 2) reconstruction. In contrast, it does not show hexagonal symmetry but rather a sort of thiol pairing, leading to a shift in the binding position of every second molecule. The described structure is believed to be an intermediate phase close to desorption.     

Characterization of transparent conducting oxide surfaces using self-assembled electroactive monolayers

The electronic properties of various transparent conducting oxide (TCO) surfaces are probed electrochemically via self-assembled monolayers (SAMs). A novel graftable probe molecule having a tethered trichlorosilyl group and a redox-active ferrocenyl functionality (Fc(CH2) 4SiCl3) is synthesized for this purpose. This molecule can be self-assembled via covalent bonds to form monolayers on various TCO surfaces. On as-received ITO, saturation coverage of 6.6 x 10(-10) mol/cm2 by a close-packed monolayer and an electron-transfer rate of 6.65 s(-1) is achieved after 9 h of chemisorption, as determined by cyclic voltammetry (CV) and synchrotron X-ray reflectivity. With this molecular probe, it is found that O2 plasma-treated ITO has a significantly greater electroactive coverage of 7.9 x 10 (-10) mol/cm2 than as-received ITO. CV studies of this redox SAM on five different TCO surfaces reveal that MOCVD-derived CdO exhibits the greatest electroactive coverage (8.1 x 10(-10) mol/cm2) and MOCVD-derived ZITO (ZnIn2.0Sn1.5O) exhibits the highest electron transfer rate (7.12 s(-1)).     

Structural characterization of aldehyde-terminated self-assembled monolayers

The structure of aldehyde-terminated alkanethiol self-assembled monolayers (SAMs) on Au(111) is investigated using scanning tunneling microscopy (STM), atomic force microscopy (AFM), and density functional theory (DFT) calculations. For the first time, the structures of aldehyde-terminated SAMs are revealed with molecular resolution. SAMs of 11-mercapto-1-undecanal exhibit the basic (radical3xradical3)R30 degrees periodicity and form various c(4x2) superstructures upon annealing. In conjunction with DFT studies, the models of the (radical3xradical3)R30 degrees and the c(4x2) superstructures are constructed. In comparison with alkanethiol SAMs, the introduction of aldehyde-termini results in smaller domain size, lower degree of long-range order, large coverage of disordered areas, and higher density of missing molecules and other point defects within domains of closely packed molecules. The origin of these structural differences is mainly attributed to the strong dipole-dipole interactions among the aldehyde termini.     

The electrochemical characterisation of benzyl mercaptan-modified Au(111): structure and copper deposition

The behaviour of benzyl mercaptan self-assembled monolayers on Au(111) in sulfuric acid solution was studied using cyclic voltammetry and in situ scanning tunnelling microscopy. Modification of the Au(111) surface in an ethanolic solution of benzyl mercaptan leads to a disordered monolayer. However, by partial reductive desorption a striped c (15 x sqrt [3]) and a (2 x sqrt [3]) structure were obtained. The disordered benzyl mercaptan film was also used for the study of copper deposition. At -0.02 V versus SCE, that is in the underpotential deposition region, monoatomic high islands appear on the surface. Bulk deposition of copper starts at -0.08 V versus SCE with the growth of dendrites underneath the thiol film. At higher overpotentials, the growth of three-dimensional copper clusters commences.     

Thermodynamic and real-space structural evidence of a 2D critical point in phospholipid monolayers

The two-dimensional phase diagram of phospholipid monolayers at air-water interfaces has been constructed from Langmuir compression isotherms. The coexistence region between the solid and fluid phases of the monolayer ends at the critical temperature of the transition. The small-scale lateral structure of the monolayers has been imaged by atomic force microscopy in the nm to microm range at distinct points in the phase diagram. The lateral structure is immobilized by transferring the monolayer from an air-water interface to a solid mica support using Langmuir-Blodgett techniques. A transfer protocol that ensures preservation of the structure during the transfer has been established. The lateral structure reflecting the density fluctuations has been visualized and quantitatively characterized as the monolayer passes through a series of first-order phase transitions and ultimately approaches a critical point. The critical behavior inferred from the thermodynamic as well as the structural data is found to be consistent with the 2D Ising universality class. Additional results are presented demonstrating the presence of striped phases and coexisting domains in binary mixtures.     

