Exploring three-dimensional nanosystems with Raman spectroscopy: methylene blue adsorbed on thiol and sulfur monolayers on gold

Resonant Raman and surface-enhanced Raman scattering (SERS) spectroscopies, complemented with scanning tunnel microscopy and electrochemical techniques, have been used to obtain information about the amount and spatial distribution of methylene blue (MB) molecules immobilized on sulfur and four ultrathin molecular alkanethiolate films self-assembled on Au(111) and rough Au electrodes. The intensity of the Raman signals allow one to estimate the amount of immobilized MB at different organic films, whereas the decrease in the SERS intensity as a function of distance for the rough Au electrodes is used to locate the average position of the MB species with respect to the Au substrate. We found that significant amounts of cationic MB species are able to diffuse into methyl-terminated thiols, but they are stopped at the outer plane of the self-assembled monolayer (SAM) by negatively charged carboxylate groups. The relative shift of C-N stretching Raman modes indicates that the binding of MB to S is different from that found for MB on thiols. Most of the molecules immobilized on methyl- and carboxylate-terminated thiols are electrochemically inactive, suggesting that strong coupling between the Au electrode and the MB molecules is needed for charge transfer. Our results are consistent with a small population of electrochemically active MB species very close to the Au surface that reach this position driven by their lipophilic (hydrophobic) character through defects at SAMs.     

Nanografting versus solution self-assembly of alpha,omega-alkanedithiols on Au(111) investigated by AFM

The solution self-assembly of alpha,omega-alkanedithiols onto Au(111) was investigated using atomic force microscopy (AFM). A heterogeneous surface morphology is apparent for 1,8-octanedithiol and for 1,9-nonanedithiol self-assembled monolayers (SAMs) prepared by solution immersion as compared to methyl-terminated n-alkanethiols. Local views from AFM images reveal a layer of mixed molecular orientations for alpha,omega-alkanedithiols, which evidence surface structures with heights corresponding to both lying-down and standing-up orientations. For dithiol SAMs prepared by solution self-assembly, the majority of alpha,omega-alkanedithiol molecules chemisorb with both thiol end groups bound to the Au(111) surface with the backbone of the alkane chain aligned parallel to the surface. However, AFM images disclose that there are also islands of standing molecules scattered throughout the surface. To measure the thickness of alpha,omega-alkanedithiol SAMs with angstrom sensitivity, methyl-terminated n-alkanethiols with known dimensions were used as molecular rulers. Under conditions of spatially constrained self-assembly, nanopatterns of alpha,omega-alkanedithiols written by nanografting formed monolayers with heights corresponding to an upright configuration.     

In situ STM evidence for the adsorption geometry of three N-heteroaromatic thiols on Au(111)

The electrochemical behavior of three heteroaromatic thiols (MBs) (2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole (MBT), and 2-mercaptobenzoxazole (MBO)) on a Au(111) surface has been investigated by electrochemical scanning tunneling microscopy (ECSTM) and cyclic voltammetry (CV) in 0.1 M HClO(4) solution. All three thiols form oriented molecular cluster lines along the reconstruction line direction at 0.55 V. With the electrode potential shifting negatively, the molecules undergo a disordered-ordered structural transition. Molecularly resolved STM images show that all three molecules form striped adlayers in the desorption region on the Au(111) surface. The different heteroatoms in the heteroaromatic rings result in different electrochemical behavior of the MB self-assembled monolayers (SAMs). MBI, MBT, and MBO are proposed to interact with the substrate via the S-Au bonds from thiol group and the coordination interaction of N, S, and O with the substrate from the heteroaromatic ring, respectively. These results provide direct evidence of the electrochemical behavior and the adlayer structures of MB SAMs on the Au electrode.     

