Electrochemiluminescence at nitrogen doped diamond-like carbon film electrodes

In the given paper the results of investigation of nitrogen doped diamond-like carbon films (DLF) for the fabrication of electrodes of electrochemical and electrochemiluminescent (ECL) cells are presented. The surface nanomorphology of modified electrodes was studied using the atomic-force microscopy method. The mechanisms of ECL reactions with Ru(bpy) ₃ ¹⁺ /Ru(bpy) ₃ ³⁺ (recombination Ru(bpy) ₃ ³⁺ /OH^? (ECL without co-reactant) and Ru(bpy) ₃ ³⁺ /tripropylamine (ECL with co-reactant) were studied on DLF modified electrodes in the aqueous solution. The work shows advantages of DLF as an electrode material for further analytical applications.     

On the anodic decomposition of the zinc selenide electrode

The electrochemical decomposition of n-type zinc selenide has been studied in connection with the chemisorption of the OH^? groups onto the semiconductor surface, depending on the band bending. The influence of oxidizing agents such as the illumination of the electrode or the presence of ferricyanide ions in the solution, leading to injection of holes into the valence band, has also been put in evidence. In contrast with the usual decomposition models that are rather simple, a complex and multistep mechanism is proposed here in order to account for the different observations made on these electrodes: the triangular decomposition pits, the deep red layer of amorphous selenium and the bright grey layer of zinc oxide.     

Visualisation of chemical processes during corrosion of zinc using magnetic resonance imaging

Compositional and structural changes within an electrolyte solution above an electrochemically active metal surface have been visualised using magnetic resonance imaging (MRI) for the first time. In these proof-of-concept experiments, zinc metal was galvanically corroded in a saturated lithium chloride solution. Magnetic resonance relaxation maps were taken during the corrosion process and spatial variations in both T₁ and T₂ relaxation times were observed to change with time. These changes were attributed to changes in the speciation of zinc ions in the electrolyte.     

Understanding run-in behavior of diamond-like carbon friction and preventing diamond-like carbon wear in humid air

The friction behavior of diamond-like carbon (DLC) is very sensitive to the test environment. For hydrogen-rich DLC tested in dry argon and hydrogen, there was always an induction period, so-called "run-in" period, during which the friction coefficient was high and gradually decreased before DLC showed an ultralow friction coefficient (less than 0.01) behavior. Regardless of friction coefficients and hydrogen contents, small amounts of wear were observed in dry argon, hydrogen, oxygen, and humid argon environments. Surprisingly, there were no wear or rubbing scar on DLC surfaces tested in n-pentanol vapor conditions, although the friction coefficient was relatively high among the five test environments. Ex situ X-ray photoelectron and near-edge X-ray absorption fine-structure spectroscopy analyses failed to reveal any differences in chemical composition attributable to the environment dependence of DLC friction and wear. The failure of getting chemical information of oxygenated surface species from the ex situ analysis was found to be due to facile oxidation of the DLC surface upon exposure to air. The removal or wear of this surface oxide layer is responsible for the run-in behavior of DLC. It was discovered that the alcohol vapor can also prevent the oxidized DLC surface from wear in humid air conditions.     

Substoichiometric determination of trace impurities in zinc selenide

Determination of trace impurities in zinc selenide was carried out by substoichiometric neutron activation analysis. Trace impurities were separated from matrix elements by suitable procedures and determined by substoichiometric methods, i.e., Au was extracted with rhodamine-B, Ag and Cu with dithizone, Cr with sodium diethyldithiocarbamate, Co with 1-nitroso-2-naphthol, and Sb with cupferron. Two sorts of zinc selenide single crystals were supplied for analysis and the following values were obtained as impurity concentration; Au 0.36, 0.076 ppb, Ag 42, 32 ppb, Cr. 1.8, 0.63 ppm, Co 0.16, 0.0079 ppm, Sb 8.5, 5.9 ppb and Cu 1.4, 0.44 ppm. The behavior of copper by heat-treatment of zinc selenide was also studied by means of substoichiometric isotope dilution analysis.     

