He, Ne and Ar isotope compositions of fluid inclusions in hydrothermal sulfides from the TAG hydrothermal field, Mid-Atlantic Ridge

Helium, rieon and argon isotope compositions of fluid inclusions have been measured in hydrothermal sulfide samples from the TAG hydrothermal field at the Mid-Atlantic Ridge. Fluid-inclusion He-3/He-4 ratios are 2.2-13.3 times the air value (Ra), and with a mean of 7.2 Ra. Comparison with the local vent fluids (He-3/He-4=7.5-8.2 Ra) and mid-ocean ridge basalt values (He-3/He-4=6-11 Ra) shows that the variation range of He-3/He-4 ratios from sulfide-hosted fluid inclusions is significantly large. Values for Ne-20/Ne-22 are from 10.2 to 11.4, which are significantly higher than the atmospheric ratio (9.8). And fluid-inclusion Ar-40/Ar-36 ratios range from 287 to 359, which are close to the atmospheric values (295.5). These results indicate that the noble gases of fluid inclusions in hydrothermal sulfides are a mixture of mantle- and seawater-derived noble gases; the partial mantle-derived components of trapped hydrothermal fluids may be from the lower mantle; the helium of fluid inclusions is mainly from upper mantle; and the Ne and Ar components are mainly from seawater.

Indium tin oxide refractometer in the visible and near infrared via lossy mode and surface plasmon resonances with Kretschmann configuration

The following article appeared in Torres, V., Beruete, M., Del Villar, I., & Sánchez, P. (2016). Indium tin oxide refractometer in the visible and near infrared via lossy mode and surface plasmon resonances with Kretschmann configuration. Applied Physics Letters, 108(4), doi:10.1063/1.4941077, and may be found at http://dx.doi.org/10.1063/1.4941077.

Development of inversion-mode and junctionless Indium-Gallium-Arsenide MOSFETs

This PhD covers the development of planar inversion-mode and junctionless Al2O3/In0.53Ga0.47As metal-oxidesemiconductor field-effect transistors (MOSFETs). An implant activation anneal was developed for the formation of the source and drain (S/D) of the inversionmode MOSFET. Fabricated inversion-mode devices were used as test vehicles to investigate the impact of forming gas annealing (FGA) on device performance. Following FGA, the devices exhibited a subthreshold swing (SS) of 150mV/dec., an ION/IOFF of 104 and the transconductance, drive current and peak effective mobility increased by 29%, 25% and 15%, respectively. An alternative technique, based on the fitting of the measured full-gate capacitance vs gate voltage using a selfconsistent Poisson-Schrödinger solver, was developed to extract the trap energy profile across the full In0.53Ga0.47As bandgap and beyond. A multi-frequency inversion-charge pumping approach was proposed to (1) study the traps located at energy levels aligned with the In0.53Ga0.47As conduction band and (2) separate the trapped charge and mobile charge contributions. The analysis revealed an effective mobility (μeff) peaking at ~2850cm2/V.s for an inversion-charge density (Ninv) = 7*1011cm2 and rapidly decreasing to ~600cm2/V.s for Ninv = 1*1013 cm2, consistent with a μeff limited by surface roughness scattering. Atomic force microscopy measurements confirmed a large surface roughness of 1.95±0.28nm on the In0.53Ga0.47As channel caused by the S/D activation anneal. In order to circumvent the issue relative to S/D formation, a junctionless In0.53Ga0.47As device was developed. A digital etch was used to thin the In0.53Ga0.47As channel and investigate the impact of channel thickness (tInGaAs) on device performance. Scaling of the SS with tInGaAs was observed for tInGaAs going from 24 to 16nm, yielding a SS of 115mV/dec. for tInGaAs = 16nm. Flat-band μeff values of 2130 and 1975cm2/V.s were extracted on devices with tInGaAs of 24 and 20nm, respectively

Optical Characterization of Indium Gallium Nitride for Application in High-Efficiency Solar Photovoltaic Cells

The semiconductor alloy indium gallium nitride (InxGa1-xN) offers substantial potential in the development of high-efficiency multi-junction photovoltaic devices due to its wide range of direct band gaps, strong absorption and other optoelectronic properties. This work uses a variety of characterization techniques to examine the properties of InxGa1-xN thin films deposited in a range of compositions by a novel plasma-enhanced evaporation deposition system. Due to the high vapour pressure and low dissociation temperature of indium, the indium incorporation and, ultimately, control of the InxGa1-xN composition was found to be influenced to a greater degree by deposition temperature than variations in the In:Ga source rates in the investigated region of deposition condition space. Under specific deposition conditions, crystalline films were grown in an advantageous nano-columnar microstructure with deposition temperature influencing column size and density. The InxGa1-xN films were determined to have very strong absorption coefficients with band gaps indirectly related to indium content. However, the films also suffer from compositional inhomogeneity and In-related defect complexes with strong phonon coupling that dominates the emission mechanism. This, in addition to the presence of metal impurities, harms the alloy’s electronic properties as no significant photoresponse was observed. This research has demonstrated the material properties that make the InxGa1-xN alloy attractive for multi-junction solar cells and the benefits/drawbacks of the plasma-enhanced evaporation deposition system. Future work is needed to overcome significant challenges relating to crystalline quality, compositional homogeneity and the optoelectronic properties of In-rich InxGa1-xN films in order to develop high-performance photovoltaic devices.