Thiol with an unusual adsorption-desorption behavior: 6-mercaptopurine on Au(111)

A multitechnique study of 6-mercaptopurine (6MP) adsorption on Au(111) is presented. The molecule adsorbs on Au(111), originating short-range ordered domains and irregular nanosized aggregates with a total surface coverage by chemisorbed species smaller than those found for alkanethiol SAMs, as derived from scanning tunneling microscopy (STM) and electrochemical results. X-ray photoelectron spectroscopy (XPS) results show the presence of a thiolate bond, whereas density functional theory (DFT) data indicate strong chemisorption via a S-Au bond and additional binding to the surface via a N-Au bond. From DFT data, the positive charge on the Au topmost surface atoms is markedly smaller than that found for Au atoms in alkanethiolate SAMs. The adsorption of 6MP originates Au atom removal from step edges but no vacancy island formation at (111) terraces. The small coverage of Au islands after 6MP desorption strongly suggests the presence of only a small population of Au adatom-thiolate complexes. We propose that the absence of the Au-S interface reconstruction results from the lack of significant repulsive forces acting at the Au surface atoms.     

Surface‐Confined Electropolymerization of Methylene Blue on Gold Electrodes

We report on the electrochemical behaviour and electropolymerization of self‐assembled monolayers (SAMs) of methylene blue (MB) on gold electrodes. The SAMs of MB on gold electrodes were prepared by immersing the substrates into a solution of 1.0 mM MB in absolute ethanol for different times at room temperature. Cyclic voltammetry experiments exhibited that reductive desorption of MB monolayer takes place at three different potentials on polycrystalline gold electrodes, while reductive desorption of MB monolayer consists of only one peak on single crystal Au(111) substrates. Calculated charge densities for different immersion times indicated that optimal immersion time for self‐assembly of MB is 96 h. Electropolymerization of SAMs of MB on gold electrode was achieved by applying 0.95 V for 1 s in 0.1 M borate buffer solution (pH: 9.0). It was observed that poly(MB) monolayers are highly stable in acidic media. ATR‐FTIR and UV‐vis spectra exhibited differences between monomer and polymer monolayers, which are attributed to surface‐confined electropolymerization. STM image of poly(MB) monolayer on Au(111) substrate revealed a surface that is covered by well‐ordered, collateral nanowires with an average size of 3 nm.     

Time-dependent organization and wettability of decanethiol self-assembled monolayer on Au(111) investigated with STM

A detailed study on the time-dependent organization of a decanethiol self-assembled monolayer (SAM) at a designed solution concentration onto a Au(111) surface has been performed with scanning tunneling microscopy (STM). The SAMs were prepared by immersing Au(111) into an ethanol solution containing 1 microM decanethiol with different immersion times. STM images revealed the formation process and adlayer structure of the SAMs. It was found that the molecules self-organized into adlayers from random separation to a well-defined structure. From 10 s, small domains with ordered molecular organization appeared, although random molecules could be observed on Au(111) at the very initial stage. At 30 s, the SAM consisted of uniform short stripes. Each stripe consisted of sets of decanethiol mainly containing eight molecules. With the immersion time increasing, the length of the stripes increased. At 5 min, the alkyl chains overlapped each other between the adjacent stripes, indicating the start of a stacked process. After immersing Au(111) in decanethiol solution for 3 days, a densely packed adlayer with a (radical 3 x radical 3)R30 degrees structure was observed. The formation process and structure of decanethiol SAMs are well related to sample preparation conditions. The wettability of the decanethiolate SAM-modified Au(111) surface was also investigated.     

Immobilization of rhodium complexes at thiolate monolayers on gold surfaces: catalytic and structural studies

Chiral rhodium-diphosphine complexes have been incorporated into self-assembled thiolate monolayers (SAMs) on gold colloids. Catalysts of this type are of interest because they combine properties of homogeneous and heterogeneous systems. In addition, it should be possible to influence the catalytic properties of the metal center by the neighboring thiolate molecules. Colloids with a diameter of ca. 3 nm, coated with a mixed monolayer of n-octanethiolates and thiolates with chiral rhodium-PYRPHOS end groups, were studied as hydrogenation catalysts. With methyl alpha-acetamido-cinnamate as substrate, virtually the same enantioselectivities (up to 93% ee) and full conversion were obtained as with the corresponding homogeneous [Rh(COD)(PYRPHOS)]BAr(F) catalyst. The colloids were easily recovered by filtration and reused as catalysts three times without loss of enantioselectivity. STM studies of analogous SAMs on Au(111) gave a detailed picture of the structure and dynamics of mixed monolayers of this type. The STM images showed that the catalyst-bearing thiolates are distributed statistically on the surface and that the ordered structure of the n-octanethiolate SAM can be retained during incorporation of the catalyst-bearing thiols using the place-exchange methodology.     