Particle self-assembly in ionic liquid-in-water Pickering emulsions

We report the self-assembly of a single species or a binary mixture of microparticles in ionic liquid-in-water Pickering emulsions, with emphases on the interfacial self-assembled particle structure and the partitioning preference of free particles in the dispersed and continuous phases. The particles form monolayers at ionic liquid-water interfaces and are close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. In contrast to those at oil-water interfaces, no long-range-ordered colloidal lattices are observed. Interestingly, other than equilibrating at the ionic liquid-water interfaces, the microparticles also exhibit a partitioning preference in the dispersed and continuous phases: the sulfate-treated polystyrene (S-PS) and aldehyde-sulfate-treated polystyrene (AS-PS) microparticles are extracted to the ionic liquid phase with a high extraction efficiency, whereas the amine-treated polystyrene (A-PS) microparticles remain in the water phase.     

Influence of end group and surface structure on the current-voltage characteristics of alkanethiol monolayers on Au(111)

We present density functional theory calculations of the electronic structure and tunneling characteristics of alkanethiolate monolayers on Au(111). We systematically analyze radical3 x radical3 full coverage monolayers of SC6H12X molecules with different terminal groups, X=CH3, NH2, SH, OH, COOH, OCH3, on defect-free ("perfect") Au(111). We also study the influence of the surface-molecule bonding structure by comparing the properties of monolayers of SC6H12CH3 molecules on the perfect surface and on Au(111) surfaces with vacancies or adatoms. The tunneling currents (I) through the adsorbed monolayers with a single chemical contact have been calculated within the Tersoff-Hamann approach for voltages between -1 and +1 V. Computed currents are found to depend linearly on V at low voltage, with typical values of approximately 60 and 150 pA/molecule at 0.2 and 0.5 V, respectively, in good agreement with several experimental data. Computed tunneling currents show also a significant dependence on both the terminal group X and the surface structure. In particular, in order of decreasing intensities, currents for the different end groups are NH2 approximately SH>CH3>OH>OCH3>COOH. The relationships between the tunneling current, the work function of the surface+SAM, and the lineup of the HOMO with respect to the Fermi energy of the metal surface are examined.     

Ordering of TiO2-based nanostructures on SrTiO3(001) surfaces

A class of nanostructured surface phases on SrTiO3(001) is reported and characterized through atomic-resolution scanning tunneling microscopy and Auger electron spectroscopy. These surface phases are created via argon ion sputtering and UHV annealing and form close-packed domains of highly ordered nanostructures. Depending on the type of nanostructures present, the domain ordering exhibit either (6 x 2), (9 x 2), (12 x 2), (6 x 8), or (7 x 4) surface patterning. The nanostructures are composed of TiO2-derived complexes surrounded by a TiO2 surface termination. Such surface ordering phenomena introduce another level of complexity in the chemistry of perovskite oxide surfaces and provide a basis from which potential photocatalytic and molecular-ordering applications may be developed.     

Surface microscopic structure and electrochemical rectification of a branched alkanethiol self-assembled monolayer

The tert-butanethiol self-assembled monolayers (SAMs) on Au(111) surfaces were prepared from various solvents and investigated by a combination of scanning tunneling microscopy (STM) and electrochemistry in aqueous environments. High-resolution STM images reveal a (radical(7) x radical(7))R19 degrees surface lattice structure, in contrast with the conventional lattice (radical(3) x radical(3))R30 degrees structure for straight-chain alkanethiol SAMs. Interestingly, such a branched monolayer shows electrochemical rectification toward redox probes. We suggest that electrochemical rectification could be a general characteristic of short-chain branched alkanthiol SAMs, and originate in localized electronic effects.     

