Two-dimensional Molecular Phase Transition of Alkylated-TDPB on Au(111) and Cu(111) Surfaces

The derivatives of aromatic cores bearing alkyl chains with different lengths are of potential interest in on-surface chemistry, and thus have been widely investigated both at liquid-solid interfaces and in vacuum. Here, we report on the structural evaluation of self-assembled 1,3,5-tri(4-dodecylphenyl)benzene(TDPB) molecules with increased molecular coverages on both Au(111) and Cu(111) surfaces. As observed on Au(111), rhombic and herringbone structures emerge successively depending on surface coverage. In the case of Cu(111), the same process of phase conversion is also observed, but with two distinct structures. In comparison, the self-assembled structures on Au(111) surface are packed more densely than that on Cu(111) surface under the same preparation conditions. This may fundamentally result from the higher adsorption energy of TDPB molecules on Cu(111), restricting their adjustment to optimize a thermodynamically favorable molecular packing.     

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.     

Molecular self-assembly at bare semiconductor surfaces: preparation and characterization of highly organized octadecanethiolate monolayers on GaAs(001)

Through rigorous control of preparation conditions, organized monolayers with a highly reproducible structure can be formed by solution self-assembly of octadecanethiol on GaAs (001) at ambient temperature. A combination of characterization probes reveal a structure with conformationally ordered alkyl chains tilted on average at 14 +/- 1 degrees from the surface normal with a 43 +/- 5 degrees twist, a highly oleophobic and hydrophobic ambient surface, and direct S-GaAs attachment. Analysis of the tilt angle and film thickness data shows a significant mismatch of the average adsorbate molecule spacings with the spacings of an intrinsic GaAs(001) surface lattice. The monolayers are stable up to approximately 100 degrees C and exhibit an overall thermal stability which is lower than that of the same monolayers on Au[111] surfaces. A two-step solution assembly process is observed: rapid adsorption of molecules over the first several hours to form disordered structures with molecules lying close to the substrate surface, followed by a slow densification and asymptotic approach to final ordering. This process, while similar to the assembly of alkanethiols on Au[111], is nearly 2 orders of magnitude slower. Finally, despite differences in assembly rates and the thermal stability, exchange experiments with isotopically tagged molecules show that the octadecanethiol on GaAs(001) monolayers undergo exchange with solute thiol molecules at roughly the same rate as the corresponding exchanges of the same monolayers on Au[111].     

Structures of 17,19-hexatriacontadiyne monolayers on Au(111) studied by infrared reflection absorption spectroscopy and scanning tunneling microscopy

The aggregation and reaction of 17,19-hexatriacontadiyne molecules are studied on a Au(111) surface. The molecular orientation and arrangement are elucidated by infrared reflection absorption spectroscopy (IRAS) and scanning tunneling microscopy (STM). A vapor-deposited monolayer and a multilayered film formed by adsorption from the solution provide IRA spectra with bands due to the antisymmetric and symmetric stretching of methylenes in the gauche conformation. After the adsorbed film is rinsed with the solvent, however, the spectrum loses the gauche bands and is characterized by the enhanced C-H(distal) and C-H(proximal) stretching bands, which means that all-trans molecules are laid flat. Only STM images for the rinsed film display columnar structures on the herringbones of the reconstructed Au(111) surface; the alkyl chain direction is found to be parallel to the Au atom row. The results indicate that an ordered monolayer is formed first at the liquid-solid interface, and then, disordered overlayers with the gauche conformation are grown but removed by a rinse. Upon exposure to UV light, thus obtained monomer columns are converted into oligomers with flexible backbones and an increased gauche population in the alkyl chains, which resemble red phase polydiacetylenes in LB films.     

Infrared studies of the potential controlled adsorption of sodium dodecyl sulfate at the Au(111) electrode surface

Quantitative subtractively normalized interfacial Fourier transform infrared reflection spectroscopy (SNIFTIRS) was used to determine the conformation and orientation of sodium dodecyl sulfate (SDS) molecules adsorbed at the single crystal Au(111) surface. The SDS molecules form a hemimicellar/hemicylindrical (phase I) structure for the range of potentials between -200 ≤ E < 450 mV and condensed (phase II) film for electrode potentials ≥500 mV vs Ag/AgCl. The SNIFTIRS measurements indicate that the alkyl chains within the two adsorbed states of SDS film are in the liquid-crystalline state rather than the gel state. However, the sulfate headgroup is in an oriented state in phase I and is disordered in phase II. The newly acquired SNIFTIR spectroscopy measurements were coupled with previous electrochemical, atomic force microscopy, and neutron reflectivity data to improve the current existing models of the SDS film adsorbed on the Au(111) surface. The IR data support the existence of a hemicylindrical film for SDS molecules adsorbed at the Au(111) surface in phase I and suggest that the structure of the condensed film in phase II can be more accurately modeled by a disordered bilayer.     

