Electrochemical reduction of oxygen on gold and boron-doped diamond electrodes in ambient temperature, molten acetamide-urea-ammonium nitrate eutectic melt

The electrochemical reduction of oxygen has been studied on gold, boron-doped diamond (BDD) and glassy carbon (GC) electrodes in a ternary eutectic mixture of acetamide (CH3CONH2), urea (NH2CONH2) and ammonium nitrate (NH4NO3). Cyclic voltammetry (CV), differential pulse voltammetry (DPV), chronoamperometry and rotating disk electrode (RDE) voltammetry techniques have been employed to follow oxygen reduction reaction (ORR). The mechanism for the electrochemical reduction of oxygen on polycrystalline gold involves 2-step. 2-electron pathways of O-2 to H2O2 and further reduction of H2O2 to H2O. The first 2-electron reduction of O-2 to H2O2 passes through superoxide intermediate by 1-electron reduction of oxygen. Kinetic results suggest that the initial 1-electron reduction of oxygen to HO2 is the rate-determining step of ORR on gold surfaces. The chronoamperometric and ROE studies show a potential dependent change in the number of electrons on gold electrode. The oxygen reduction reaction on boron-doped diamond (BOO) seems to proceed via a direct 4-electron process. The reduction of oxygen on the glassy carbon (GC) electrode is a single step, irreversible, diffusion limited 2-electron reduction process to peroxide. (C) 2010 Elsevier Ltd. All rights reserved.

Anomalous dielectric behavior of some ferrites

The dielectric behavior of some powdered polycrystalline samples has been studied in the frequency range of 200 Hz–100 kHz. It is shown that the dielectric behavior in these systems below the Curie temperature is not purely relaxational in its character and cannot be described by any of the models of the dielectric relaxation hitherto put forward. It is also shown that ‘‘isolation’’ of the particles in the powder samples plays a very important role. The origin of this abnormality is thought to be due to the mechanical resonance arising out of the magnetostrictive property of the material.

A comparative study of the magnetic and electrical properties of perovskite oxides and the corresponding two-dimensional oxides of K2NiF4

Electrical and magnetic properties of several oxide systems of K2NiF4 structure have been compared to those of the corresponding perovskites. Members of the La1−xSr1+xCoO4 system are all semiconductors with a high activation energy for conduction unlike La1−xSrxCoO3 (x ≥ 0.3) which is metallic; the latter oxides are ferromagnetic. La0.5Sr1.5CoO4 shows a magnetization of 0.5 μB at 0 K (compared to 1.5 μB of La0.5Sr0.5CoO3), but the high-temperature susceptibilities of the two systems are comparable. In SrO · (La0.5Sr0.5MnO3)n, both magnetization and electrical conductivity increase with the increase in n approaching the value of the perovskite La0.5Sr0.5MnO3. LaSrMn0.5Ni0.5(Co0.5)O4 shows no evidence of long-range ferromagnetic ordering unlike the perovskite LaMn0.5Ni0.5(Co0.5)O3; high-temperature susceptibility behavior of these two insulating systems is, however, similar. LaSr1−xBaxNiO4 exhibits high electrical resistivity with the resistivity increasing proportionately with the magnetic susceptibility (note that LaNiO3 is a Pauli-paramagnetic metal). High-temperature susceptibility of LaSrNiO4 and LaNiO3 are comparable. Susceptibility measurements show no evidence for long-range ordering in LaSrFe1−xNixO4 unlike in LaFe1−xNixO3 (x ≤ 0.35) and the electrical resistivity of the former is considerably higher. Electrical resistivity of Sr2RuO4 is more than an order of magnitude higher than that of SrRuO3. Some generalizations of the properties of two- and three-dimensional oxide systems have emerged from these experimental observations.

