On-surface products from de-fluorination of C60F48 on Ag(111): C60, C60Fx and silver fluoride formation.

By employing diverse surface sensitive synchrotron radiation spectroscopies we demonstrate that the fluorine content of initial C60F48 deposited at room temperature on Ag(111) varies with molecular coverage. At the very early stages of deposition, C60F48 fully de-fluorinates and transforms into C60. Strong indications of silver fluoride formation are provided. The chemical footprint of fluorinated fullerenes emerges at relatively low molecular coverage indicating that the degree of fullerene de-fluorination decreases (from total to partial de-fluorination) as molecules are deposited. Full de-fluorination stops well before the substrate surface is completely covered by fullerenes. At the molecular level, the fluorine loss observed by spectroscopic techniques is supported by scanning tunneling microscopy imaging. Both molecules and metal surface are importantly involved in the process.

Intramolecular Force Contrast and Dynamic Current-Distance Measurements at Room Temperature.

Scanning probe microscopy can be used to probe the internal atomic structure of flat organic molecules. This technique requires an unreactive tip and has, until now, been demonstrated only at liquid helium and liquid nitrogen temperatures. We demonstrate intramolecular and intermolecular force contrast at room temperature on PTCDA molecules adsorbed on a Ag/Si(111)-(√[3]×√[3]) surface. The oscillating force sensor allows us to dynamically measure the vertical decay constant of the tunneling current. The precision of this method is increased by quantifying the transimpedance of the current to voltage converter and accounting for the tip oscillation. This measurement yields a clear contrast between neighboring molecules, which we attribute to the different charge states.

Structure formation in diindenoperylene thin films on copper(111).

First-principles calculations were combined with scanning tunneling microscopy (STM) measurements to analyze the adsorption of diindenoperylene (DIP) molecules on Cu(111) surfaces. The influence of the substrate on the geometry of single adsorbed molecules, their diffusion barriers, as well as the role of step-edges and intermolecular interactions for molecular self-assembly and structure growth are studied. Long-range ordered arrangements of DIP molecules are found to be most favorable irrespective of the terrace width. Energetically less favored short-range order structures, however, are observed as well.

Strong water-mediated friction asymmetry and surface dynamics of zwitterionic solids at ambient conditions: L-alanine as a case study.

Water molecules strongly interact with freshly cleaved (011) surfaces of L-alanine single crystals at low relative humidity (below 10%) promoting diffusion of L-alanine molecules. Species mobility is enhanced above ~40% leading to the formation of two-dimensional islands with long-range order through Ostwald ripening. Scanning force microscopy experiments reveal that both, islands and terraces, are identical in nature (composition and crystallographic structure) but a relevant friction asymmetry appearing upon water-surface interaction evidences that orientation dependent properties exist between them at the molecular level. We interpret this observation as due to water incorporation in the topmost surface crystal structure. Eventually, for high humidity values, surface dissolution and roughening occur.

Contrast inversion in non-contact Dynamic Scanning Force Microscopy: what is high and what is low?

The present work proves that when non-contact Dynamic Scanning Force Microscopy (DSFM) is performed in ambient conditions wrong height measurements of heterogeneous samples can be obtained. In some extreme cases even contrast inversion can be observed. Alkanethiol islands on Au (111) have been used as model system, where contrast inversion is observed with different DSFM modes and various data acquisition parameters. To understand this effect, spectroscopy measurements have been used to show that contrast inversion is really a consequence of the differences in the interaction measured between tip and sample on the bare Au substrate and on the alkanethiol islands. We propose that this interaction is mainly induced by liquid necks forming between tip and sample, which is much stronger on the hydrophilic Au substrate than on the hydrophobic alkanethiol islands.

Exploring the tilt-angle dependence of electron tunneling across molecular junctions of self-assembled alkanethiols.

Electronic transport mechanisms in molecular junctions are investigated by a combination of first-principles calculations and current-voltage measurements of several well-characterized structures. We study self-assembled layers of alkanethiols grown on Au(111) and form tunnel junctions by contacting the molecular layers with the tip of a conductive force microscope. Measurements done under low-load conditions permit us to obtain reliable tilt-angle and molecular length dependencies of the low-bias conductance through the alkanethiol layers. The observed dependence on tilt-angle is stronger for the longer molecular chains. Our calculations confirm the observed trends and explain them as a result of two mechanisms, namely, a previously proposed intermolecular tunneling enhancement as well as a hitherto overlooked tilt-dependent molecular gate effect.

Grafting of monocarboxylic substituted polychlorotriphenylmethyl radicals onto a COOH-functionalized self-assembled monolayer through copper (II) metal ions.

A monocarboxylic substituted polychlorotriphenylmethyl radical (PTMCOOH) has been grafted onto a COOH-functionalized SAM (mercaptohexadecanoic acid, MHDA SAM), using copper (II) metal ions as linkers between the carboxyl groups of the SAM and the ligand. The metal-radical adlayer has been characterized thoroughly using different surface analysis techniques, such as contact angle, IRRAS, XPS, SPR, ToF-SIMS, SFM, and NEXAFS. The magnetic character was confirmed by EPR. The density of unoccupied states was investigated using X-ray absorption spectroscopy. A low-energy peak in the NEXAFS spectrum directly revealed the presence of partially occupied electronic levels, thus proving the open-shell character of the grafted ligands. SEM measurements on a laterally patterned sample prepared by muCP of MHDA in a matrix of hexadecane thiolate (a CH 3-terminated SAM) was performed to demonstrate that the metal-assisted anchoring of the open-shell ligand occurs selectively on the COOH terminated SAM. These results represent an easy and new approach to anchor organic radicals on surfaces and constitute a first step toward the growth of magnetic metal-organic radical-based frameworks on solid substrates.

Nanomechanical properties of surface-modified titanium alloys for biomedical applications.

The mechanical properties of the oxide layers developed at elevated temperature on three vanadium-free titanium alloys of interest for biomedical applications were investigated by means of the nanoindentation technique. The as-received alloys (Ti-13Nb-13Zr, Ti-15Zr-4Nb and Ti-7Nb-6Al) and their oxide scales formed by reaction with air at 750 degrees C for several oxidation times were analysed comparatively. In particular, the hardness and the Young's modulus exhibit larger values for the thermally oxidized alloys than for the untreated specimens. However, the Ti-7Nb-6Al alloy shows a different tendency to that of the TiNbZr alloys, which seems to be related to a different oxide layer growth as a function of the oxidation time.

Real time scanning force microscopy observation of a structural phase transition in self-assembled alkanethiols.

We present here a new approach based on high resolution scanning force microscopy that permits molecular determination and frictional discrimination between coexisting molecular configurations of alkanethiols on Au(111). The method has allowed visualizing in real time a phase transition between two differently ordered self-assembled configurations, which spontaneously takes place with time at constant coverage and under ambient conditions. Frictional force measurements indicate that the molecular rearrangement observed occurs via an order-disorder-order process.

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.