Investigation of the scanning tunneling microscopy image, the stacking pattern, and the bias-voltage-dependent structural instability of 1,10'-phenanthroline molecules adsorbed on Au(111) in terms of electronic structure calculations

A self-assembled monolayer of 1,10'-phenanthroline (phen) molecules on Au(111) was found to undergo a structural phase transition when the bias voltage is switched in scanning tunneling microscopy (STM) experiments (Phys. Rev. Lett. 1995, 75, 2376; Surf. Sci. 1997, 389, 19). The nature of two bright spots representing each phen molecule in the high-resolution STM images of phen molecules on Au(111) was identified by calculating the partial density plots for a monolayer of phen molecules adsorbed on Au(111) with tight-binding electronic structure calculations. The stacking pattern of chains of phen molecules on Au(111) was explained by studying the intermolecular interactions between phen molecules on the basis of first-principles electronic structure calculations for a phen dimer, (phen)(2). The structural instability of phen molecule arrangement caused by the bias-voltage switch was probed by estimating the adsorbate-surface interaction energy with the point-charge approximation for Au(111).     

Dynamic in situ characterization of organic monolayer formation via a Novel substrate-mediated mechanism

Ultrahigh vacuum scanning tunneling microscopy data investigating octylsilane (C8H17SiH3) monolayer pattern formation on Au(111) are presented. The irregular monolayer pattern exhibits a 60 A length scale. Formation of the octylsilane monolayer relaxes the Au(111) 23 x square root3 surface reconstruction and ejects surface Au atoms. Au adatom diffusion epitaxially extends the Au(111) crystal lattice via step edge growth and island formation. The chemisorbed monolayer covers the entire Au surface at saturation exposure. Theoretical and experimental data suggest the presence of two octylsilane molecular adsorption phases: an atop site yielding a pentacoordinate Si atom and a surface vacancy site yielding a tetracoordinate Si atom. Theoretical simulations investigating two-phase monolayer self-assembly dynamics on a solid surface suggest pattern formation results from strain-induced spinodal decomposition of the two adsorption phases. Collectively, the theoretical and experimental data indicate octylsilane monolayer pattern formation is a result of interfacial Au-Si interactions and the alkyl chains play a negligible role in the monolayer pattern formation mechanism.     

Oriented organic islands and one-dimensional chains on a Au(111) surface fabricated by electrodeposition: an STM study

Organic islands and oriented one-dimensional (1D) chains are fabricated on a Au(111) surface by electrodeposition. The cyclic voltammograms (CVs) of Au(111) in solutions containing nitrobenzene and picric acid show an electrochemical reaction in a negative potential region, which results in irreversible reductive deposition. The deposition process is monitored by in situ electrochemical scanning tunneling microscopy (ECSTM). At the double layer potential region, for example, nitrobenzene molecules form a well-defined adlayer in a (square root(3) x square root(3)) structure. With potential shifting negative to the reductive region, nitrobenzene is reduced to hydroxyaminobenzene. Organic islands were formed first and then aggregated into ordered 1D chains. The formation of these organic islands and 1D chains is completely potential-dependent. Intriguingly, the so-prepared islands and 1D chains are well-oriented along the reconstructed lines of the underlying Au(111) substrate and stable under ambient conditions even if the sample was removed from electrolyte solution. The results reported here provide a simple and effective method to fabricate oriented organic nanodots and nanowires on a solid surface by an electrochemical technique.     

