Temperature-dependent facet development in the deposition of GaInP on non-planar surfaces

The low-pressure (20 mbar) organometallic vapour-phase epitaxy (LP-OMVPE) of GaInP on non-planar {001} GaAs substrates has been examined. The encountered and {1 0} faceting features develop along the bottom corner and the top edge configurations of the inverted and dovetail grooves, respectively. At higher temperatures (T ≥ 720°C) these features are no longer present. The results have been compared to computer simulations of surface concentration profiles, whereby the inversely proportional relation between temperature and supersaturation, along with varying growth rate on adjacent surfaces of different crystallographic orientations, is found to be the driving force behind the occurrence of these features. The stability of the observed facets is related to the decrease in dangling-bond densities upon surface reconstruction.     

Separation of enantiomers in a diol monolayer studied by fluorescence microscopy and grazing incidence X-ray diffraction

Summary Monolayers of a racemic mixture and of the pure S- and R-enantiomers of 3-hexadecyloxy-propane-1,2-diol have been investigated by fluorescence microscopy and grazing incidence X-ray diffraction. Above the transition pressureΠ _c domains with a polygonal shape appear. On compressing the monolayers shape instabilities occur. While the spirals of the S-enantiomer turn clockwise and the spirals of the R-enantiomer turn counterclockwise, the spirals from one domain of the racemate exhibit opposite handedness. This behaviour is explained by a separation of enantiomers on the molecular level. At all pressures investigated the enantiomers exhibit an oblique lattice. The tilt angle of the molecules decreases with increasing pressure. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Adsorption of some substituted ethylene molecules on Pt(111) at 95 K Part 1: NEXAFS, XPS and UPS studies

The present work examines the interactions of propanoic acid, acrylic acid, acrolein and methylmethacrylate (MMA) with Pt(111) at 95 K to identify the nature of the interactions on this surface. The investigations are carried out by XPS, UPS and NEXAFS on monolayer and multilayer. Theoretical molecular orbital calculations are firstly performed to determine the nature of the bonding and antibonding orbitals of these molecules. The NEXAFS results show that the condensed multilayers of acrylic acid and acrolein are almost oriented parallel to the surface when propanoic acid and MMA are randomly oriented. The monolayer formed at 95 K for all these molecules are also oriented flat on Pt(111). However two different interaction processes are observed depending on the chemical structure of the compound: acrolein and propanoic acid are physisorbed when MMA and acrylic acid are in strong interaction with the metal but with an uncertainty on the chemisorption mode between a π-bonded state or a “di-σ like” state.     

Hierarchical interfaces in random media II: The Gibbs measures

We continue the analysis of hierarchical interfaces in random media started in earlier work. We show that from the estimates on the renormalized random variables established in that work, it follows that these models possess unique Gibbs states describing mostly flat interfaces in dimensionD > 3, if the disorder is weak and the temperature low enough. In the course of the proof we also present very explicit formulas for expectations of local observables.     

Substrate-induced freezing of alkane monolayers adsorbed on Au(1 1 1) dependant on the alkane/gold misfit

The molecular structure of the interfaces between pure C_nH_2n+2 (n=10, 12, 14, 16) and Au(1 1 1) surface has been studied by scanning tunneling microscopy. At 291 K, self-organized monolayers with a lamella structure are formed with these alkanes. The ordered monolayers are melting at temperature higher by 46, 28, 15, 5 K than the melting point of bulk C_nH_2n+2 crystals with n=10, 12, 14, 16, respectively. Two kinds of melting process were observed: (i) a direct solid/liquid phase transition within the monolayer for C₁₀H₂₂, C₁₂H₂₆ and C₁₄H₃₀ molecules, (ii) an intermediate phase for C₁₆H₃₄ molecules. This mesophase corresponds to a two-dimensional liquid crystal formed by molecules moving along their axis and along Au1 1 0. These results agree well with calculations using a geometric model taking in account the misfit between the CH₂–CH₂–CH₂ period along alkyl chain and the gold lattice along 1 1 0 direction.     