Protein adsorption on oligo(ethylene glycol)-terminated alkanethiolate self-assembled monolayers: The molecular basis for nonfouling behavior

A study of protein resistance of oligo(ethylene glycol) (OEG), HS(CH2)11(OCH2CH2)nOH (n = 2, 4, and 6), self-assembled monolayers (SAMs) on Au(111) surfaces is presented here. Hydroxyl-terminated OEG-SAMs are chosen to avoid the hydrophobic effect observed with methyl-terminated OEG-SAMs, particularly at high packing densities. The structure of the OEG-SAM surfaces is controlled by adjusting the assembly solvent. These SAMs were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Protein adsorption on these surfaces was investigated by surface plasmon resonance (SPR). OEG-SAMs assembled from mixed ethanol and water solutions show higher packing density on gold than those from pure ethanol solution. For EG2OH- and EG4OH-SAMs, proteins (i.e., fibrinogen and lysozyme) adsorb more on the densely packed SAMs prepared from mixed ethanol and water solutions, while EG6OH-SAMs generally resist protein adsorption regardless of the assembly solvent used.     

Dependence of patterned binary alkanethiolate self-assembled monolayers on "UV-photopatterning" conditions and evolution with time, terminal group, and methylene chain length

We have investigated the mechanism of UV photopatterning of binary alkanethiolate self-assembled monolayers (SAMs) adsorbed on Au(111) using time-of-flight secondary ion mass spectrometry. The SAMs were photopatterned using a 500 W Hg arc lamp. The patterning process is strongly dependent on the wavelength of light used. When an unfiltered arc lamp is employed, IR light impinges on the sample and causes considerable sample heating. Methyl-terminated SAMs with less than 14 carbons in the chain melt at the temperatures reached and become very disordered and so can be easily displaced by a second SAM. This leads to significant pattern degradation ("erosion"). SAMs with greater than 14 carbons undergo a transition to an incommensurate phase but remain stable on the surface, and the pattern is retained. When the IR light is filtered out, a different behavior is observed. UV-photopatterned methyl-terminated SAMs with 10 carbons in the chain are stable. Terminal group interactions, such as H-bonding, provide extra stabilization energy during photopatterning, so some patterns with shorter carbon chains may also be stable. The displacement of the photooxidized SAMs on the patterned surface follows kinetics similar to that of large-area SAM formation.     

An STM study on nonionic fluorosurfactant zonyl FSN self-assembly on Au(111): large domains, few defects, and good stability

Nonionic Fluorosurfactant Zonyl FSN self-assembly on Au(111) is investigated with scanning tunneling microscopy under ambient conditions. STM reveals that the FSN forms SAMs on Au(l11) with very large domain size and almost no defects. A (mean square root of 3 x mean square root of 3)R3 degree arrangement of the FSN SAM on Au(111) is observed. The SAMs show excellent chemical stability and last for at least a month in atmospheric conditions. The structure and stability of the FSN SAMs are compared with those of alkanethiols SAMs. It is expected that FSN may serve as a new kind of molecule to form SAMs for surface modification, which would benefit wider applications for various purposes.     

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.     

Formation of ordered self-assembled monolayers by adsorption of octylthiocyanates on Au(111)

Self-assembled monolayers (SAMs) were formed by the spontaneous adsorption of octythiocyanate (OTC) on Au(111) using both solution and ambient-pressure vapor deposition methods at room temperature and 50 degrees C. The surface structures and adsorption characteristics of the OTC SAMs on Au(111) were characterized by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). The STM observation showed that OTC SAMs formed in solution at room temperature have unique surface structures including the formation of ordered and disordered domains, vacancy islands, and structural defects. Moreover, we revealed for the first time that the adsorption of OTC on Au(111) in solution at 50 degrees C led to the formation of SAMs containing small ordered domains, whereas the SAMs formed by vapor deposition at 50 degrees C had long-range ordered domains, which can be described as (radical3 x 2 radical19)R5 degrees structures. XPS measurements of the peaks in the S 2p and N 1s regions for the OTC SAMs showed that vapor deposition is the more effective method as compared to solution deposition for obtaining high-quality SAMs by adsorption of OTC on gold. The results obtained will be very useful in understanding the SAM formation of organic thiocyanates on gold surfaces.     

