Direct Li+ incorporation during the anodic formation of compact TiO2 layers.

In this work, compact titanium oxide layers are formed by anodization in 1 M H3PO4 aqueous electrolyte containing LiClO4. Elastic Recoil Detection Analysis (ERDA) measurements demonstrate that incorporation of lithium ions occurs during anodization, and cell-voltage transient measurements evidence the different electronic properties of Li-doped TiO2 layers. The mechanism of direct incorporation of Li during the fabrication of TiO2 layers is discussed.

Electrochemical de-alloying in two dimensions: role of the local atomic environment.

We investigate by in situ scanning tunnelling microscopy (STM) the potential dependence of the electrochemical dealloying of NiPd monoatomic layers electrodeposited on Au(111). The dealloying process is achieved by Ni selective dissolution and was studied as a function of NiPd composition: for an alloy with a Ni content ≥70%, quasi-complete Ni dissolution is achieved at a potential of -0.9 VMSE whereas for a Ni content <70%, Ni dissolution at the same potential drastically slows down after the removal of small amounts of Ni. The alloy morphology at this "passivation state" is characterized by the presence of holes in the alloy monolayer with evidence for the Pd enrichment at the hole edges. These findings are confirmed by Monte Carlo simulations. Further Ni dissolution at passivation was achieved by applying more positive potentials which depend on the alloy composition. These results allowed us to determine the correlation between the Ni dissolution onset potential and the local Pd content.

Quantitative IR readout of fulgimide monolayer switching on Si(111) surfaces.

Creating photoactive monolayers of photochromes is of considerable technological interest. This paper describes the construct of fulgimide monolayers on silicon surfaces and presents a quantitative IR analysis studies of their composition and switching properties. The scheme on top shows the structure of the starting C-form terminated Si(111) surface and the graph below sketches the surface composition at the photostationnary states under visisble and UV irradiation, as derived from in situ IR spectroscopy after several UV/vis irradiation cycles.

Molecular monolayers on silicon as substrates for biosensors.

(111) silicon surfaces can be controlled down to atomic level and offer a remarkable starting point for elaborating nanostructures. Hydrogenated surfaces are obtained by oxide dissolution in hydrofluoric acid or ammonium fluoride solution. Organic species are grafted onto the hydrogenated surface by a hydrosilylation reaction, providing a robust covalent Si-C bonding. Finally, probe molecules can be anchored to the organic end group, paving the way to the elaboration of sensors. Fluorescence detection is hampered by the high refractive index of silicon. However, improved sensitivity is obtained by replacing the bulk silicon substrate by a thin layer of amorphous silicon deposited on a reflector. The development of a novel hybrid SPR interface by the deposition of an amorphous silicon-carbon alloy is also presented. Such an interface allows the subsequent linking of stable organic monolayers through Si-C bonds for a plasmonic detection. On the other hand, the semiconducting properties of silicon can be used to implement field-effect label-free detection. However, the electrostatic interaction between adsorbed species may lead to a spreading of the adsorption isotherms, which should not be overlooked in practical operating conditions of the sensor. Atomically flat silicon surfaces may allow for measuring recognition interactions with local-probe microscopy.

Semiquantitative study of the EDC/NHS activation of acid terminal groups at modified porous silicon surfaces.

Infrared spectroscopy is used to investigate the transformation of carboxyl-terminated alkyl chains immobilized on a surface into succinimidyl ester-terminated chains by reaction with an aqueous solution of N-ethyl-N'-(3-(dimethylamino)propyl)carbodiimide (EDC) and N-hydroxysuccinimide (NHS). The acid chains are covalently grafted at the surface of hydrogenated porous silicon whose large specific surface area allows for assessing the activation yield in a semiquantitative way by infrared (IR) spectroscopy and detecting trace amounts of surface products and/or reaction products of small IR cross section. In this way, we rationalize the different reaction paths and optimize the reaction conditions to obtain as pure as possible succinimidyl ester-terminated surfaces. A diagram mapping the surface composition after activation was constructed by systematically varying the solution composition. Results are accounted for by NHS surface adsorption and a kinetic competition between the various EDC-induced surface reactions.

Highly sensitive and reusable fluorescence microarrays based on hydrogenated amorphous silicon-carbon alloys.

We have designed a new architecture of fluorescent microarrays based on a thin layer of hydrogenated amorphous silicon-carbon alloy (a-Si(0.85)C(0.15):H) deposited on an aluminium-on-glass back reflector. These substrates are modified with an organic monolayer anchored through Si-C bonds and terminated with carboxyl groups, allowing for the covalent immobilization of biological probes. The fluorescence yield is maximized by optimization of the a-Si(0.85)C(0.15):H layer thickness. This approach is assessed for DNA recognition, demonstrating an increase in sensitivity by over one order of magnitude as compared to commercial slides, and the possibility of following in situ the molecular recognition event (hybridization). The immobilization chemistry provides these substrates with a superior chemical stability toward ageing or long-term exposure to physiological buffers, which allows for many successive hybridization/dehybridization cycles without measurable changes in performance.

Selective growth and dissolution of Ni on a PdAu bimetallic surface by in situ STM: determining the relative adsorbate-substrate interaction energy.