Self-assembled monolayers of benzylmercaptan and p-cyanobenzylmercaptan on Au(111) surfaces: structural and spectroscopic characterization

The formation of self-assembled monolayers of benzylmercaptan (BM) and p-cyanobenzylmercaptan (pCBM) on Au(111) surfaces is investigated by a combination of X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and scanning tunneling microscopy (STM). The NEXAFS results of pCBM are supported by ab initio calculations. It is found that BM as well as pCBM form well-ordered monolayers with the molecules oriented almost perpendicular to the surface. BM forms a ( radical 3 x radical 3)R30 degrees structure whereas pCBM forms a slightly different c(7 x 7) hexagonal structure. No phase separation is detected for the adsorption of a 1:1 mixture of the two molecules. The implications of the results for the covalent attachment of transition-metal complexes to thiol-functionalized surfaces are discussed.     

Molecular ordering and phase transitions in alkanol monolayers at the water-hexane interface

The interface between bulk water and bulk hexane solutions of n-alkanols (H(CH(2))(m)OH, where m=20, 22, 24, or 30) is studied with x-ray reflectivity, x-ray off-specular diffuse scattering, and interfacial tension measurements. The alkanols adsorb to the interface to form a monolayer. The highest density, lowest temperature monolayers contain alkanol molecules with progressive disordering of the chain from the -CH(2)OH to the -CH(3) group. In the terminal half of the chain that includes the -CH(3) group the chain density is similar to that observed in bulk liquid alkanes just above their freezing temperature. The density in the alkanol headgroup region is 10% greater than either bulk water or the ordered headgroup region found in alkanol monolayers at the water-vapor interface. We conjecture that this higher density is a result of water penetration into the headgroup region of the disordered monolayer. A ratio of 1:3 water to alkanol molecules is consistent with our data. We also place an upper limit of one hexane to five or six alkanol molecules mixed into the alkyl chain region of the monolayer. In contrast, H(CH(2))(30)OH at the water-vapor interface forms a close-packed, ordered phase of nearly rigid rods. Interfacial tension measurements as a function of temperature reveal a phase transition at the water-hexane interface with a significant change in interfacial excess entropy. This transition is between a low temperature interface that is nearly fully covered with alkanols to a higher temperature interface with a much lower density of alkanols. The transition for the shorter alkanols appears to be first order whereas the transition for the longer alkanols appears to be weakly first order or second order. The x-ray data are consistent with the presence of monolayer domains at the interface and determine the domain coverage (fraction of interface covered by alkanol domains) as a function of temperature. This temperature dependence is consistent with a theoretical model for a second order phase transition that accounts for the domain stabilization as a balance between line tension and long range dipole forces. Several aspects of our measurements indicate that the presence of domains represents the appearance of a spatially inhomogeneous phase rather than the coexistence of two homogeneous phases.     

Surface vibrations in alkanethiol self-assembled monolayers of varying chain length

The effect of chain length on the low-energy vibrations of alkanethiol striped phase self-assembled monolayers on Au(111) was studied. We have examined the low-energy vibrational structure of well-ordered, low-density 1-decanethiol (C10), 1-octanethiol (C8), and 1-hexanethiol (C6) to further understand the interaction between adsorbate and substrate. Dispersionless Einstein mode phonons, polarized perpendicularly to the surface, were observed for the striped phases of C10, C8, and C6 at 8.0, 7.3, and 7.3 meV, respectively. An overtone at 12.3 meV was also observed for C6/Au(111). These results, in concert with molecular dynamics simulations, indicate that the forces between the adsorbate and substrate can be described using simple van der Waals forces between the hydrocarbon chains and the Au substrate with the sulfur chemisorbed in the threefold hollow site.     

Long-range self-assembly of a polyunsaturated linear organosilane at the n-tetradecane/Au(111) interface studied by STM

We report on the formation of self-assembled monolayers of 13-(trimethylsilyl)-1-tridecene-6,12-diyne [C13H17-Si(CH3)3], an organosilane derivative with a linear polyunsaturated chain, on Au(111) substrates. Molecular resolution STM images recorded at the liquid-solid interface between gold and tetradecane reveal a long-range and densely packed hexagonal lattice with a ( radical3 x radical3)R30 degrees -like structure commensurate against gold adlattice.     