Self-assembly of 1,4-benzenedithiolate/tetrahydrofuran on a gold surface: a Monte Carlo simulation study

We report a Monte Carlo simulation study of the self-assembly of 1,4-benzenedithiolate (BDT), tetrahydrofuran (THF), and their mixtures on a Au (111) surface. We use the grand canonical Monte Carlo method to obtain the equilibrium adsorption coverage. Canonical ensemble (NVT) simulation is then used to explore further the structural information of the equilibrated systems. Our results indicate that BDT molecules adsorb onto the Au (111) surface with one of the sulfur atoms bonded to Au atoms. THF molecules form clusters on the surface. For BDT-THF mixtures, BDT can selectively adsorb on Au (111) to form a monolayer, whereas the solvent THF molecules either float above BDT monolayer or occupy vacancies on the surface that are not covered by BDT molecules. BDT molecules adsorb on a Au (111) surface with an average tilt angle of about 18-35 degrees to the surface normal. The tilting angle decreases as the coverage increases. In addition, the BDT monolayer constitutes an ordered herringbone structure on the Au (111) surface, and the ordering pattern is insensitive to the BDT coverage. In comparison, the THF molecules exhibit amorphous structure on the Au surface. Interestingly, simulations indicate that the bonding behavior of BDT molecules on Au (111) is coverage-dependent. BDT bonds preferably on the Au top site when the surface coverage is low. As coverage increases, most BDT molecules bond on the bridge and fcc hollow sites.     

Geometry for self-assembling of spherical hydrocarbon cages with methane thiolates on au(111)

An organodisulfide with a pair of adamantane moieties was synthesized, and its self-assembled monolayer (SAM) was formed on Au(111). The adamantane moieties are almost spherical and much bulkier than alkyl chains. The structure was characterized by scanning tunneling microscopy. Two-dimensional crystals of the SAM were found to be four orientationally different hexagonals with almost the same lattice constant with 4 radical 3a/3 and 7a/3 (a = 0.2884 nm, the Au lattice constant). The structure is assigned to four of the high-order commensurate adlayers. The present study of geometry and energetics for self-assembling of such an organosulfur compound with spherical cages provides a new insight into the probable SAM structure of various thiolate derivatives on Au(111).     

4-Mercaptopyridine on Au(111): a scanning tunneling microscopy and spectroscopy study

The adsorption of 4-mercaptopyridine (4MPy) molecules on reconstructed Au(111) is investigated by Scanning Tunneling Microscopy (STM) and Spectroscopy (STS) at low temperature and under ultra-high vacuum (UHV) conditions. As made visible by STM, at low coverage (<10%) 4MPy adsorbs preferentially at elbow sites of the Herringbone reconstruction and at step edges of the Au(111). Increasing coverage (but still <30%) results in formation of molecular chains followed, at even higher coverage, by a 3-dimensional growth. Detailed analysis of z-V spectroscopy (ramping the tunneling bias V while keeping the tunneling current constant) provides information on the bias dependent apparent height of a single 4MPy/Au(111) as well as on the local density of states (LDOS) of single and chain 4MPy molecules in comparison to the bare Au(111) surface revealing a significant shift of the lowest unoccupied molecular orbital (LUMO) towards lower energy for molecules within chains. Additionally, the data provide no evidence that for these samples prepared in UHV the adsorption of 4MPy on Au(111) requires mediating Au adatoms. Also, clear indications are given that the adsorption does not induce a strong reduction of the Au DOS close to its Fermi energy. Finally, in context of the apparent STM height of 4MPy molecules, the behavior of the differential barrier height Φ(diff)(V) = (?(z)?(V)I/?(V)I)(2) on bare Au(111) and 4MPy/Au(111) is analyzed and the corresponding experimental values are applied to recover the LDOS of the molecule for unoccupied states according to a previously published numerical recipe [B. Koslowski, H. Pfeifer and P. Ziemann, Phys. Rev. B, 2009, 80, 165419 and M. Ziegler, N. Néel, A. Sperl, J. Kr?ger, and R. Berndt, Phys. Rev. B, 2009, 80, 125402]. In this way, one obtains a spectrum comprising a constant DOS of the Shockley-like surface state of Au(111) and a Lorentzian line attributed to the LUMO of 4MPy.     

Effect of amino,hydroxyl, and carboxyl terminal groups of alkyl chains of self-assembled monolayers on the adsorption pattern of gold nanoparticles

The adsorption pattern of gold nanoparticles (AuNPs) on functionalized self-assembled monolayers (SAMs) produced on a Au(111) surface was characterized. The Au(111) was modified with 11-amino-1-undecanethiol hydrochloride (AUT), 11-mercapto-1-undecanol (MUT), or 11-mercaptoundecanoic acid (MUA) at an elevated temperature and pressure. The AuNPs aggregated on the AUT-SAM surface, whereas they were well dispersed on the MUT-SAM surface and localized on the MUA-SAM surface. The results suggest that interactions between AuNPs differ according to the degree of peeling of citrate-layer-capped AuNPs. The degree of peeling, which is related to both the surface randomness of the SAMs and the functional characteristics of the terminal group of each SAM, was discussed on the basis of scanning tunneling microscopy observations, X-ray photoelectron spectroscopic analyses, and contact angle measurements. Our study shows that AuNP patterns can be controlled by changing the terminal group of the alkyl thiol SAM on a Au(111) surface.     

