Dependence of ultra-thin gate oxide reliability on surface cleaning approach

In this paper, we investigate the effect of silicon surface cleaning prior to oxidation on the reliability of ultra-thin oxides. It is demonstrated that chemical preoxide grown in H2SO4/H2O2 (SPM) solution prior to oxidation provides better oxide integrity than both HF-based solution dipping and preoxide grown in RCA SC1 or SC2 solutions. It is also found that the oxides with SPM preoxide exhibit better hot-carrier immunity than the RCA cleaned oxides.

A DNA nanomachine induced by single-walled carbon nanotubes on gold surface

Single-walled carbon nanotubes (SWNTs) can selectively induce human telomeric i-motif DNA formation at pH 7.0. Based on this property, we design a DNA nanomachine induced by SWNTs on gold surface. The motor DNA is human telomeric G-quadruplex DNA. The reversible hybridization between the motor DNA and its complementary human telomeric i-motif DNA can be modulated by SWNTs without changing solution pH. Up to now, to our knowledge, there is no report to show that a DNA nanomachine is induced by SWNTs or a DNA nanomachine can detect i-motif formation at pH 7.0. Our work may provide a new concept for designing an SWNT-induced DNA nanomachine and for the detection of i-motif DNA structure at pH 7.0. DNA hybridization, conformational transition and i-motif formation have been characterized on surface or in solution by fluorescence confocal microscopy, circular dichroism, DNA melting and gel electrophoresis. The folding and unfolding kinetics of the DNA nanomachine on gold surface were studied by Fourier transform-surface plasmon resonance (FT-SPR). All these results indicate that SWNTs can induce the DNA nanomachine to work efficiently and reversibly.

Application of Ru(bpy)(3)(2+) in control and formation of gold surface nanostructure through oxidation-reduction cycling

It was studied that the nanostructure formed on a gold surface via a simple oxidation-reduction cycles (ORC) in 0.1 M KCl containing Ru(bpy)(3)(2+) with different concentrations. Atomic force microscopy (AFM) and energy-dispersed spectroscopy (EDS) were used to characterize the nanostructure formed on the gold surface. Sweep-step voltammetry and corresponding electroluminescence (ECL) response, in situ electrochemical quartz crystal microbalance (EQCM) measurement were used to monitor the ORC. procedure. It was found that the surface structure became more uniform in the presence of Ru(bpy)(3)(2+), and the surface roughness was decreasing with the increasing of Ru(bpY)(3)(2+) concentration, suggesting a simple and effective method to control the formation of nanostructure on the gold surface.

A method for cathodic polymerization of aniline by in situ electrogenerated intermediate at gold surface

Polyaniline (PANI) was cathodically synthesized at an evaporated gold electrode using an in situ electrogenerated intermediate as oxidant during reduction of the dissolved oxygen. The obtained PANI layer showed an electrochemical response similar to that synthesized by the conventionally anodic polymerization, and the average rate for the growth of PANI layer at polycrystalline gold electrode was 1.59 nm h(-1), while that at the Au (111) electrode was 4.93 nm h(-1). Based on these results, the thickness of the resulted layer can be easily controlled at molecular level for potential nanodevice applications. The obtained PANI layer showed morphology from an island-like nanostructure to an ultrathin film, depending on the crystal orientation of the electrode used.

Self-assembling process of alkanethiol monolayers on gold surface via underpotential deposition

It was demonstrated feasible that underpotential deposition(UPD) of copper on a monolayer-modified gold substrate can be used to determine the gold electrode area. The deposition and stripping of a Cu adlayer can take Place reversibly and stably at a bared or a self-assembled monolayer modified gold electrode. The growth kinetics of decanethiol/Au was also investigated via Cu UPD. The difference between the assembling kinetics determined by UPD and that by quartz crystal microbalance measurements reveals the configuration transmutation of the assembled molecules from a disordered arrangement to an ordered arrangement during the self-assembling processes.

DNA-templated assembly and electropolymerization of aniline on gold surface

Biomolecule template gives new opportunities for the fabrication of novel materials with special features. Here we report a route to the formation of DNA-polyaniline (PAn) complex, using immobilized DNA as a template. A gold electrode was first modified with monolayer of 2-aminoethanethiol by self-assembly. Thereafter, by simply immersing the gold electrode into DNA solution, DNA molecules can be attached onto the gold surface, followed by the DNA-templated assembly and electropolymerization of protonated aniline. The electrostatic interactions between DNA and aniline can keep the aniline monomers aligning along the DNA strands. Investigations by surface plasmon resonance (SPR), electrochemistry and reflection absorption UV/Vis-Near IR spectroscopy substantially convince that PAn can be electrochemically grown around DNA template on gold surface. This work may be provides fundamental aspects for building PAn nanowires with DNA as template on solid surface if DNA molecules can be individually separated and stretched.