Communication: Scanning tunneling microscopy study of the reaction of octanethiolate self-assembled monolayers with atomic chlorine

Scanning tunneling microscopy was used to investigate the reaction of octanethiolate self-assembled monolayers (SAMs) with atomic chlorine. We have found that exposing a SAM to low fluxes of radical Cl results primarily in the formation of new defects in areas with close-packed alkanethiolates, but has little to no effect on the domain boundaries of the SAM. Dosing high quantities of atomic chlorine results in the near-complete loss of surface order at room temperature, but not the complete removal of the thiolate monolayer. These observations are in stark contrast to the results of previous measurements of the reaction of atomic hydrogen with alkanethiolate SAMs.     

Observation from scanning tunneling microscopy of a striped phase for octanethiol adsorbed on Au(111) from solution

A self-assembled monolayer of 1-octanethiol was prepared on a Au(111) surface via liquid-phase adsorption. An investigation of the surface using ultrahigh-vacuum scanning tunneling microscopy revealed a striped phase of the octanethiol molecules under the conditions examined. This phase resembles the well-known "pinstripe" structure of alkanethiols on Au(111), with a registry that is similar to that of the previously observed p x radical3 structures. We discuss the nature of this structure with respect to those that have been observed for other n-alkanethiols.     

New insights in the c(4 x 2) reconstruction of hexadecanethiol on Au(111) revealed by grazing incidence X-ray diffraction

The c(4 x 2) structure of C16H33SH alkanethiol monolayers self-assembled on Au(111) has been studied by grazing incidence X-ray diffraction. This structure coexists on the surface with the (radical3x radical3)R30 degrees phase. The structural refinement of the c(4 x 2) phase has been accomplished by omitting the fractional order reflections common to both structures. The surface unit cell consists of four symmetry-independent molecules with atomic displacements related by couples, such that only two nonequivalent chains are present in the surface cell. The stability between neighbor chains is due to van der Waals interactions. The substrate plays an important and non-negligible role in the c(4 x 2) reconstruction. The lateral and normal substrate relaxations to the surface plane are small, and gold atom displacements are lower than 0.25 angstroms but contribute very strongly to the fractional order intensities. The molecular chains form a close packed structure tilted by 37 degrees from the surface normal with no indications of dimer formation between closest S atoms.     

Studies on 2D hybrid films of half surfactant-covered Au nanoparticles at the air/water interface

A hybrid monolayer film of Au nanoparticles, half-covered with dioctadecyldimethylammonium chloride (DODAC), was prepared at the air/water interface and characterized using transmission electron microscopy (TEM), a quartz-crystal microbalance, and infrared spectra measurements. TEM images of the hybrid film showed that the distribution of Au nanoparticles depends on the surface density of DODAC and reaction time. IR spectral data provided evidence for a surface-enhanced effect of the Au nanoparticles. The wavenumber of CH(2)-stretch vibrations of DODAC in the infrared external reflection spectra revealed that the DODAC molecules were adsorbed onto the Au nanoparticles in a close-packed crystalline state for any surface density of DODAC, which is different from the usual behavior of Langmuir monolayers.     

Significance of local density of states in the scanning tunneling microscopy imaging of alkanethiol self-assembled monolayers

A systematic scanning tunneling microscopy (STM) study of alkanethiol self-assembled monolayers (SAMs) is presented as a function of the bias voltage, tunneling current, and tip-termini separation. Stable and etch-pit free SAMs of close-packed undecanethiol/Au(111) were obtained after annealing in ultrahigh vacuum. STM revealed two distinct c(4x2) structures with four nonequivalent molecules per unit cell. For both structures, reversible contrast variations occur upon systematically tuning the bias voltage, the current, and the tip-termini distance. These contrast transitions originate from probing the corresponding local density of states (LDOS) of each molecule and not from the reorientation of the alkanethiol chains. The STM contrast is particularly sensitive to the tip-termini separation in the range of 0.5-2.5 A, reflecting the distance-dependence of LDOS. At a fixed tip elevation, the STM contrast is less sensitive to changes in bias within 0.1-1.2 V. For the first time, we demonstrate that LDOS may override the physical height variations in the STM topographic contrast for alkanethiol SAM systems.