Epitaxial supramolecular assembly of fullerenes formed by using a coronene template on a Au(111) surface in solution

Characteristic properties of the coronene layer formed on Au(111) for the epitaxial growth of various fullerenes are described. The electrochemical behavior of the coronene adlayer prepared by immersing a Au(111) substrate into a benzene solution containing coronene was investigated in 0.1 M HClO4. The as-prepared coronene adlayer on Au(111) revealed a well-defined (4 x 4) structure. Structural changes of the array of coronene molecules induced by potential manipulation were clearly observed by in situ scanning tunneling microscopy (STM). Supramolecularly assembled layers of fullerenes such as C60, C70, C60-C60 dumbbell dimer (C120), C60-C70 cross-dimer (C130), and C60 triangle trimer (C180) were formed on the well-defined coronene adlayer on the Au(111) surface by immersing the coronene-adsorbed Au(111) substrate into benzene solutions containing those molecules. The adlayers thus prepared were characterized by comparison with those which were directly attached to the Au(111) surface. The C60 molecules formed a honeycomb array with an internal structure in each C60 cage on the coronene adlayer, whereas C70 molecules were one-dimensionally arranged with the same orientations. The dimers, C120 and C130 molecules, formed an identical structure with c(11 x 4 radical3)rect symmetry. For the C130 cross-dimer molecule, C60 and C70 cages were clearly recognized at the molecular level. It was difficult to identify the adlayer of the C180 molecule directly attached to Au(111); however, individual C180 molecules could be recognized on the coronene-modified Au(111) surface. Thus, the adlayer structures of those fullerenes were strongly influenced by the underlying coronene adlayer, suggesting that the insertion of a coronene adlayer plays an important role in the formation of supramolecular assemblies of fullerenes.     

Novel cyanoterphenyl self-assembly monolayers on Au(111) studied by ellipsometry, x-ray photoelectron spectroscopy, and vibrational spectroscopies

The self-assembled monolayers (SAMs) of two asymmetric disulfides derivatives (namely, LC1 and LC2) were prepared on Au(111). The disulfides contain a pure alkyl chain and an alkyl chain terminated by a cyanoterphenyl group. LC1 and LC2 differ by the way the cyanoterphenyl group is attached onto the alkyl chain: it is expected to be aligned with the alkyl chain in the case of LC1 and perpendicular to it in the case of LC2 (T shape). The consequences in terms of surface coverage, chemical composition, and molecular conformation of the two SAMs are studied using ellipsometry, x-ray photoelectron spectroscopy (XPS), reflection absorption infrared spectroscopy (RAIRS), and broadband femtosecond sum-frequency generation (SFG). A model of coverage and tilt angle based on ellipsometry and XPS results shows that the SAM "manages" the large size of the terphenyl group by lowering the terphenyl containing chain coverage and by increasing the tilt. In the case of LC2, the disulfide breaks during molecular assembly, less terphenyl chains adsorb than pure alkyl chains, and the overall chain coverage is smaller than for LC1. RAIRS and SFG results show that these differences in surface coverage correspond to a drastically different orientation of the terphenyl axis, which lies nearly parallel to the surface for LC2, while it is tilted by approximately 28 degrees for LC1. This shows that the terphenyl group takes much more space on the surface in the case of LC2 and explains why the terphenyl coverage is found smaller for LC2. The anomalous SFG relative intensities observed in the region of CH stretch between CH2 and CH3 modes, and symmetric and antisymmetric modes, show that the chains are not in the fully stretched, all-trans conformation, LC2 being probably more distorted than LC1. These distorsions allow the molecules to occupy the space available below the large terphenyl group. The relative intensities of symmetric and antisymmetric modes are discussed qualitatively for some typical molecular conformations and orientations of the alkyl chain.     