By studying the electrochemical growth and dissolution of a Ni monolayer on a PdAu bimetallic surface with in situ STM, we demonstrate that Ni grows preferentially on Au(111) in a wide potential range. In contrast, a Ni monolayer covering the entire bimetallic surface can be selectively dissolved from Pd islands. We show that the Ni-substrate interactions play a key role in this selectivity, and we estimate the binding energy of Ni to Pd to be 80 meV smaller than that of Ni to Au.

The titration of carboxyl-terminated monolayers revisited: in situ calibrated fourier transform infrared study of well-defined monolayers on silicon.

The acid-base equilibrium at the surface of well-defined mixed carboxyl-terminated/methyl-terminated monolayers grafted on silicon (111) has been investigated using in situ calibrated infrared spectroscopy (attenuated total reflectance (ATR)) in the range of 900-4000 cm (-1). Spectra of surfaces in contact with electrolytes of various pH provide a direct observation of the COOH <--> COO (-) conversion process. Quantitative analysis of the spectra shows that ionization of the carboxyl groups starts around pH 6 and extends over more than 6 pH units: approximately 85% ionization is measured at pH 11 (at higher pH, the layers become damaged). Observations are consistently accounted for by a single acid-base equilibrium and discussed in terms of change in ion solvation at the surface and electrostatic interactions between surface charges. The latter effect, which appears to be the main limitation, is qualitatively accounted for by a simple model taking into account the change in the Helmholtz potential associated with the surface charge. Furthermore, comparison of calculated curves with experimental titration curves of mixed monolayers suggests that acid and alkyl chains are segregated in the monolayer.

Single-step electrochemical nanolithography of metal thin films by localized etching with an AFM tip.

This work introduces electrochemical nanolithography (ENL), a single-step method in which a metal thin film is locally etched without application of a mask on a 100 nm length scale with an electrochemical atomic force microscope (AFM). The method requires the application of ultra-short voltage pulses on the tip (nanosecond range duration, 2-4 V amplitude), while both the sample and the metalized tip are under independent potentiostatic control for full control of interface reactions in an AFM electrochemical cell. It is demonstrated that Cu films as well as Co and Cu/Co sandwich magnetic films can be patterned if negative voltage pulses are applied to the tip. This method also applies to films deposited on an insulating substrate. Moreover the lateral dimension of lithographed structures is tunable, from a few micrometers down to 150 nm, by appropriate choice of ENL conditions. Simulation of the dissolution process is discussed.

Mechanisms of thermal decomposition of organic monolayers grafted on (111) silicon.

The thermal stability of different organic layers on silicon has been investigated by in situ infrared spectroscopy, using a specially designed variable-temperature cell. The monolayers were covalently grafted onto atomically flat (111) hydrogenated silicon surfaces through the (photochemical or catalytic) hydrosilylation of 1-decene, heptadecafluoro-1-decene or undecylenic acid. In contrast to alkyl monolayers, which desorb as alkene chains around 300 degrees C by the breaking of the Si-C bond through a beta-hydride elimination mechanism, the alkyl layers functionalized with a carboxylic acid terminal group undergo successive chemical transformations. At 200-250 degrees C, the carboxyl end groups couple forming anhydrides, which subsequently decompose at 250-300 degrees C by loss of the functional group. In the case of fluorinated alkyl chains, the C-C bond located between CH2 and CF2 units is first broken at 250-300 degrees C. In either case, the remaining alkyl layer is stable up to 350 degrees C, which is accounted for by a kinetic model involving chain pairing on the surface.

Water exclusion at the nanometer scale provides long-term passivation of silicon (111) grafted with alkyl monolayers.

This work is a quantitative study of the conditions required for a long-term passivation of the interface silicon-alkyl monolayers prepared by thermal hydrosilyation of neat 1-alkenes on well-defined H-Si(111) surfaces. We present electrochemical capacitance measurements (C-U) in combination with ex situ atomic force microscopy (AFM) observations and X-ray photoelectron spectroscopy (XPS) measurements. Capacitance measurements as a function of the reaction time and XPS data reveal close correlations between the chemical composition at the interface and its electronic properties. A very low density of states is found if suboxide formation is carefully prevented. The monitoring of C-U plots and AFM imaging upon exposure of the sample in diverse conditions indicate that the initial electronic properties and structure of the interface are long-lasting only when the monolayer surface coverage is theta > 0.42. A model demonstrates that this threshold value corresponds to a monolayer with intermolecular channels narrower than approximately 2.82 A, which is equal to the diameter of a water molecule. Water exclusion from the monolayer promotes long-term passivation of the silicon surface against oxidation in air and water as well as perfect corrosion inhibition in 20% NH(4)F. We provide two criteria to assess when a sample is optimized: The first one is an effective dielectric constant <2.5, and the second one is a very characteristic energy diagram at open circuit potential.

Electrochemical micromachining

The application of ultrashort voltage pulses between a tool electrode and a workpiece in an electrochemical environment allows the three-dimensional machining of conducting materials with submicrometer precision. The principle is based on the finite time constant for double-layer charging, which varies linearly with the local separation between the electrodes. During nanosecond pulses, the electrochemical reactions are confined to electrode regions in close proximity. This technique was used for local etching of copper and silicon as well as for local copper deposition.