Self-Assembled Monolayers of Symmetrical and Mixed Alkyl Fluoroalkyl Disulfides on Gold. 1. Synthesis of Disulfides and Investigation of Monolayer Properties

The synthesis of a variety of symmetrical bis(alkyl) and bis(fluoroalkyl) disulfides as well as mixed alkyl fluoroalkyl disulfides containing ester or amide groups is described. Self-assembled monolayers of these compounds on gold formed by spontaneous adsorption from solution are studied by contact angle measurements and polarized grazing incidence Fourier transform infrared spectroscopy (FTIR). The contact angles indicate tight packing of the molecules and the incorporation of both alkyl and fluoroalkyl chains in the monolayers. By means of FTIR, the typical tilted orientation of the alkyl chains is confirmed for monolayers derived from symmetrical alkyl disulfides, whereas, in self-assembled monolayers of the symmetrical fluorocarbon and the mixed disulfides, the molecules are oriented much closer to the surface normal direction. The wetting properties and the FTIR spectra of monolayers formed by coadsorption of an n-alkanethiol and a perfluorinated thiol are comparable to those formed by the self-assembly of the corresponding mixed disulfide. There is no indication for phase separation in any of the systems studied at room temperature. The mixed alkyl fluoroalkyl disulfides promise to form suitable monolayers on gold for the investigation of heat-induced phase separation on the gold surface

Structural properties and Raman spectroscopy of lipid Langmuir monolayers at the air-water interface

Spectra of octadecylamine (ODA) Langmuir monolayers and egg phosphatidylcholine (PC)/ODA-mixed monolayers at the air-water interface have been acquired. The organization of the monolayers has been characterized by surface pressure-area isotherms. Application of polarized optical microscopy provides further insight in the domain structures and interactions of the film components. Surface-enhanced Raman scattering (SERS) data indicate that enhancement in Raman spectra can be obtained by strong interaction between headgroups of the surfactants and silver particles in subphase. By mixing ODA with phospholipid molecules and spreading the mixture at the air-water interface, we acquired vibrational information of phospholipid molecules with surfactant-aided SERS effect.Comment: 8 pages, 9 figure

Evolution of the interfacial structure of LaAlO3 on SrTiO3

The evolution of the atomic structure of LaAlO3 grown on SrTiO3 was investigated using surface x-ray diffraction in conjunction with model-independent, phase-retrieval algorithms between two and five monolayers film thickness. A depolarizing buckling is observed between cation and oxygen positions in response to the electric field of polar LaAlO3, which decreases with increasing film thickness. We explain this in terms of competition between elastic strain energy, electrostatic energy, and electronic reconstructions. The findings are qualitatively reproduced by density-functional theory calculations. Significant cationic intermixing across the interface extends approximately three monolayers for all film thicknesses. The interfaces of films thinner than four monolayers therefore extend to the surface, which might affect conductivity

Crystallization of Isotactic Poly(methylmethacrylate) in Monolayers and Thin Films

Langmuir-Blodgett monolayers of isotactic PMMA exhibit a pressure-induced transition upon compression, that can be described in terms of a two-dimensional crystallization process, analogous to a normal melt crystallization. These water surface crystallized monolayers can be used to prepare highly crystalline thin films of isotactic PMMA with tailor-made orientational characteristics.

Synthesis and Characterization of Mixed Methyl/Allyl Monolayers on Si(111)

The formation of mixed methyl/allyl monolayers has been accomplished through a two-step halogenation/alkylation reaction on Si(111) surfaces. The total coverage of alkylated Si, the surface recombination velocities, and the degree of surface oxidation as a function of time have been investigated using X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and microwave conductivity measurements. The total coverage of alkyl groups, the rate of oxidation, and the surface recombination velocities of Si(111) terminated by mixed monolayers were found to be close to those observed for CH_3−Si(111) surfaces. Hence, the mixed-monolayer surfaces retained the beneficial properties of CH_3−Si(111) surfaces while allowing for convenient secondary surface functionalization

1-octadecene monolayers on Si(111) hydrogen-terminated surfaces: effects of substrate doping

We have studied the electronic properties, in relation to their structural properties, of monolayers of 1-octadecene attached on a hydrogen-terminated (111) silicon surface. The molecules are attached using the free-radical reaction between C=C and Si-H activated by an ultraviolet illumination. We have compared the structural and electrical properties of monolayers formed on silicon substrate of different types (n-type and p-type) and different doping concentrations from low-doped (~1E14 cm-3) to highly doped (~1E19 cm-3) silicon substrates. We show that the monolayers on n-, p- and p+ silicon are densely packed and that they act as very good insulating films at a nanometer thickness with leakage currents as low as ~1E-7 A.cm-2 and high quality capacitance-voltage characteristics. The monolayers formed on n+-type silicon are more disordered and therefore exhibit larger leakage current densities (>1E-4 A.cm-2) when embedded in a silicon/monolayer/metal junction. The inferior structural and electronic properties obtained with n+-type silicon pinpoint the important role of surface potential and of the position of the surface Fermi level during the chemisorption of the organic monolayers.Comment: 33 pages, 8 figures, to be published J. Appl. Phy

Adhesive and conformational behaviour of mycolic acid monolayers

We have studied the pH-dependent interaction between mycolic acid (MA) monolayers and hydrophobic and hydrophilic surfaces using molecular (colloidal probe) force spectroscopy. In both cases, hydrophobic and hydrophilic monolayers (prepared by Langmuir-Blodgett and Langmuir-Schaefer deposition on silicon or hydrophobized silicon substrates, respectively) were studied. The force spectroscopy data, fitted with classical DLVO (Derjaguin, Landau, Verwey, and Overbeek) theory to examine the contribution of electrostatic and van der Waals forces, revealed that electrostatic forces are the dominant contribution to the repulsive force between the approaching colloidal probe and MA monolayers. The good agreement between data and the DLVO model suggest that beyond a few nm away from the surface, hydrophobic, hydration, and specific chemical bonding are unlikely to contribute to any significant extent to the interaction energy between the probe and the surface. The pH-dependent conformation of MA molecules in the monolayer at the solid-liquid interface was studied by ellipsometry, neutron reflectometry, and with a quartz crystal microbalance. Monolayers prepared by the Langmuir-Blodgett method demonstrated a distinct pH-responsive behaviour, while monolayers prepared by the Langmuir-Schaefer method were less sensitive to pH variation. It was found that the attachment of water molecules plays a vital role in determining the conformation of the MA monolayers. (C) 2010 Elsevier B.V. All rights reserved