How cracks in SiOx-coated polyester films affect gas permeation

In this paper theoretical models have been established that can account for the gas transmission through nanocomposite laminates, consisting of an oxide layer of finite permeability containing defects, on a polymer sheet of finite thickness. The defect shapes can either be in the form of long cracks or rectangular holes. The models offer a choice of exact numerical calculations or fast and intuitive analytical approximations. The experimental measurements of oxygen permeation through four different SiOx/poly (ethylene terephthalate) samples that were strained to produce distributions or cracks showed good agreement when compared with predicted results from the approximate analytic model. As a consequence of this observation, a key practical conclusion is that, because of the logarithmic dependence of transmission on the width of a crack, for a given strain it is better to have a small number of large cracks rather than a large number of small cracks. (C) 2001 Elsevier Science B.V. All rights reserved.

A common inhibitory binding site for zinc and odorants at the voltage-gated K+ channel of rat olfactory receptor neurons

This study compared the effects of zinc and odorants on the voltage-gated K+ channel of rat olfactory neurons. Zinc reduced current magnitude, depolarized the voltage activation curve and slowed activation kinetics without affecting inactivation or deactivation kinetics. Zinc inhibition was potentiated by the NO compound, S-nitroso-cysteine. The pH- and diethylpyrocarbonate-dependence of zinc inhibition suggested that zinc acted by binding to histidine residues. Cysteine residues were eliminated as contributing to the zinc-binding site. The odorants, acetophenone and amyl acetate, also reduced current magnitude, depolarized the voltage activation curve and selectively slowed activation kinetics. Furthermore, the diethylpyrocarbonate- and pH-dependence of odorant inhibition implied that the odorants also bind to histidine residues. Zinc inhibitory potency was dramatically diminished in the presence of odorants, implying competition for a common binding site. These observations indicate that the odorants and zinc share a common inhibitory binding site on the external surface of the voltage-gated K+ channel.

KrP laser CVD of chromium oxide by photodissociation of Cr(CO)(6)

This work reports on the synthesis of chromium oxide thin films prepared by photodissociation of Cr(CO)(6) in an oxidizing atmosphere, using a pulsed UV laser (KrF, lambda = 248 nm). The experimental conditions, which should enable the synthesis of CrO2, are discussed and results on the deposition of CrxOy films on Al2O3 (0001) substrates are presented.

Structural and Microanalytical Studies of CrO2 Thin Films on c-Sapphire by High Resolution Electron Microscopy Methods

Chromium dioxide (CrO2) has been extensively used in the magnetic recording industry. However, it is its ferromagnetic half-metallic nature that has more recently attracted much attention, primarily for the development of spintronic devices. CrO2 is the only stoichiometric binary oxide theoretically predicted to be fully spin polarized at the Fermi level. It presents a Curie temperature of ∼ 396 K, i.e. well above room temperature, and a magnetic moment of 2 mB per formula unit. However an antiferromagnetic native insulating layer of Cr2O3 is always present on the CrO2 surface which enhances the CrO2 magnetoresistance and might be used as a barrier in magnetic tunnel junctions.

Structural, electrical and magnetic studies of Co:SnO2 and (Co,Mo):SnO2 films prepared by pulsed laser deposition

Here we report on the structural, optical, electrical and magnetic properties of Co-doped and (Co,Mo)-codoped SnO2 thin films deposited on r-cut sapphire substrates by pulsed laser deposition. Substrate temperature during deposition was kept at 500 degrees C. X-ray diffraction analysis showed that the undoped and doped films are crystalline with predominant orientation along the [1 0 1] direction regardless of the doping concentration and doping element. Optical studies revealed that the presence of Mo reverts the blue shift trend observed for the Co-doped films. For the Co and Mo doping concentrations studied, the incorporation of Mo did not contribute to increase the conductivity of the films or to enhance the ferromagnetic order of the Co-doped films. (C) 2012 Elsevier B.V. All rights reserved.

Cobalt and Zinc Compounds Bearing 1,10-Phenanthroline-5,6-dione or 1,3,5-Triaza-7-phosphaadamantane Derivatives - Synthesis, Characterization, Cytotoxicity, and Cell Selectivity Studies

The compounds [mPTA][CoCl4] (1, mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [CoCl(H2O)(DION)(2)][BF4] (2, DION = 1,10-phenanthroline-5,6-dione), [Zn(DION)(2)]Cl-2 (3) and [ZnCl(O-PTA=O)(DION)][BF4] (4) were synthesized by reaction of CoCl2 with [mPTA]I or DION and ZnCl2 with DION or 1,3,5-triaza-7-phosphaadamantane-7-oxide (PTA=O) and DION, respectively. All complexes are water soluble and have been characterized by IR, far-IR, H-1, C-13 and P-31{H-1} NMR spectroscopy, ESI-MS, elemental analyses and single-crystal X-ray diffraction structural analysis (for 1). They were screened against the human tumour cell lines HCT116, HepG2 and MCF7. Complexes 2 and 3 exhibit the highest in vitro cytotoxicity and show lower cytotoxic activities in normal human fibroblast cell line than in HCT116 tumour cell line, which demonstrates their slight specificity for this type of tumour cell.