On the paradoxical relation between the melting temperature and forbidden energy gap of nanoparticles

We comment on the paradox that seems to exist about a correlation between the size-dependent melting temperature and the forbidden energy gap of nanoparticles. By analyzing the reported expressions for the melting temperature and the band gap of nanoparticles, we conclude that there exists a relation between these two physical quantities. However, the variations of these two quantities with size for semiconductors are different from that of metals. (C) 2010 American Institute of Physics.[doi:10.1063/1.3466920].

Microstructure related influence on the electrical properties of pulsed laser ablated (Ba, Sr)TiO3 thin films

The microstructural dependence of electrical properties of (Ba, Sr)TiO3(BST) thin films were studied from the viewpoint of dc and ac electrical properties. The films were grown using a pulsed laser deposition technique in a temperature range of 300 to 600 degrees C, inducing changes in grain size, structure, and morphology. Consequently, two different types of films were realized, of which type I, was polycrystalline, multigrained, while type II was [100] oriented possessing a densely packed fibrous microstructure. Leakage current measurements were done at elevated temperatures to provide evidence of the conduction mechanism present in these films. The results revealed a contribution from both electronic and ionic conduction. In the case of type I films, two trapping levels were identified with energies around 0.5 and 2.73 eV, which possibly originate from oxygen vacancies V-O and Ti3+ centers, respectively. These levels act as shallow and deep traps and are reflected in the current-voltage characteristics of the BST thin films. The activation energy associated with oxygen vacancy motion in this case was obtained as 1.28 eV. On the contrary, type II films showed no evidence of deep trap energy levels, while the identified activation energy associated with shallow traps was obtained as 0.38 eV. The activation energy obtained for oxygen vacancy motion in type II films was around 1.02 eV. The dc measurement results were further elucidated through ac impedance analysis, which revealed a grain boundary dominated response in type I in comparison to type II films where grain response is highlighted. A comparison of the mean relaxation time of the two films revealed three orders of magnitude higher relaxation time in the case of type I films. Due to smaller grain size in type I films the grains were considered to be completely depleted giving rise to only grain boundary response for the bulk of the film. The activation energy obtained from conductivity plots agree very well with that of dc measurements giving values 1.3 and 1.07 eV for type I and type II films, respectively. Since oxygen vacancy transport have been identified as the origin of resistance degradation in BST thin films, type I films with their higher value of activation energy for oxygen ion mobility explains the improvement in breakdown characteristics under constant high dc field stress. The role of microstructure in controlling the rate of degradation is found useful in this instance to enhance the film properties under high electric field stresses. (C) 2000 American Institute of Physics. [S0021-8979(00)00418-7].

High-pressure studies on Ge-Te glasses. Evidence for a critical composition in IV-VI chalcogenide glassy systems

The electrical resistivity of bulk GexTe100-x glasses has been measured as a function of temperature and pressure. Under high pressure, all the glasses were found to undergo sharp discontinuous transitions from glassy semiconductors to crystalline metal. Several of the observed properties such as the transition pressure, conductivity activation energy and pre-exponential factor, exhibit anomalous trends at a composition x = 20. These results suggest that the x = 20 composition in the Ge-Te system should possess salient structural features. A model based on the unusual stability of structural units is proposed for explaining the anomaly at 20 at.% Ge concentration.

Computer estimation of the Cd---Hg---Te phase diagram

The compounds CdHgTe and its constituent binaries CdTe, HgTe, and CdHg are semiconductors which are used in thermal, infrared, nuclear, thermoelectric and other photo sensitive devices. The compound CdHgTe has a Sphaleritic structure of possible type A1IIB1IIC6VI. The TERCP program of Kaufman is used to estimate the stable regions of the ternary phase diagram using available thermodynamic data. It was found that there was little variation in stochiometry with temperature. The compositions were calculated for temperatures ranging from 325K to 100K and the compositional limits were Cd13−20Hg12−01Te75−79, Hg varying most. By comparison with a similar compound, Cd In2Te4 of forbidden band width. 88 to .90 e.V., similar properties are postulated for Cd1Hg1Te6 with applications in the infra red region of the spectrum at 300K where this composition is given by TERCP at the limit of stability.