Molecular tilting and its impact on frictional properties of n-alkane self-assembled monolayers

Hydrophobic, methyl-terminated self-assembled monolayer (SAM) surfaces can be used to reduce friction. Among methyl-terminated SAMs, the frictional properties of alkanethiol SAMs and silane SAMs have been well-studied. In this research, we investigated friction of methyl-terminated n-hexatriacontane (C36) SAM and compared its friction properties with the alkanethiol and silane SAMs. Alkane SAM does not have an anchoring group. The alkane molecules stand on the surface by physical adsorption, which leads to a higher surface mobility of alkane molecules. We found that C36 SAM has a higher coefficient of friction than that of octadecyltrichlorosilane (OTS) silane. When an atomic force microscope (AFM) tip was swiped across the alkane SAM with a loading force, we found that the alkane SAM can withstand the tip loading pressure up to 0.48 GPa. Between 0.48 and 0.49Ga, the AFM tip partially penetrated the SAM. When the tip moved away, the deformed SAM healed and maintained the structural integrity. When the loading pressure was higher than 0.49 GPa, the alkane SAM was shaved into small pieces by the tip. In addition, we found that the molecular tilting of C36 molecules interacted with the tribological properties of the alkane SAM surface. On one hand, a higher loading force can push the rod-like alkane molecules to a higher tilting angle; on the other hand, a higher molecular tilting leads to a lower friction surface.     

Comparative electrochemical scanning tunneling microscopy study of nonionic fluorosurfactant zonyl FSN self-assembled monolayers on Au(111) and Au(100): a potential-induced structural transition

We investigate the structure of nonionic fluorosurfactant zonyl FSN self-assembled monolayers on Au(111) and Au(100) in 0.05 M H(2)SO(4) as a function of the electrode potential by electrochemical scanning tunneling microscopy (ECSTM). On Au(111), a (3(1/2) × 3(1/2))R30° arrangement of the FSN SAMs is observed, which remains unchanged in the potential range where the redox reaction of FSN molecules does not occur. On Au(100), some parallel corrugations of the FSN SAMs are observed, which originate from the smaller distance and the repulsive interaction between FSN molecules to make the FSN molecules deviate from the bridging sites, and ECSTM reveals a potential-induced structural transition of the FSN SAMs. The experimental observations are rationalized by the effect of the intermolecular interaction. The smaller distance between molecules on Au(100) results in the repulsive force, which increases the probability of structural change induced by external factors (i.e., the electrode potential). The appropriate distance and interactions of FSN molecules account for the stable structure of FSN SAMs on Au(111). Surface crystallography may influence the intermolecular interaction through changing the molecular arrangements of the SAMs. The results benefit the molecular-scale understanding of the behavior of the FSN SAMs under electrochemical potential control.     

Tail molecule dependence of thiolate adsorption on Au(111) surface: Theoretical study

The adsorption of thiolates with various tail molecules on the Au(111) surface has been investigated by first-principles calculations. We have considered six typical thiolate molecules, that is, methylthiolate, ethylthiolate, ethylenethiolate, acetylenethiolate, benzenethiolate, and thiophenethiolate. It is found that these thiolates exhibit little difference in their stable adsorption geometries. They are adsorbed at the bridge site with being significantly tilted from the surface normal. The adsorption energy of thiolate on Au, on the other hand, largely varies depending on the type of tail molecule, and is linearly proportional to the binding energy of thiolate with H. We discuss the tail molecule dependence in terms of the bonding environment around the C atom connected to the head S atom.     