Adsorption states of dialkyl ditelluride autooxidized monolayers on Au(111)

Organic ditellurides (R2Te2 where R = n-butyl (C4), n-octyl (C8), and n-cetyl (C16)) were synthesized, and their adsorption states after oxidation on Au(111) surfaces were studied by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), theoretical analyses, near-edge X-ray absorption fine structure (NEXAFS) measurements, contact angle measurements, and atomic force microscopy (AFM). The obtained results show that dialkyl ditellurides form autooxidized monolayers (AMs) on the surfaces under ambient conditions and that the oxidation process is accelerated by ambient light. XPS, UPS, and theoretical analyses suggest that the autooxidized ditelluride species consist of polymers or oligomers with Te-O-Te-O network structures stabilized by oxygen bridges between tellurium molecules following the cleavage of tellurium-gold bonds. NEXAFS and contact angle measurements indicate that the average tilt angles of the alkyl chains from the surface normal are smaller for the AMs of dialkyl ditellurides having longer alkyl chains. AFM measurements show defects and roughness features around a few angstroms in height on the surfaces of the dialkyl ditelluride AMs.     

Kondo effect in single cobalt phthalocyanine molecules adsorbed on Au(111) monoatomic steps

The Kondo effect in single dehydrogenated cobalt phthalocyanine (CoPc) molecules adsorbed on Au(111) monoatomic steps was studied with a low temperature scanning tunneling microscope. The CoPc molecules adsorbed on Au(111) monoatomic steps show two typical configurations, which can be dehydrogenated to reveal Kondo effect. Moreover, the Kondo temperatures (T(K)) measured for different molecules vary in a large range from approximately 150 to approximately 550 K, increasing monotonically with decreasing Co-Au distance. A simple model consisting of a single Co 3d(z) (2) orbital and a Au 6s orbital is considered and gives a qualitative explanation to the dependence. The large variation of T(K) is attributed to the variation of the interaction between the magnetic-active cobalt ion and the Au substrate resulted from different Co-Au distances.     

Self-assembly of phospholipid molecules at a Au(111) electrode surface

We described the first scanning tunneling microscopy study of spreading unilamellar vesicles of 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) at a Au(111) electrode surface. At the initial stage of the film formation, the molecular resolution images revealed that DMPC molecules are adsorbed flat with the acyl chains oriented parallel to the surface. The molecules assemble into double rows by aligning the acyl chains in the nearest neighbor direction of the reconstructed Au(111) surface and assuming a 90 +/- 10 degrees angle with respect to line of the molecular row. After approximately 30 min, this film is transformed into a hemimicellar state with long rows characteristic for the formation of hemicylindrical surface micelles. At hydrophilic surfaces such as glass, spreading of vesicles involves adsorption, rupture, and sliding of a single bilayer on a lubricating film of the solvent. We have provided the first evidence that a different mechanism is involved in spreading the vesicles at gold. The molecules released by rupture of vesicles self-assemble into an ordered film, and the assembly is controlled by the chain-substrate interaction.     

Does the Surface Matter? Hydrogen‐Bonded Chain Formation of an Oxalic Amide Derivative in a Two‐ and Three‐Dimensional Environment

We report on a multi‐technique investigation of the supramolecular organisation of N,N‐diphenyl oxalic amide under differently dimensioned environments, namely three‐dimensional (3D) in the bulk crystal, and in two dimensions on the Ag(111) surface as well as on the reconstructed Au(111) surface. With the help of X‐ray structure analysis and scanning tunneling microscopy (STM) we find that the molecules organize in hydrogen‐bonded chains with the bonding motif qualitatively changed by the surface confinement. In two dimensions, the chains exhibit enantiomorphic order even though they consist of a racemic mixture of chiral entities. By a combination of the STM data with near‐edge X‐ray absorption fine‐structure spectroscopy, we show that the conformation of the molecule adapts such that the local registry of the functional group with the substrate is optimized while avoiding steric hindrance of the phenyl groups. In the low coverage case, the length of the chains is limited by the Au(111) reconstruction lines restricting the molecules into fcc stacked areas. A kinetic Monte Carlo simulated annealing is used to explain the selective assembly in the fcc stacked regions.     

Self-assembled monolayers based on phenanthroline-gold(111) bonding

The self-assembly of long-alkyl-chain substituted phenanthroline derivatives on highly oriented pyrolitic graphite (HOPG) and gold(111) is compared. Whereas the adsorption on HOPG is controlled by the affinity of alkyl chains for the substrate, which leads to flat-lying adsorbed molecules, alignments of upright-oriented molecules are formed on gold(111). This situation is explained by the bonding of chelating species with gold(111) surfaces and by the pi-stacking interaction between conjugated moieties. This intermediate situation between strong thiol-like chemical bonding and the weak n-alkane-like physical adsorption opens the route toward laterally organized functional molecular assemblies.