Electrochemistry in Room-Temperature Ionic Liquids: Potential Windows at Mercury Electrodes

The cathodic and anodic: potential limit of eleven different ionic liquids were determined at a mercury hemisphere electrode. Ionic liquids containing the phosphonium cation (tri(n-hexyl)tetradecylphosphonium, [P-14.6,P-6.6](+)) give the largest potential window, especially When Coupled to a trifluorotris(pentafluoroethyl)- [FAP](-). or bis(trifluoromethanesulfonyl)imide, [NTf2](-), anion.

Electrochemical Determination of Manganese Solubility in Mercury via Amalgamation and Stripping in the Room Temperature Ionic Liquid n-Hexyltriethylammonium Bis(trifluoromethanesulfonyl)imide, [N-6,N-2,N-2,N-2][NTf2]

The solubility of manganese in mercury was determined electrochemically via amalgamation and stripping in the room temperature ionic liquid n-hexyltriethylammonium bis(trifluoromethanesulfonyl)imide, [N-6,N-2,N-2,N-2][NTf2]. A hemispherical mercury electrode was made by electrodepositing mercury onto a planar platinum microelectrode. Cyclic voltammetry of Mn2+ in [N-6,N-2,N-2,N-2][NTf2] at the mercury microhemisphere electrode was investigated at temperatures of 298, 303 and 313 K. The solubility of Mn in Hg was determined on the basis of the charge under the reduction peak (Mn2+ --> Mn-0) and the corresponding reoxidation.

DEPENDENCE OF LIGHT OUTPUT FROM NOMINALLY SMOOTH AL-OX-AU TUNNEL-JUNCTIONS ON ELECTRODE MORPHOLOGY

The light output from nominally smooth Al-Ox-Au tunnel junctions is observed to be substantially independent of the deposition rate of the Au film electrode. Films deposited quickly (2 nm s-1) and those deposited slowly (0.16 nm s-1) have similar spectral dependences and intensities. (This is in contrast to roughened films where those deposited quickly give out less light, especially towards the blue end of the spectrum.) The behaviour can be interpreted in terms of the ratio l(ph)/l(em) where l(ph) and l(em) are the mean free paths of surface plasmons between external photon emissions and internal electromagnetic absorptions respectively. Once l(ph)/l(em) exceeds 100, as it does on smooth films, grain size has little further effect on the spectral shape of the light output. In fast-deposited films there are two compensating effects on the output intensity: grain boundary scattering decreases it and greater surface roughness increases it.

Plasma chloriding of thin-film silver - A novel process in silver-silver chloride reference electrode fabrication

Silver thin films were modified using a novel plasma modification process for the development of thin-film silver-silver chloride reference electrodes. The surface, physical, and electrochemical properties of these electrodes were investigated by atomic force microscopy, thickness and resistivity measurement techniques, as well as impedance spectroscopy and potentiometry. After plasma treatment, thin-film growth was observed and the electrodes, in general, exhibited low interface impedance and a roughened surface. Evidence of a complex surface reorganization was found. Correlating plasma conditions with film properties suggested that increasing pressure and exposure duration increased species availability, therefore governing the reaction rates, while input power appeared to influence the type of surface chemical reactions. Results also indicated that Ar/Cl-2 mixtures should be employed rather than pure chlorine plasmas. (C) 2002 The Electrochemical Society.

Thickness-induced stabilization of ferroelectricity in SrRuO3/Ba0.5Sr0.5TiO3/Au thin film capacitors

Pulsed-laser deposition has been used to fabricate Au/Ba0.5Sr0.5TiO3/SrRuO3/MgO thin film capacitor structures. Crystallographic and microstructural investigations indicated that the Ba0.5Sr0.5TiO3 (BST) had grown epitaxially onto the SrRuO3 lower electrode, inducing in-plane compressive and out- of-plane tensile strain in the BST. The magnitude of strain developed increased systematically as film thickness decreased. At room temperature this composition of BST is paraelectric in bulk. However, polarization measurements suggested that strain had stabilized the ferroelectric state, and that the decrease in film thickness caused an increase in remanent polarization. An increase in the paraelectric-ferroelectric transition temperature upon a decrease in thickness was confirmed by dielectric measurements. Polarization loops were fitted to Landau-Ginzburg-Devonshire (LGD) polynomial expansion, from which a second order paraelectric-ferroelectric transition in the films was suggested at a thickness of similar to500 nm. Further, the LGD analysis showed that the observed changes in room temperature polarization were entirely consistent with strain coupling in the system. (C) 2002 American Institute of Physics.