Molecular simulation study of water interactions with oligo (ethylene glycol)-terminated alkanethiol self-assembled monolayers

Molecular simulations were performed to study a system consisting of protein (e.g., lysozyme) and self-assembled monolayers (SAMs) terminating with different chemical groups in the presence of explicit water molecules and ions. Mixed SAMs of oligo (ethylene glycol) [S(CH2)4(OCH2CH2)4OH, (OEG)] and hydroxyl-terminated SAMs [S(CH2)4OH] with a mole fraction of OEG at chiOEG = 0.2, 0.5, 0.8, and 1.0 were used in this study. In addition, methyl-terminated SAMs [S(CH2)11CH3] were also studied for comparison. The structural and dynamic behavior of hydration water, the flexibility and conformation state of SAMs, and the orientation and conformation of protein were examined. Simulation results were compared with those of experiments. It appears that there is a correlation between OEG surface resistance to protein adsorption and the surface density of OEG chains, which leads to a large number of tightly bound water molecules around OEG chains and the rapid mobility of hydrated SAM chains.     

Ultrafast shock compression of self-assembled monolayers: a molecular picture

Simulations of self-assembled monolayers (SAMs) are performed to interpret experimental measurements of ultrafast approximately 1 GPa (volume compression deltaV approximately 0.1) planar shock compression dynamics probed by vibrational sum-frequency generation (SFG) spectroscopy (Lagutchev, A. S.; Patterson, J. E.; Huang, W.; Dlott, D. D. J. Phys. Chem. B 2005, 109, XXXX). The SAMs investigated are octadecanethiol (ODT) and pentadecanethiol (PDT) on Au(111) and Ag(111) substrates, and benzyl mercaptan (BMT) on Au(111). In the alkane SAMs, SFG is sensitive to the instantaneous orientation of the terminal methyl; in BMT it is sensitive to the phenyl orientation. Computed structures of alkane SAMs are in good agreement with experiment. In alkanes, the energies of gauche defects increase with increasing number and depth below the methyl plane, with the exception of ODT/Au where both single and double gauche defects at the two uppermost dihedrals have similar energies. Simulations of isothermal uniaxial compression of SAM lattices show that chain and methyl tilting is predominant in PDT/Au, ODT/Ag and PDT/Ag, whereas single and double gauche defect formation is predominant in ODT/Au. Time-resolved shock data showing transient SFG signal loss of ODT/Au and PDT/Au are fit by calculations of the terminal group orientations as a function of deltaV and their contributions to the SFG hyperpolarizability. The highly elastic response of PDT/Au results from shock-generated methyl and chain tilting. The viscoelastic response of ODT/Au results from shock generation of single and double gauche defects. Isothermal compression simulations help explain and fit the time dependence of shock spectra but generally underestimate the magnitude of SFG signal loss because they do not include effects of high-strain-rate dynamics and shock front and surface irregularities.     

Chemical force titrations of functionalized Si(111) surfaces

Chemical force titrations-plots of the adhesive force between an atomic force microscope tip and sample as a function of pH-were acquired on alkyl monolayer-derivatized Si(111) surfaces. Gold-coated AFM tips modified with thioalkanoic acid self-assembled monolayers (SAM) were employed. Alkyl monolayer-derivatized Si(111) surfaces terminated with methyl, carboxyl, and amine groups were produced via hydrosilylation reactions between 1-alkene reagents and H-terminated silicon. The functionalized surfaces were characterized using standard surface science techniques (AFM, FTIR, and XPS). Titration of the methyl-terminated surface using the modified (carboxyl-terminated) atomic force microscope tip resulted in a small pH-independent hydrophobic interaction. Titration of the amine-terminated surface using the same tip resulted in the determination of a surface pKa of 5.8 for the amine from the pH value from the maximum in the force titration curve. A pK(1/2) of 4.3 was determined for the carboxyl-terminated Si(111) in a similar way. These results will be discussed in relation to the modified Si(111) surface chemistry and organic layer structure, as well as with respect to existing results on Au surfaces modified with SAMs bearing the same functional groups.     

Electrochemical stability of self-assembled monolayers on nanoporous Au

Desorption of thiolate self-assembled monolayers (SAMs) seriously limits the fabrication of thiol-based devices. Here we demonstrate that nanoporous Au produced by dealloying Au-Ag alloys exhibits high electrochemical stability against thiolate desorption. Nanoporous Au has many defective sites, lattice strain and residual Ag on the ligament surface. First-principles calculations indicate that these surface aspects increase the binding energy between a SAM and the surface of nanoporous Au.     

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).