Effect of sintering on optical, structural and photoluminescence properties of ZnO thin films prepared by sol-gel process

Zinc oxide (ZnO) thin films have been deposited on glass substrates via sol-gel technique using zinc acetate dihydrate as precursor by spin coating of the sol at 2000 rpm. Effects of annealing temperature on optical, structural and photo luminescence properties of the deposited ZnO films have been investigated. The phase transition from amorphous to polycrystalline hexagonal wurtzite structure was observed at an annealing temperature of 400 degrees C. An average transmittance of 87% in the visible region has been obtained at room temperature. The optical transmittance has slightly increased with increase of annealing temperature. The band gap energy was estimated by Tauc's method and found to be 3.22 eV at room temperature. The optical band gap energy has decreased with increasing annealing temperature. The photoluminescence (PL) intensity increased with annealing temperature up to 200 degrees C and decreased at 300 degrees C. (c) 2010 Elsevier B.V. All rights reserved.

Effect of substrate roughness on growth of diamond by hot filament CVD

Polycrystalline diamond coatings are grown on Si (100) substrate by hot filament CVD technique. We investigate here the effect of substrate roughening on the substrate temperature and methane concentration required to maintain high quality, high growth rate and faceted morphology of the diamond coatings. It has been shown that as we increase the substrate roughness from 0.05 mu m to 0.91 mu m (centre line average or CLA) there is enhancement in deposited film quality (Raman peak intensity ratio of sp (3) to non-sp (3) content increases from 1.65 to 7.13) and the substrate temperature can be brought down to 640A degrees C without any additional substrate heating. The coatings grown at adverse conditions for sp (3) deposition has cauliflower morphology with nanocrystalline grains and coatings grown under favourable sp (3) condition gives clear faceted grains.

Thin film amorphous semiconductor microwave switches

Microwave switches operating in the X band were designed and fabricated using amorphous chalcogenide semiconductors of composition GexTeyAsz. Threshold devices were shown to operate as microwave modulators at modulation frequencies of up to 100 MHz. No delay time was observed at the highest frequency although the modulation efficiency decreased above 10 MHz owing to the finite recovery time which was approximately 0.3 × 10−8s. The devices can also be used as variolossers, the insertion loss being 0.5 dB in the OFF state and increasing on switching from 5 dB at 1 mA device current to 18 dB at 100 mA.The behaviour of the threshold switches can be explained in terms of the formation of a conducting filament in the ON state with a constant current density of 2 × 104Acm−2 that is shunted by the device capacitance. The OFF state conductivity σ varies as ωn (0.5 < n < 1) which is characteristic of hopping in localized states. However, there was evidence of a decrease in n or a saturation of the conductivity at high frequencies.As a result of phase separation memory switches require no holding current in the ON state and may be used as novel latching semiconductor phase-shifters.

Reactivity Of Pph3 Toward Ruiiruiiicl(O2car)4 - Syntheses, Molecular-Structures, And Spectroscopic And Electrochemical Properties Of Ruiiruiii(Oh2)Cl(Mecn)(O2car)4(Pph3)2 And Ruii2(Oh2)(Mecn)2(O2car)4(Pph3)2

