A very mild method was developed for the attachment of high-quality organic monolayers on crystalline silicon surfaces. By using visible light sources, from 447 to 658 nm, a variety of 1-alkenes and 1-alkynes were attached to hydrogen-terminated Si(100) and Si(111) surfaces at room temperature. The presence and the quality of the monolayers were evaluated by static water contact angles, X-ray photoelectron spectroscopy, and IR spectroscopy. Monolayers prepared by thermal, UV light, or visible light initiation were compared. Additionally, the ability of infrared reflection-absorption spectroscopy to study organic monolayers on silicon was explored. A reaction mechanism is discussed on the basis of investigations of the reaction behavior of 1-alkenes with silicon wafers with varying types and levels of doping. Finally, a series of mixed monolayers derived from the mixed solutions of a 1-alkene and an omega-fluoro-1-alkene were investigated to reveal that the composition of the mixed monolayers was directly proportional to the molar ratio of the two compounds in the solutions.

On H-Si(111), monolayer assembly with 1-alkenes results in alkyl monolayers with a Si-C-C linkage to the silicon substrate, while 1-alkynes yield alkenyl monolayers with a Si-C=C linkage. To investigate the influence of the different linkage groups on the final monolayer structure, organic monolayers were prepared from 1-alkenes and 1-alkynes with chain lengths from C(12) to C(18), and the final monolayer structures were studied in detail by static water contact angles measurements, ellipsometry, attenuated total reflectance infrared (ATR-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The thicknesses, tilt angles, and packing densities of the alkyl monolayers are in good agreement with literature values, whereas increased thicknesses, reduced tilt angles, and improved packing densities were observed for the alkenyl monolayers. Finally, the surface coverages for alkyl monolayers were determined to be 50-55% (in line with literature values), while those for the alkenyl monolayers increased with the chain length from 55% for C(12) to as high as 65% for C(18)! The latter value is very close to the theoretical maximum of 69% obtainable on H-Si(111). Such enhanced monolayer quality and increased surface coverage of the alkenyl monolayers, in combination with the oxidation-inhibiting nature of the Si-C=C linkage, significantly increases the chance of successful implementation of organic monolayers on oxide-free silicon in molecular electronic and biosensor devices, especially in view of the importance of a defect-free monolayer structure and the corresponding stability of the monolayer-silicon interface.

A family of amphiphilic cyclodextrins (6, 7) has been prepared through 6-S-alkylation (alkyl=n-dodecyl and n-hexadecyl) of the primary side and 2-O-PEGylation of the secondary side of alpha-, beta-, and gamma-cyclodextrins (PEG=poly(ethylene glycol)). These cyclodextrins form nonionic bilayer vesicles in aqueous solution. The bilayer vesicles were characterized by transmission electron microscopy, dynamic light scattering, dye encapsulation, and capillary electrophoresis. The molecular packing of the amphiphilic cyclodextrins was investigated by using small-angle X-ray diffraction of bilayers deposited on glass and pressure-area isotherms obtained from Langmuir monolayers on the air-water interface. The bilayer thickness is dependent on the chain length, whereas the average molecular surface area scales with the cyclodextrin ring size. The alkyl chains of the cyclodextrins in the bilayer are deeply interdigitated. Molecular recognition of a hydrophobic anion (adamantane carboxylate) by the cyclodextrin vesicles was investigated by using capillary electrophoresis, thereby exploiting the increase in electrophoretic mobility that occurs when the hydrophobic anions bind to the nonionic cyclodextrin vesicles. It was found that in spite of the presence of oligo(ethylene glycol) substituents, the beta-cyclodextrin vesicles retain their characteristic affinity for adamantane carboxylate (association constant K(a)=7.1 x 10(3) M(-1)), whereas gamma-cyclodextrin vesicles have less affinity (K(a)=3.2 x 10(3) M(-1)), and alpha-cyclodextrin or non-cyclodextrin, nonionic vesicles have very little affinity (K(a) approximately 100 M(-1)). Specific binding of the adamantane carboxylate to beta-cyclodextrin vesicles was also evident in competition experiments with beta-cyclodextrin in solution. Hence, the cyclodextrin vesicles can function as host bilayer membranes that recognize small guest molecules by specific noncovalent interaction.

We describe the formation of alkyl monolayers on silicon carbide (SiC) and silicon-rich silicon nitride (SixN4) surfaces, using UV irradiation in the presence of alkenes. Both the surface preparation and the monolayer attachment were carried out under ambient conditions. The stable coatings obtained in this way were studied by water contact angle measurements, infrared reflection absorption spectroscopy, X-ray reflectivity, and X-ray photoelectron spectroscopy. Besides unfunctionalized 1-alkenes, methyl undec-10-enoate, and 2,2,2-trifluoroethyl undec-10-enoate were also grafted onto both substrates. The resulting ester-terminated surfaces could then be further reacted after hydrolysis using amide chemistry to easily allow the attachment of amine-containing compounds.