Semiconducting thin films of zinc selenide quantum dots

A novel chemical route for deposition of zinc selenide quantum dots in thin film form is developed. The deposited films are characterized with very high purity in crystallographic sense, and behave as typical intrinsic semiconductors. Evolution of the average crystal size, lattice constant, lattice strain and the optical properties of the films upon thermal treatment is followed and discussed. The band gap energy of as-deposited ZnSe films is blue-shifted by ≈0.50 eV with respect to the bulk value, while upon annealing treatment it converges to 2.58 eV. Two discrete electronic states which originate from the bulk valence band are observed in the UV-VIS spectra of ZnSe 3D quantum dots deposited in thin film form via allowed electronic transitions to the 1S electronic state arising from the bulk conduction band—appearing at 3.10 and 3.50 eV. The splitting between these two states is approximately equal to the spin-orbit splitting in the case of bulk ZnSe. The electronic transitions in the case of non-quantized annealed films are discussed in terms of the direct allowed band-to-band transitions with the spin-orbit splitting of the valence band of 0.40 eV. The effective mass approximation model (i.e., the Brus model) with the static relative dielectric constant of bulk ZnSe fails to predict correctly the size dependence of the band gap energy, while only a slight improvement is obtained when the hyperbolic band model is applied. However, when substantially smaller value for ε_r (2.0 instead of 8.1) is used in the Brus model, an excellent agreement with the experimental data is obtained, which supports some earlier indications that the quantum dots ε_r value could be significantly smaller than the bulk material value. The ionization energy of a deep donor impurity level calculated on the basis of the temperature dependence of the film resistivity is 0.82 eV at 0 K.     

Electrochemical formation of zinc selenide from acidic aqueous solutions

An investigation on electrochemical ZnSe thin film growth from acidic aqueous baths of Se(IV) and Zn(II) species is described. The range of co-deposition potentials is predicted on a thermodynamic basis according to a known electrochemical model. A study on the voltammetric behavior of Ti and Ni electrode substrates in the working solutions at various temperatures provides the main features of the applied electrochemical process. Cathodic electrodeposition at high temperatures (>65 °C) results in the formation of polycrystalline cubic, randomly oriented, ZnSe crystallites suffering, in general, from the presence of a crystalline Se phase in excess. Annealing of as-grown films adjusts the stoichiometry and leads to the production of semiconductive ZnSe with a band gap width of 2.7 eV. Electronic Publication     

Polyadamantane as a source of diamond-like carbon

The literature data concerning the effect of high pressures (9 GPa) and temperatures (1800°C) on polyadamantane is revised. A new diamond-like carbon is formed, whose structure is similar to that of natural skeletal diamond.     

k-Restoring processes at carbon depleted ultralow-k surfaces

In this study we investigate the silylation of OH groups with different silazanes. In particular we use density functional theory and the nudged elastic band method to study the different reaction mechanisms. For the silylation reaction of hexamethyldisilazane and trimethylaminosilane with silanol, the minimum energy paths as well as the activation and reaction energies are discussed in detail. From minimum energy reaction paths we found that all studied silazanes react exothermically. Bis(dimethylamino)dimethylsilane shows the most exothermic silylation reaction with the lowest activation energies. Therefore, it is a good candidate for the chemical repair of porous films in the semiconductor k-restoring process.     

The stoichiometry of single nanoparticles of copper zinc tin selenide

Cu(2)ZnSnSe(4) nanoparticles have high potential to be used as ink for printable solar cells. Using transmission electron microscopy we show that these nanoparticles exhibit a broad range of chemical heterogeneity. These results are contrary to the interpretation of previous experimental work and will have considerable impact on the development of these nanoparticles.     