By the reaction of Ru2Cl(O2CAr)4 (1) and PPh3 in MeCN-H2O the diruthenium(II,III) and diruthenium(II) compounds of the type Ru2(OH2)Cl(MeCN)(O2CAr)4(PPh3)2 (2) and Ru2(OH2)(MeCN)2(O2CAr)4(PPh3)2 (3) were prepared and characterized by analytical, spectral, and electrochemical data (Ar is an aryl group, C6H4-p-X; X = H, OMe, Me, Cl, NO2). The molecular structure of Ru2(OH2)Cl(MeCN)(O2CC6H4-p-OMe)4(PPh3)2 was determined by X-ray crystallography. Crystal data are as follows: triclinic, P1BAR, a = 13.538 (5) angstrom, b = 15.650 (4) angstrom, c = 18.287 (7) angstrom, alpha = 101.39 (3)-degrees, beta = 105.99 (4)-degrees, gamma = 97.94 (3)-degrees, V = 3574 angstrom 3, Z = 2. The molecule is asymmetric, and the two ruthenium centers are clearly distinguishable. The Ru(III)-Ru(II), Ru(III)-(mu-OH2), and Ru(II)-(mu-OH2) distances and the Ru-(mu-OH2)-Ru angle in [{Ru(III)Cl(eta-1-O2CC6H4-p-OMe)(PPh3)}(mu-OH2)(mu-O2CC6H4-p-OMe)2{Ru(II)(MeCN)(eta-1-O2CC6H4-p-OMe)(PPh3)}] are 3.604 (1), 2.127 (8), and 2.141 (10) angstrom and 115.2 (5)-degrees, respectively. The compounds are paramagnetic and exhibit axial EPR spectra in the polycrystalline form. An intervalence transfer (IT) transition is observed in the range 900-960 nm in chloroform in these class II type trapped mixed-valence species 2. Compound 2 displays metal-centered one-electron reduction and oxidation processes near -0.4 and +0.6 V (vs SCE), respectively in CH2Cl2-TBAP. Compound 2 is unstable in solution phase and disproportionates to (mu-aquo)diruthenium(II) and (mu-oxo)diruthenium(III) complexes. The mechanistic aspects of the core conversion are discussed. The molecular structure of a diruthenium(II) compound, Ru2(OH2)(MeCN)2(O2CC6H4-p-NO2)4(PPh3)2.1.5CH2Cl2, was obtained by X-ray crystallography. The compound crystallizes in the space group P2(1)/c with a = 23.472 (6) angstrom, b = 14.303 (3) angstrom, c = 23.256 (7) angstrom, beta = 101.69 (2)-degrees, V = 7645 angstrom 3, and Z = 4. The Ru(II)-Ru(II) and two Ru(II)-(mu-OH2) distances and the Ru(II)-(mu-OH2)-Ru(II) angle in [{(PPh3)-(MeCN)(eta-1-O2CC6H4-p-NO2)Ru}2(mu-OH2)(mu-O2CC6H4-p-NO2)2] are 3.712 (1), 2.173 (9), and 2.162 (9) angstrom and 117.8 (4)-degrees, respectively. In both diruthenium(II,III) and diruthenium(II) compounds, each metal center has three facial ligands of varying pi-acidity and the aquo bridges are strongly hydrogen bonded with the eta-1-carboxylato facial ligands. The diruthenium(II) compounds are diamagnetic and exhibit characteristic H-1 NMR spectra in CDCl3. These compounds display two metal-centered one-electron oxidations near +0.3 and +1.0 V (vs SCE) in CH2Cl2-TBAP. The overall reaction between 1 and PPh3 in MeCN-H2O through the intermediacy of 2 is of the disproportionation type. The significant role of facial as well as bridging ligands in stabilizing the core structures is observed from electrochemical studies.

Solar rechargeable battery—principle and materials

A brief survey of the historical development of a photoelectrochemical solar cell is given. The principle and future of solar chargeable battery is compared with a wet and a dry type photovoltaic cell. A solar chargeable battery, with or without a membrane and with an aqueous solution or with solid-state electrolytes is discussed. A new unique type of configuration “Sharon-Schottky” junction solar cell is described which can be used either as a charger for any secondary batteries or could be used for photoelectrolysis of water. All these configurations and their relative merits are discussed. A review on the various semiconductors and types of solar chargeable batteries is made. Finally, a conclusion is drawn for future direction of research for developing an economically viable photoelectrochemical (PEC) solar cell based on either the principle of a solar charger (to charge a Ni---Cd battery or lead—acid battery) and/or solar chargeable battery with or without without a membrane. Some new innovative ideas for the preparation of materials is discussed. The entire discussion is geared towards answering a relevant question: what has gone wrong to result in the stagnation and failure in commercialization of a PEC based solar cell?