Density functional theory study on the activation of molecular oxygen on a stepped gold surface in an aqueous environment: a new approach for simulating reactions in solution

The activation of oxygen molecules is an important issue in the gold-catalyzed partial oxidation of alcohols in aqueous solution. The complexity of the solution arising from a large number of solvent molecules makes it difficult to study the reaction in the system. In this work, O-2 activation on an Au catalyst is investigated using an effective approach to estimate the reaction barriers in the presence of solvent. Our calculations show that O-2 can be activated, undergoing OOH* in the presence of water molecules. The OOH* can readily be formed on Au(211) via four possible pathways with almost equivalent free energy barriers at the aqueous-solid interface: the direct or indirect activation of O-2 by surface hydrogen or the hydrolysis of O-2 following a Langmuir-Hinshelwood mechanism or an Eley-Rideal mechanism. Among them, the Eley-Rideal mechanism may be slightly more favorable due to the restriction of the low coverage of surface H on Au(211) in the other mechanisms. The results shed light on the importance of water molecules on the activation of oxygen in gold-catalyzed systems. Solvent is found to facilitate the oxygen activation process mainly by offering extra electrons and stabilizing the transition states. A correlation between the energy barrier and the negative charge of the reaction center is found. The activation barrier is substantially reduced by the aqueous environment, in which the first solvation shell plays the most important role in the barrier reduction. Our approach may be useful for estimating the reaction barriers in aqueous systems.

Sonogashira coupling on an extended gold surface in vacuo: reaction of phenylacetylene with iodobenzene on Au(111)

Temperature-programmed reaction measurements supported by scanning tunneling microscopy have shown that phenylacetylene and iodobenzene react on smooth Au(111) under vacuum conditions to yield biphenyl and diphenyldiacetylene, the result of homocoupling of the reactant molecules. They also produce diphenylacetylene, the result of Sonogashira cross-coupling, prototypical of a class of reactions that are of paramount importance in synthetic organic chemistry and whose mechanism remains controversial. Roughened Au(111) is completely inert toward all three reactions, indicating that the availability of crystallographically well-defined adsorption sites is crucially important. High-resolution X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy show that the reactants are initially present as intact, essentially flat-lying molecules and that the temperature threshold for Sonogashira coupling coincides with that for C−I bond scission in the iodobenzene reactant. The fractional-order kinetics and low temperature associated with desorption of the Sonogashira product suggest that the reaction occurs at the boundaries of islands of adsorbed reactants and that its appearance in the gas phase is rate-limited by the surface reaction. These findings demonstrate unambiguously and for the first time that this heterogeneous cross-coupling chemistry is an intrinsic property of extended, metallic pure gold surfaces: no other species, including solvent molecules, basic or charged (ionic) species are necessary to mediate the process.

Fast assembly of non-thiolated DNA on gold surface at lower pH

In a typical protocol for attaching DNA to a gold electrode, thiolated DNA is incubated with the electrode at neutral pH overnight. Here we report fast adsorption of non-thiolated DNA oligomers on gold electrodes at acidic pH (i.e., pH ~3.0). The peak-to-peak potential difference and the redox peak currents in typical cyclic voltammetry of [Fe(CN)6]3- are investigated to monitor the attachment. Compared with incubation at neutral pH, the lower pH can significantly promote the adsorption processes, enabling efficient adsorption even in 30min. The adsorption rate is DNA concentration-dependent, while the ionic strength shows no influence. Moreover, the adsorption is base-discriminative, with a preferred order of A>C≫G, T, which is attributed to the protonation of A and C at low pH and their higher binding affinity to gold surface. The immobilized DNA is functional and can hybridize with its complementary DNA but not a random DNA. This work is promising to provide a useful time-saving strategy for DNA assembly on gold electrodes, allowing fast fabrication of DNA-based biosensors and devices. © 2013 Elsevier Inc.

Release of Cyanopyridine from a Ruthenium Complex Adsorbed on Gold: Surface-Enhanced Raman Scattering, Electrochemistry, and Density Functional Theory Analyses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Development and evaluation of a pollution prevention technology for surface cleaning and decontamination : cooperative research and development agreement with Cold Jet, Inc.

Mode of access: Internet.

Development and optimisation of protocols for surface cleaning of cultural heritage metals

The conservation and valorisation of cultural heritage is of fundamental importance for our society, since it is witness to the legacies of human societies. In the case of metallic artefacts, because corrosion is a never-ending problem, the correct strategies for their cleaning and preservation must be chosen. Thus, the aim of this project was the development of protocols for cleaning archaeological copper artefacts by laser and plasma cleaning, since they allow the treatment of artefacts in a controlled and selective manner. Additionally, electrochemical characterisation of the artificial patinas was performed in order to obtain information on the protective properties of the corrosion layers. Reference copper samples with different artificial corrosion layers were used to evaluate the tested parameters. Laser cleaning tests resulted in partial removal of the corrosion products, but the lasermaterial interactions resulted in melting of the desired corrosion layers. The main obstacle for this process is that the materials that must be preserved show lower ablation thresholds than the undesired layers, which makes the proper elimination of dangerous corrosion products very difficult without damaging the artefacts. Different protocols should be developed for different patinas, and real artefacts should be characterised previous to any treatment to determine the best course of action. Low pressure hydrogen plasma cleaning treatments were performed on two kinds of patinas. In both cases the corrosion layers were partially removed. The total removal of the undesired corrosion products can probably be achieved by increasing the treatment time or applied power, or increasing the hydrogen pressure. Since the process is non-invasive and does not modify the bulk material, modifying the cleaning parameters is easy. EIS measurements show that, for the artificial patinas, the impedance increases while the patina is growing on the surface and then drops, probably due to diffusion reactions and a slow dissolution of copper. It appears from these results that the dissolution of copper is heavily influenced by diffusion phenomena and the corrosion product film porosity. Both techniques show good results for cleaning, as long as the proper parameters are used. These depend on the nature of the artefact and the corrosion layers that are found on its surface.

Avaliação da limpeza de CDtrodo construídos a partir de CD de ouro gravável/fita adesiva de galvanoplastia

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)