Efficacy of zinc and tourmaline in mitigating corrosion of carbon steel in non-flow mode

Laboratory corrosion immersion tests were carried out to investigate the effectiveness of a physical water treatment (PWT) using zinc and ceramic tourmaline-based catalytic materials for the control of carbon steel corrosion in acidic still water (i.e., pH 4.5–5). The tests were carried out at different water temperatures over 168 h. Our results showed a maximum of 22 % reduction in the corrosion rate using PWT in comparison with the control case. Furthermore, the corrosion products depicted more agglomerated particles after the PWT treatment. In both cases, differences were observed in the crystal structures, showing in general lower corrosion activity when PWT was used. The present results could find potential applications in water distribution systems and where metallic materials are exposed to stagnant acidic water.     

Electrochemical performance of silicon thin film anodes covered by diamond-like carbon with various surface coating morphologies

Four different kinds of diamond-like carbon (DLC) coating morphologies on the surface of silicon films were prepared directly on a copper foil by using radio frequency plasma-enhanced chemical vapor deposition at 200 °C. A thin double layer film consisting of DLC (60 nm) and silicon film (250 nm) was fabricated for use as the anode material of lithium secondary batteries, and its electrochemical performance was also examined with special attention being paid to the surface coverage of the DLC film. The full coverage of silicon by the DLC film resulted in poor capacity due to the ensuing low reactivity with the lithium ions. On the other hand, the partial coating of the DLC film on the silicon film not only reduced the capacity fading, but also increased the discharge capacity during the charge/discharge cycles. These results indicated that the good dispersion of the DLC coating, obtained by using a smaller coating sector on the silicon film, improved the integrity of the electrode structure, thus giving higher capacities and reduced capacity fading.     

Local atomic structure of zinc selenide films: EXAFS data

This paper presents the results of our study of the structural state and local atomic structure of zinc selenide films obtained by thermal evaporation in supervacuum at condensation temperatures of ?150°C, 0, and 150°C. Structure-sensitive methods such as X-ray diffraction, atomic force microscopy, and EXAFS spectroscopy were used. The parameters of the local atomic environment (interatomic distances, coordination numbers) of zinc and selenium atoms were obtained by Fourier transformation.     

Kinetics of elementary processes at the surface of a solid

A simple model of a multiphonon transition is discussed in relation to a continuous spectrum in the initial state; estimates are given the relative probabilities of volume and surface processes.     

Study of the corrosion products formed on carbon steel surface in hydrochloric acid solution

Effect of an antibacterial drug, sulfacetamide, IUPAC name N-[(4-aminophenyl) sulfonyl] acetamide (APSA), on the corrosion products formed on carbon steel surface in 1.0?mol?L^?1 HCl solution has been investigated using mass loss, X-ray photoelectron spectroscopy (XPS), and simultaneous thermal and differential scanning calorimetry/differential thermal analysis (TG/DSC/DTA). Mass loss measurements reveal that the corrosion rate of carbon steel is retarded by APSA and that the inhibition efficiency of this inhibitor increases with increasing the concentration. XPS analysis shows that, at this stage, the main product of corrosion is a non-stoichiometric Fe³⁺ oxyhydroxide, consisting of a mixture of FeO(OH) in anhydrous or hydrated forms, containing Cl^? inclusions and adsorbed APSA molecules. The mechanism of inhibition was discussed in light of the chemical structure of the investigated inhibitor. The corrosion products were analyzed using TG/DSC/DTA technique.     

Characterization of different diamond-like carbon electrodes for biosensor design

Diamond-like carbon (DLC) films are gaining big interest in electrochemistry research area. DLC electrodes made with different ratio of sp³/sp² carbon hybridization or doped with different percentages of nickel were characterized electrochemically by cyclic voltammetry and by amperometric measurements towards hydrogen peroxide. SiCAr1 and SiCNi5% were chosen as sensitive transducers for the elaboration of amperometric glucose biosensors. Immobilization of glucose oxidase was carried out by cross-linking with glutaraldehyde. Measurements were made at a fixed potential + 1.0 V in 40 mM phosphate buffer pH 7.4. SiCAr1 seems to be more sensitive for glucose, 0.6875 μA/mM, than SiCNi5%, 0.3654 μA/mM. Detections limits were 20 μM and 30 μM, respectively. Apparent Michaelis-Menten constants were found around 3 mM. Forty-eight percent and 79% of the original response for 0.5 mM glucose remained after 10 days for both biosensors, respectively.     