Defect related luminescence in Hg0.2Cd0.8Te nano- and micro-crystals grown by the solvothermal method

The photoluminescence (PL) properties of nano- and micro-crystalline Hg1-xCdxTe (x approximate to 0.8) grown by the solvothermal method have been studied over the temperature range 10-300 K. The emission spectra of the samples excited with 514.5 nm Ar+ laser consist of five prominent bands around 0.56, 0.60, 0.69, 0.78 and 0.92 eV. The entire PL band in this NIR region is attributed to the luminescence from defect centers. The features like temperature independent peak energy and quite sensitive PL intensity, which has a maximum around 50 K is illustrated by the configuration coordinate model. After 50 K, the luminescence shows a thermal quenching behavior that is usually exhibited by amorphous semiconductors, indicating that the defects are related to the compositional disorder. (C) 2010 Elsevier B.V. All rights reserved.

Direct Growth of Gold Nanorods on Gold and Indium Tin Oxide Surfaces: Spectral, Electrochemical, and Electrocatalytic Studies

The surfactant-assisted seed-mediated growth method was used for the formation of gold nanorods (GNRs) directly on gold (Au) and indium tin oxide (ITO) surfaces. Citrate-stabilized similar to 2.6 nm spherical gold nanoparticles (AuNPs) were first self-assembled on ITO or Au surfaces modified with (3-mercaptopropyl)-trimethoxysilane (MPTS) sol-gel film and then immersed in a cationic surfactant growth solution to form GNRs. The growth of GNRs on the MPTS sol gel film modified ITO surface was monitored by UV-visible spectroscopy. The ITO surface with the attached spherical AuNPs shows a surface plasmon resonance band at 550 nm. The intensity of this absorption band increases while increasing the immersion time of the AuNP-modified ITO surface into the growth solution, and after 5 h, an additional shoulder band around 680 nm was observed. The intensity of this shoulder band increases, and it was shifted to longer wavelength as the immersion time of the AuNP-modified ITO surface into the growth solution increases. After 20 h, a predominant wave at 720 nm was observed along with a band at 550 nm. Further immersion of the modified ITO surface into the growth solution did not change the absorption characteristics. The bands observed at 550 and 720 nm were characteristics of GNRs, corresponding to transverse and longitudinal waves, respectively. The AFM images showed the presence of GNRs on the surface of the MPTS sol gel modified ITO surface with a typical length of similar to 100-120 nm and a width of similar to 20-22 nm in addition to a few spherical AuNPs, indicating that seeded spherical AuNPs were not completely involved in the GNRs' formation. Finally, the electrocatalytic activity of the surface-grown GNRs on the MPTS sol gel film modified Au electrode toward the oxidation of ascorbic acid (AA) was studied. Unlike a polycrystalline Au electrode, the surface-grown GNR-modified electrode shows two well-defined voltammetric peaks for AA at 0.01 and 0.35 V in alkaline, neutral, and acidic pHs. The cause for the observed two oxidation peaks for AA was due to the presence of both nanorods and spherical nanoparticles on the electrode surface. The presence of spherical AuNPs on the MPTS sol gel film oxidized AA at more positive potential, whereas the GNRs oxidized AA at less positive potential. The observed 340 mV less positive potential shift in the oxidation of AA suggested that GNRs are better electrocatalysts for the oxidation of AA than the spherical AuNPs.

An EXAFS investigation of the Zn environment in K2ZnCl4 during solid-to-solid phase transformations

Extended X-ray absorption fine structure (EXAFS) spectroscopy is applied to an investigation of the structural environment around Zn in polycrystalline K2ZnCi4 over the temperature range associated with its solid-to-solid phase transformations at 127 degrees C and 282 degrees C. The results show a reversible increase in thermal disorder and in the tetrahedral distortion of the ZnCl42- anion upon transformation into the incommensurate phase.