Photoluminescence and electrical study of fluctuating potentials in Cu2ZnSnS4-based thin films

In this work, we investigated structural, morphological, electrical, and optical properties from a set of Cu2ZnSnS4 thin films grown by sulfurization of metallic precursors deposited on soda lime glass substrates coated with or without molybdenum. X-ray diffraction and Raman spectroscopy measurements revealed the formation of single-phase Cu2ZnSnS4 thin films. A good crystallinity and grain compactness of the film was found by scanning electron microscopy. The grown films are poor in copper and rich in zinc, which is a composition close to that of the Cu2ZnSnS4 solar cells with best reported efficiency. Electrical conductivity and Hall effect measurements showed a high doping level and a strong compensation. The temperature dependence of the free hole concentration showed that the films are nondegenerate. Photoluminescence spectroscopy showed an asymmetric broadband emission. The experimental behavior with increasing excitation power or temperature cannot be explained by donor-acceptor pair transitions. A model of radiative recombination of an electron with a hole bound to an acceptor level, broadened by potential fluctuations of the valence-band edge, was proposed. An ionization energy for the acceptor level in the range 29–40 meV was estimated, and a value of 172 ±2 meV was obtained for the potential fluctuation in the valence-band edge.

Study of optical and structural properties of Cu2ZnSnS4 thin films

Cu2ZnSnS4 is a promising semiconductor to be used as absorber in thin film solar cells. In this work, we investigated optical and structural properties of Cu2ZnSnS4 thin films grown by sulphurization of metallic precursors deposited on soda lime glass substrates. The crystalline phases were studied by X-ray diffraction measurements showing the presence of only the Cu2ZnSnS4 phase. The studied films were copper poor and zinc rich as shown by inductively coupled plasma mass spectroscopy. Scanning electron microscopy revealed a good crystallinity and compactness. An absorption coefficient varying between 3 and 4×104cm−1 was measured in the energy range between 1.75 and 3.5 eV. The band gap energy was estimated in 1.51 eV. Photoluminescence spectroscopy showed an asymmetric broad band emission. The dependence of this emission on the excitation power and temperature was investigated and compared to the predictions of the donor-acceptor-type transitions and radiative recombinations in the model of potential fluctuations. Experimental evidence was found to ascribe the observed emission to radiative transitions involving tail states created by potential fluctuations.

Detection of ZnS phases in CZTS thin-films by EXAFS

Copper zinc tin sulfide (CZTS) is a promising Earthabundant thin-film solar cell material; it has an appropriate band gap of ~1.45 eV and a high absorption coefficient. The most efficient CZTS cells tend to be slightly Zn-rich and Cu-poor. However, growing Zn-rich CZTS films can sometimes result in phase decomposition of CZTS into ZnS and Cu2SnS3, which is generally deleterious to solar cell performance. Cubic ZnS is difficult to detect by XRD, due to a similar diffraction pattern. We hypothesize that synchrotron-based extended X-ray absorption fine structure (EXAFS), which is sensitive to local chemical environment, may be able to determine the quantity of ZnS phase in CZTS films by detecting differences in the second-nearest neighbor shell of the Zn atoms. Films of varying stoichiometries, from Zn-rich to Cu-rich (Zn-poor) were examined using the EXAFS technique. Differences in the spectra as a function of Cu/Zn ratio are detected. Linear combination analysis suggests increasing ZnS signal as the CZTS films become more Zn-rich. We demonstrate that the sensitive technique of EXAFS could be used to quantify the amount of ZnS present and provide a guide to crystal growth of highly phase pure films.

Properties of tantalum oxynitride thin films produced by magnetron sputtering: the influence of processing parameters

The main purpose of this work is to present and to interpret the change of structure and physical properties of tantalum oxynitride (TaNxOy) thin films, produced by dc reactive magnetron sputtering, by varying the processing parameters. A set of TaNxOy films was prepared by varying the reactive gases flow rate, using a N2/O2 gas mixture with a concentration ratio of 17:3. The different films, obtained by this process, exhibited significant differences. The obtained composition and the interpretation of X-ray diffraction results, shows that, depending on the partial pressure of the reactive gases, the films are: essentially dark grey metallic, when the atomic ratio (N + O)/Ta < 0.1, evidencing a tetragonal β-Ta structure; grey-brownish, when 0.1 < (N + O)/Ta < 1, exhibiting a face-centred cubic (fcc) TaN-like structure; and transparent oxide-type, when (N + O)/Ta > 1, evidencing the existence of Ta2O5, but with an amorphous structure. These transparent films exhibit refractive indexes, in the visible region, always higher than 2.0. The wear resistance of the films is relatively good. The best behaviour was obtained for the films with (N + O)/Ta ≈ 0.5 and (N + O)/Ta ≈ 1.3.