Saturation of surfactant structure at the single-walled carbon nanotube surface

Density gradient ultracentrifugation (DGU) and fluorescence spectroscopy are used to probe the limiting behaviors of the dynamic response of surfactant structure at the single-walled carbon nanotube (SWNT) surface to reorganizing forces, including changes in surfactant concentration and electrolyte screening. DGU results indicate that, as surfactant (sodium dodecyl sulfate, SDS) concentration is increased, SDS adsorbed on metallic SWNTs becomes limited in its ability to reorganize before SDS adsorbed on semiconducting species. A diameter-dependent enhancement is observed in photoluminescence intensities from semiconducting SWNTS upon initial titration with NaCl. This response to electrostatic screening diminishes as SDS concentration is increased. The results are understood as a saturation of the surfactant structural response, defined as both a loss in ability to increase SDS loading at the SWNT surface and a loss in ability to reorient surface structure in response to a reorganizing force. Saturation of response is found to be reversible and also occurs as a result of restricting SDS mobility. These results confirm several aspects of recent molecular dynamics simulations of SDS behavior on SWNTs and have important implications for tunability of density-based separation approaches using cosurfactant systems that include SDS.     

A kinetic method of determination of cobalt in zinc and cadmium selenide

Summary A kinetic method of cobalt determination has been applied for the determination of this element in zinc and cadmium selenides. The method is based on the catalytic effect of cobalt on the oxidation of Direct Blue 6B (C. I. 24410) by hydrogen peroxide at pH=10.8 and in the presence of tiron as an activator. The trace amounts of cobalt have been separated from the bulk zink and cadmium by means of the ion exchanger Lewatit 5080. In samples of 20–100 mg cobalt can be determined in the range of 7.1·10^–5%–2.4·10^–4%.

---

Eine kinetische Methode zur Bestimmung von Kobalt in Zink- und Cadmiumselenid

Zusammenfassung Das Verfahren beruht auf dem katalytischen Effekt von Kobalt bei der Oxydation von Direkt Blau 6B (C. I. 24410) durch Wasserstoffperoxid bei pH 10,8 in Gegenwart von Tiron als Aktivator. Die Kobaltspuren wurden von der Hauptmenge Zink und Cadmium mit Hilfe des Ionenaustauschers Lewatit 5080 abgetrennt. In 20–100 mg Probe kann Kobalt in Mengen von 7,1·10^-5 bis 2,4·10^–4% bestimmt werden.

     

Effect of processes at the reactor surface on the low-pressure hydrogen f lame

The interaction of the low-pressure flame of a 2H₂-O₂ mixture with a quartz reactor surface was studied by the resonance fluorescence technique. The results confirmed the fundamental statement of N. N. Semenov’s theory concerning chain propagation in the gas and termination on the surface in the kinetic region of chain termination (quadratic decay in the heterogeneous negative chain interaction) and in the diffusion region (linear decay). The kinetic curves observed in the kinetic and diffusion chain termination regions on the wall were well matched using N. N. Semenov’s theory, taking into account the heterogeneous catalytic chain initiation and interaction processes occurring on the wall with a variable “rate constant.” The interaction of chains on the wall markedly retards ignition in the gas in the kinetic region and has almost no influence on chain propagation in the gas in the diffusion region of the heterogeneous chain termination. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1301–1308, August, 2006.     

Electrosynthesis of cadmium selenide films on a selenium-modified gold surface

A two-step method for the growth of CdSe films is described that is based on the initial chemical modification of a polycrystalline gold surface with a selenium overlayer. In the second step, this overlayer is cathodically stripped as Se²⁻ in a Se(IV)-free electrolyte medium (0.1 M Na₂SO₄) that is dosed with the requisite amount of Cd²⁺ ions. Unlike the classical cathodic route, this new approach does not suffer from problems with excess Se admixed with CdSe. The two-step approach is validated using a combination of voltammetry, microgravimetry, and photoelectrochemical experiments.