A new method is described to prepare strongly bonded, compact monolayer films of alkyl- or arylphosphonates on the native oxide surface of Si (SiO(2)/Si). This method is illustrated for octadecyl- and alpha-quarterthiophene-2-phosphonates. For both cases, AFM shows comprehensive coverage of the SiO(2)/Si surface. The thickness of the continuous film of 4TP/SiO(2)/Si was measured both by AFM and by X-ray reflectivity to be ca. 18 A. Direct gravimetric analysis shows surface coverage by alpha-quarterthiophene-2-phosphonate to be about 0.66 nmol/cm(2), which corresponds to molecular packing in the film close to that of crystalline alpha-quarterthiophene. Coverage by octadecylphosphonate was ca. 0.90 nmol/cm(2), corresponding to a cross-sectional area of about 18.5 A(2)/molecule, consistent with close-packed alkyl chains.

We have investigated the controversy surrounding the (sqrt[3] x sqrt[3]) R30 degrees structure of self-assembled monolayers of methylthiolate on Au(111) by first principles molecular dynamics simulations, energy and angle resolved photoelectron diffraction, and grazing incidence x-ray diffraction. Our simulations find a dynamic equilibrium between bridge site adsorption and a novel structure where 2 CH3S radicals are bound to an Au adatom that has been lifted from the gold substrate. As a result, the interface is characterized by a large atomic roughness with both adatoms and vacancies. This result is confirmed by extensive photoelectron and grazing incidence x-ray diffraction measurements.

We use a seeded supersonic molecular beam to control the kinetic energy of pentacene (C22H14) during deposition and growth on Ag(111). Highly ordered thin films are grown at low substrate temperatures (approximately 200 K) at kinetic energies of a few electron volts, as shown by low energy He diffraction and x-ray reflectivity spectra. In contrast, deposition of thermal molecules yields only amorphous films. Growth at room or higher temperature substrates yields films of poorer quality irrespective of the depositing beam energy. We find that after the first wetting layer is completed, a new ordered phase is formed, whose in-plane lattice spacings match one of the bulk crystal planes. The high quality of the films can be interpreted as the result of local annealing induced by the impact of the impinging high-energy molecules.

Although self-assembled monolayers made of long chains of n-alkanethiols [CH3(CH2) n - 1SH] on Au(111) have been extensively studied in the past, the driving forces behind the appearance of the (3 × 2√3) superlattice observed at full coverage are still not completely understood. To focus on the role played by the sulfur headgroup minimizing the interactions between chains and to prevent a possible X-ray-induced damage, we have carried out a He atom diffraction study of the adsorption of the shortest (n = 1) thiol radical, obtained by dissociative adsorption of (CH3S)2, on the Au(111) surface. Contrary to current literature reports, domains of the hexagonal (√3 × √3)R30° structure are observed to convert into the well-ordered (3 × 2√3) superstructure after annealing times of a few hours. The observation of peaks forbidden by the (3 × 2√3) model proposed by Fenter et al. (Fenter, P.; Eberhardt, A.; Eisenberger, P. Science 1994, 266, 1216) suggests a distortion of the symmetry of the unit cell. The observed chemisorption and physisorption energies were in good agreement with the literature.

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