Studies on polypyrrole film in room temperature melt

A bluish-black shining free standing polypyrrole film (PPy) of electronic conductivity 130 S cm-1 has been prepared by electrochemical oxidative polymerization of pyrrole on Pt/transparent glass conducting electrode resistance 15 O cm-1, using a room temperature melt as an electrolyte, composed of 1:3 stoichiometric ratio of cetyl pyridinium chloride and anhydrous aluminum chloride at 0.58 V versus Al wire as a reference electrode. The film possessed a charge transfer resistance of 132 O, and showed two absorption peaks at 457 and 1264 nm in the UV-vis–NIR diffused reflectance spectra. The morphology of the film was hexagonal. The potential step technique suggested a layered structure. This thin film can easily be peeled off from the electrode surface after three cycles and can be used for various applications like dissipation of electrostatic charge, battery electrode materials, solid electrolytic capacitor, electrochromic windows and displays, microactuators etc. It was also characterized by IR, thermal and SEM studies.

Electrode field penetration: A new interpretation of tunneling currents in barium strontium titanate (BST) thin films

This paper shows that penetration of the applied electric field into the electrodes of a ferroelectric thin film capacitor produces both an interfacial capacitance and an effective mechanism for electron tunneling. The model predictions are compared with experimental results on Au-BST-SrRuO3 capacitors of varying thicknesses, and the agreement is excellent.

The effect of tungsten trioxide thin films at ferroelectric-electrode boundaries on fatigue behaviour

A conventional thin film capacitor heterostructure, consisting of sol-gel deposited lead zirconium titanate (PZT) layers with sputtered platinum top and bottom electrodes, was subjected to fatiguing pulses at a variety of frequencies. The fatigue characteristics were compared to those of a similarly processed capacitor in which a ~20nm tungsten trioxide layer had been deposited, using pulsed laser deposition, between the ferroelectric and upper electrode. The expectation was that, because of its ability to accommodate considerable oxygen non-stoichiometry, tungsten trioxide (WO3) might act as an efficient sink for any oxygen vacancies flushed to the electrode-ferroelectric boundary layer during repetitive switching, and hence would improve the fatigue characteristics of the thin film capacitor. However, it was found that, in general, the addition of tungsten trioxide actually increases the rate of fatigue. It appears that any potential benefit from the WO3, in terms of absorbing oxygen vacancies, is far outweighed by it causing dramatically increased charge injection in the system.

Thin film capacitor cut from single crystals using focused ion beam milling

The focused ion beam microscope (FIB) has been used to fabricate thin parallel-sided ferroelectric capacitors from single crystals of BaTiO3 and SrTiO3. A series of nano-sized capacitors ranging in thickness from similar to660 nm to similar to300 nm were made. Cross-sectional high resolution transmission electron microscopy (HRTEM) revealed that during capacitor fabrication, the FIB rendered around 20 nm of dielectric at the electrode-dielectric interface amorphous, associated with local gallium impregnation. Such a region would act electrically in series with the single crystal and would presumably have a considerable negative influence on the dielectric properties. However, thermal annealing prior to gold electrodes deposition was found to fully recover the single crystal capacitors and homogenise the gallium profile. The dielectric testing of the STO ultra-thin single crystal capacitors was performed yielding a room temperature dielectric constant of similar to300, as is the case in bulk. Therefore, there was no evidence of a collapse in dielectric constant associated with thin film dimensions.

