Electron transport through rectifying self-assembled monolayer diodes on silicon: Fermi-level pinning at the molecule-metal interface.

We report the synthesis and characterization of molecular rectifying diodes on silicon using sequential grafting of self-assembled monolayers of alkyl chains bearing a pi group at their outer end (Si/sigma-pi/metal junctions). We investigate the structure-performance relationships of these molecular devices, and we examine the extent to which the nature of the pi end group (change in the energy position of their molecular orbitals) drives the properties of these molecular diodes. Self-assembled monolayers of alkyl chains (different chain lengths from 6 to 15 methylene groups) functionalized by phenyl, anthracene, pyrene, ethylene dioxythiophene, ethylene dioxyphenyl, thiophene, terthiophene, and quaterthiophene were synthesized and characterized by contact angle measurements, ellipsometry, Fourier transform infrared spectroscopy, and atomic force microscopy. We demonstrate that reasonably well-packed monolayers are obtained in all cases. Their electrical properties were assessed by dc current-voltage characteristics and high-frequency (1-MHz) capacitance measurements. For all of the pi groups investigated here, we observed rectification behavior. These results extend our preliminary work using phenyl and thiophene groups (Lenfant et al., Nano Lett. 2003, 3, 741). The experimental current-voltage curves were analyzed with a simple analytical model, from which we extracted the energy position of the molecular orbital of the pi group in resonance with the Fermi energy of the electrodes. We report experimental studies of the band lineup in these silicon/alkyl pi-conjugated molecule/metal junctions. We conclude that Fermi-level pinning at the pi group/metal interface is mainly responsible for the observed absence of a dependence of the rectification effect on the nature of the pi groups, even though the groups examined were selected to have significant variations in their electronic molecular orbitals.

Evidence of a charge-density threshold for optimum efficiency of biocidal cationic surfaces.

The deposition of organic monolayers containing quaternary ammonium groups has been shown by many authors to confer biocidal properties on a large variety of solid surfaces. In a search for the controlling factors, the authors have grafted quaternized poly(vinylpyridine) chains on glass surfaces by two different methods and varied the charge density within the organic layer between 10(12) and 10(16) positive charges per cm2. The measurements show that this parameter has a large influence on the killing efficiency. Bacterial death occurs in less than 10 min in the quiescent state above a threshold value. The value is smaller for bacteria in the growth state. It also depends on the bacterial type. An electrostatic mechanism based on the exchange of counterions between the functionalized cationic surface and the bacterial membrane is proposed and appears consistent with the results.

Plasma surface modification of organic materials: comparison between polyethylene films and octadecyltrichlorosilane self-assembled monolayers.

Low-pressure low-frequency NH3 plasmas have been used for the surface modification of bulk polyethylene films and of octadecyltrichlorosilane (OTS) self-assembled monolayers deposited on oxidized silicon wafers. The incorporation of nitrogen-containing groups by the plasma treatment has been followed by contact angle measurements and by X-ray photoelectron spectroscopy. The surface degradation of the OTS monolayers due to plasma etching has been measured separately by optical ellipsometry with subnanometric accuracy. Our data show clear evidence for the existence of an optimum treatment time, yielding a high density of NH2 functional groups without significant variation of the structural features of the organic material. Self-assembled monolayers appear as excellent model systems to characterize the effects of plasma discharges on polyolefins. In particular, they allow testing the influence of molecular orientation, packing density, and crystallinity on the final results.

Influence of multivalent counterions adsorption on Langmuir films.

It has been shown recently by neutron and X-ray reflectivity that nanometer-sized multivalent counterions (Keggin salts) can assemble as a dense monomolecular sublayer beneath a charged Langmuir monolayer of opposite sign. We have conducted experiments that examine the surface pressure isotherms of docosamine surfactant monolayers under such conditions and have shown that they undergo dramatic modifications when the Keggin salts are added. We model these experimental results by a close-packed sublayer of counterions on which charged surfactants can organize and form complexes. We then provide a thermodynamic description of the surface/sublayer system by giving an expression for surface free energy and surface pressure. We compare the results of this discrete model to traditional mean-field descriptions where the counterions form a diffuse continuous layer. The new features are: i) modifications in the shape of the surface pressure isotherm; ii) appearance of a phase separation in the surfactant layer. Finally, we show that the model is in satisfactory agreement with the experimental isotherms and a best fit yields numerical estimates of the different interaction parameters.

Structures in colloidal physical chemistry.

The vast range of technological and industrial application of colloidal systems is largely a direct result of their diversity of structure on microscopic and mesoscopic scales. Recent progress in understanding these structures allows for greater control of the macroscopic properties, as well as providing new avenues of fundamental research in physics, chemistry and materials science.

Quantitative studies of evanescent wave intensity profiles using optical fluorescence.

The fluorescence of uniformly distributed chromophores in an organic solution has been used to probe the energy density profile of an optical evanescent wave, generated by total internal reflection at the solid-solution interface. The results obtained in the case of an aqueous fluorescein solution in contact with a highly polished silica surface are in good quantitative agreement with the expected exponential decay of the optical energy at the interface. It also justifies the use of the newly developed evanescent wave-induced fluorescence technique to study adsorption and depletion layers of polymer in solution close to solids walls. In such experiments the fluorescence intensity is assumed to be the Laplace transform of the concentration profile of the fluorescently labeled polymer chains. The present data validate the above assumption.

Light-scattering studies of the monomer-dimer states of gramicidin A.

Measurements of the intensity and autocorrelation function of ligh quasielastically scattered by gramicidin A indicate that the molecules exist as dimers in methanol and dioxane and monomers in dimethyl sulfoxide when solute concentrations range from 18 to 50 mg/ml. This gives further evidence that gramicidin A can dimerize in low-polarity media such as the hydrocarbon part of the membrane bilayers.