Electrochemical and analytical investigation of passive films formed on stainless steels in alkaline media

Passive films were grown in potentiodynamic mode, by cyclic voltammetry on AISI 316 and AISI 304 stainless steels. The composition of these films was investigated by X-ray photoelectron spectroscopy (XPS). The electrochemical behaviour and the chemical composition of the passive films formed by cyclic voltammetry were compared to those of films grown under natural conditions (by immersion at open circuit potential, OCP) in alkaline solutions simulating concrete. The study included the effect of pH of the electrolyte and the effect of the presence of chloride ions. The XPS results revealed important changes in the passive film composition, which becomes enriched in chromium and depleted in magnetite as the pH decreases. On the other hand, the presence of chlorides promotes a more oxidised passive layer. The XPS results also showed relevant differences on the composition of the oxide layers for the films formed under cyclic voltammetry and/or under OCP.

Fabrication of electrochemically reduced graphene oxide/cobalt oxide composite for charge storage electrodes

Electrochemically-reduced graphene oxide (Er-GO) and cobalt oxides (CoOx) were co-electrodeposited by cyclic voltammetry, from an electrolyte containing graphene oxide and cobalt nitrate, directly onto a stainless steel substrate to produce composite electrodes presenting high charge storage capacity. The electrochemical response of the composite films was optimized by studying the parameters applied during the electrodeposition process, namely the number of cycles, scan rate and ratio between GO/Co(NO3)(2) concentrations in the electrolyte. It is shown that, if the appropriate conditions are selected, it is possible to produced binder-free composite electrodes with improved electrochemical properties using a low-cost, facile and scalable technique. The optimized Er-GO/CoOx developed in this work exhibits a specific capacitance of 608 F g(-1) at a current density of 1 A g(-1) and increased reversibility when compared to single CoOx. (C) 2015 Elsevier B.V. All rights reserved.

Effect of selenization conditions on the growth and properties of Cu2ZnSn(S,Se)4 thin films

The opto-electronic properties of copper zinc tin sulfide can be tuned to achieve better cell efficiencies by controlled incorporation of selenium. In this paper we report the growth of Cu2ZnSn(S,Se)4 (CZTSSe) using a hybrid process involving the sequential evaporation of Zn and sputtering of the sulfide precursors of Cu and Sn, followed by a selenization step. Two approaches for selenization were followed, one using a tubular furnace and the other using a rapid thermal processor. The effects of annealing conditions on the morphological and structural properties of the films were investigated. Scanning electron microscopy and energy dispersive spectroscopy were employed to investigate the morphology and composition of the films. Structural analyses were done using X-ray diffraction (XRD) and Raman spectroscopy. Structural analyses revealed the formation of CZTSSe. This study shows that regardless of the selenization method a temperature above 450 °C is required for conversion of precursors to a compact CZTSSe layer. XRD and Raman analysis suggests that the films selenized in the tubular furnace are selenium rich whereas the samples selenized in the rapid thermal processor have higher sulfur content.

Engineering of metal oxide nanoparticles for application in electrochemical devices

The growing demand for materials and devices with new functionalities led to the increased inter-est in the field of nanomaterials and nanotechnologies. Nanoparticles, not only present a reduced size as well as high reactivity, which allows the development of electronic and electrochemical devices with exclusive properties, when compared with thin films. This dissertation aims to explore the development of several nanostructured metal oxides by sol-vothermal synthesis and its application in different electrochemical devices. Within this broad theme, this study has a specific number of objectives: a) research of the influence of the synthesis parameters to the structure and morphology of the nanoparticles; b) improvement of the perfor-mance of the electrochromic devices with the application of the nanoparticles as electrode; c) application of the nanoparticles as probes to sensing devices; and d) production of solution-pro-cessed transistors with a nanostructured metal oxide semiconductor. Regarding the results, several conclusions can be exposed. Solvothermal synthesis shows to be a very versatile method to control the growth and morphology of the nanoparticles. The electrochromic device performance is influenced by the different structures and morphologies of WO3 nanoparticles, mainly due to the surface area and conductivity of the materials. The dep-osition of the electrochromic layer by inkjet printing allows the patterning of the electrodes without wasting material and without any additional steps. Nanostructured WO3 probes were produced by electrodeposition and drop casting and applied as pH sensor and biosensor, respectively. The good performance and sensitivity of the devices is explained by the high number of electrochemical reactions occurring at the surface of the na-noparticles. GIZO nanoparticles were deposited by spin coating and used in electrolyte-gated transistors, which promotes a good interface between the semiconductor and the dielectric. The produced transistors work at low potential and with improved ON-OFF current ratio, up to 6 orders of mag-nitude. To summarize, the low temperatures used in the production of the devices are compatible with flexible substrates and additionally, the low cost of the techniques involved can be adapted for disposable devices.