Progressive loss of ferroelectricity under bipolar pulsed fields and experimental determination of non-switchable polarization in Au/Ba0.5Sr0.5TiO3/SrRuO3 thin-film capacitors

175 nm-thick Ba0.5Sr0.5TiO3 (BST) thin film fabricated by pulsed laser deposition (PLD) technique is found to be a mixture of two distributions of material. We discuss whether these two components are nano-regions of paraelectric and ferroelectric phases, or a bimodal grain-size distribution, or an effect of oxygen vacancy gradient from the electrode interface. The fraction of switchable ferroelectric phase decreases under bipolar pulsed fields, but it recovers after removal of the external fields. The plot of capacitance in decreasing dc voltage (C(Vdown arrow) versus that in increasing dc 61 voltage C(Vup arrow) is a superposition of overlapping of two triangles, in contrast to one well-defined triangle for typical ferroelectric SrBi2Ta2O9 thin films.

Demonstration of a novel, flexible, photocatalytic oxygen-scavenging polymer film

The preparation of a novel, flexible, photocatalytic, oxygen-scavenging polymer film is described. The film incorporates nanocrystalline titania particles in an ethyl cellulose polymer film, with or without an added sacrificial electron donor of triethanolamine. When coated on the inside of a glass vessel its UV-driven light-scavenging action is demonstrated by platinum octaethyl porphyrin coated glass beads sealed inside, since their luminescence increases with increasing UV-irradiation time. When used as a flexible film, work with an oxygen electrode shows that the film is able to scavenge oxygen at an average rate of 0.017 cm(3) O-2 h(-1) cm(-2) over a 24 h period, which compares favourably to other, well-established oxygen-scavenger systems. The potential of using such as system for oxygen scavenging in packaging is discussed briefly. (c) 2005 Elsevier B.V. All rights reserved.

Influence of the interfacing with an electrically inhomogeneous bottom electrode on the ferroelectric properties of epitaxial PbTiO3

The influence of an electrically inhomogeneous epitaxial bottom layer on the ferroelectric and electrical properties has been explored in epitaxial PbTiO3 (PTO)/La0.7Sr0.3MnO3 (LSMO) submicron structures using atomic force microscopy. The submicron LSMO-dot structures underneath the ferroelectric PTO film allow exploring gradual changes in material properties. The LSMO interfacial layer influences significantly both electrical and ferroelectric properties of the upper PTO layer. The obtained results show that the as-grown polarization state of an epitaxial ferroelectric layer is strongly influenced by the properties of the layer on top of which it is deposited. (C) 2013 AIP Publishing LLC.

Extruded colour-based plastic film for the measurement of dissolved CO2

Dissolved CO2 measurements are usually made using a Severinghaus electrode, which is bulky and can suffer from electrical interference. In contrast, optical sensors for gaseous CO2, whilst not suffering these problems, are mainly used for making gaseous (not dissolved) CO2 measurements, due to dye leaching and protonation, especially at high ionic strengths (>0.01 M) and acidity (<pH 4). This is usually prevented by coating the sensor with a gas-permeable, but ion-impermeable, membrane (GPM). Herein, we introduce a highly sensitive, colourimetric-based, plastic film sensor for the measurement of both gaseous and dissolved CO2, in which a pH-sensitive dye, thymol blue (TB) is coated onto particles of hydrophilic silica to create a CO2-sensitive, TB-based pigment, which is then extruded into low density polyethylene (LDPE) to create a GPM-free, i.e. naked, TB plastic sensor film for gaseous and dissolved CO2 measurements. When used for making dissolved CO2 measurements, the hydrophobic nature of the LDPE renders the film: (i) indifferent to ionic strength, (ii) highly resistant to acid attack and (iii) stable when stored under ambient (dark) conditions for >8 months, with no loss of colour or function. Here, the performance of the TB plastic film is primarily assessed as a dissolved CO2 sensor in highly saline (3.5 wt%) water. The TB film is blue in the absence of CO2 and yellow in its presence, exhibiting 50% transition in its colour at ca. 0.18% CO2. This new type of CO2 sensor has great potential in the monitoring of CO2 levels in the hydrosphere, as well as elsewhere, e.g. food packaging and possibly patient monitoring.