Magnetism in low dimensionality

The collective creativity of those working in the field of surface magnetism has stimulated an impressive range of advances. Once wary, theorists are now eager to enter the field. The present article attempts to take a snapshot of where the field has been, with an eye to the more speculative issue of where it is going. Selective examples are used to highlight three general areas of interest: (i) characterization techniques, (ii) materials properties, and (iii) theoretical/simulational advances. Emerging directions are identified and discussed, including laterally confined nanomagnetism and spintronics.     

Mössbauer study of the structure of liquid nanophases trapped in porous silicate and solid microemulsion matrix

Mössbauer spectra of liquid solutions fixed as submicroscopic (nanosize) droplets in solid carriers were taken at room temperature and 77 K. A porous silicate (“thirsty glass”) and microemulsions prepared with a paraffin/naphthalene mixture as dispersion medium served as carriers. Solutions of Mössbauer-active tin(IV) and iron(II) complexes were incorporated in these carriers as nanosize droplets. The Mössbauer effect was observed at temperatures above the freezing point of the solutions. For comparison, the systems were also studied in frozen state. Depending on the nature of the system (carrier-solute-solvent) the presence of three types of species was shown in the droplets on the basis of the Mössbauer parameters: (a) situated in bulk position with no interaction with the walls; (b) adsorbed on the internal surface of the holes in the carrier and (c) in bulk position, but with Mössbauer parameters reflecting the influence of the carrier. In some cases surface-bound and bulk species were present together in the sample. The appearance of the Mössbauer effect in liquid state reveals that the Mössbauer-active atoms are fixed in the nanosize pores by a network of hydrogen bonds which form between the solvent molecules, between solvent and solute molecules and between the solvent molecules and the walls of the pores in the carrier. The main parameters determining the rigidity of the network and the situation of the probe molecules are the hydrogen-bonding ability and the polarity of the components of the system. On the basis of the above observations, a new procedure was elaborated for the Mössbauer study of solutions fixed as nanosize droplets in rigid carriers. The analysis of the Mössbauer parameters gives a qualitative picture regarding the solution structure in the interior of the pores, and the adsorption and wetting properties of the system.     

Characterization of the interaction of poly(ethylene oxide) with nanosize fumed silica: Surface effects on crystallization

Poly(ethylene oxide) (PEO) of 4600 molar mass (PEO‐4600) was crystallized from methanol in the presence of hydrophilic fumed silicas (A380, A200, and OX50) with nominal surface areas of 380, 200, and 50 m²/g and a hydrophobic fumed silica (R812s) modified with methyl groups. The composites were characterized by thermogravimetric analysis and differential scanning calorimetry. The inhibition of crystallization and the tendency for chain reorganization after melting were in the order of A380 > A200 > OX50 > R812s, respectively, that is, both were least for the hydrophobic silica and increased with increasing specific surface area for the hydrophilic silica. The interaction of PEO with the silica increased in the melt state as compared with the solution‐cast samples, resulting in enhanced suppression of crystallization. The following took place at a high silica content: (1) crystallization occurred at crystallization temperatures [T_c < T_c (bulk)], suggesting that the silica inhibited crystallization; (2) crystallites with melt temperatures [T_m < T_m (bulk)] were observed, indictive of smaller and/or less perfect crystals; and (3) melt entropies [ΔS_m (surface) < ΔS_m (bulk)] suggested that the interaction of surface silanols, Si_sOH, with PEO decreased both the melt entropy and crystallite size/perfection. Crystallinity was observed in solution‐cast composites when there were greater than ～0.03 PEO molecules/nm² for native and ～0.01 PEO molecules/nm² for methylated fumed silica, similar to reported plateau equilibrium adsorption values from methanol. These results were consistent with a model in which PEO interacted more strongly with native fumed silica as compared with hydrophobically modified silica because of hydrogen bonding of the ether oxygens of PEO with the acidic silanols, preventing chain mobility and crystallization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1978–1993, 2003