Tandem enzyme-catalysed oxidations of alkyl phenyl sulfides and alkyl benzenes: enantiocomplementary routes to chiral phenols.

Dioxygenase-catalysed trioxygenation of alkyl phenyl sulfides and alkyl benzenes yields enantiopure cis-dihydrodiol sulfoxides and triols respectively; naphthalene cis-dihydrodiol dehydrogenase-catalysed aromatisation of these diastereoisomers gives enantiopure catechols of either configuration.

Dioxygenase-catalysed oxidation of alkylaryl sulfides: sulfoxidation versus cis-dihydrodiol formation

Toluene- and naphthalene-dioxygenase-catalysed sulfoxidation of nine disubstituted methylphenyl sulfides, using whole cells of Pseudomonas putida, consistently gave the corresponding enantioenriched sulfoxides. Using the P. putida UV4 mutant strain, and these substrates, differing proportions of the corresponding cis-dihydrodiol sulfides were also isolated. Evidence was found for the concomitant dioxygenase-catalysed cis-dihydroxylation and sulfoxidation of methyl paratolyl sulfide. A simultaneous stereoselective reductase-catalysed deoxygenation of (S)-methyl para-tolyl sulfoxide, led to an increase in the proportion of the corresponding cis-dihydrodiol sulfide. The enantiopurity values and absolute configurations of the corresponding cis-dihydrodiol metabolites from methyl ortho-and para-substituted phenyl sulfides were determined by different methods, including chemoenzymatic syntheses from the cis-dihydrodiol metabolites of para-substituted iodobenzenes. Further evidence was provided to support the validity of an empirical model to predict, (i) the stereochemistry of cis-dihydroxylation of para-substituted benzene substrates, and (ii) the regiochemistry of cis-dihydroxylation reactions of ortho-substituted benzenes, each using toluene dioxygenase as biocatalyst.

Dioxygenase-catalysed sulfoxidation of bicyclic alkylaryl sulfides and chemoenzymatic synthesis of acyclic disulfoxides

Toluene- and naphthalene-dioxygenase-catalysed oxidation of six bicyclic disulfide substrates, using whole cells of Pseudomonas putida, gave the corresponding monosulfoxides with high ee values and enantiocomplementarity, in most cases. Two alcohol-sulfoxide diastereoisomers, formed from the reaction of the (R)-1,3-benzodithiole-1-oxide metabolite with n-butyllithium and benzaldehyde, were separated and stereochemically assigned. Treatment, of enantiopure (1R,3R)-benzo-1,3-dithiole-1,3-dioxide, obtained by chemoenzymatic synthesis, with alkyllithium reagents, resulted in a novel ring-opening reaction which proceeded with inversion of configuration to yield a series of acyclic disulfoxides. (C) 2003 Elsevier Ltd. All rights reserved.

Dioxygenase-catalysed mono-, di- and tri-oxygenation of dialkyl sulfides and thioacetals: chemoenzymatic synthesis of enantiopure cis-diol sulfoxides

Toluene dioxygenase (TDO)-catalysed monooxygenation of methylsulfanylmethyl phenyl sulfide 1 and methylsulfanylmethyl 2-pyridyl sulfide 4, using whole cells of Pseudomonas putida UV4, occurred exclusively at the alkyl aryl sulfur centre to yield the alkyl aryl sulfoxides 2 and 5 respectively. These sulfoxides, accompanied by the dialkyl sulfoxides 3 and 6, were also obtained from naphthalene dioxygenase (NDO)-catalysed sulfoxidation of thioacetals 1 and 4 using intact cells of P. putida NCIMB 8859. Enzymatic oxidation of methyl benzyl sulfide 7, 2-phenyl-1,3-dithiane 19, and 2-phenyl-1,3-dithiolane 23, using TDO, gave the corresponding dialkyl sulfoxides 8, 20 and 24 as minor bioproducts. TDO-catalysed dioxygenation of the alkyl benzyl sulfides 7, 15 and 17 and the thioacetals 19 and 23, with P. putida UV4, yielded the corresponding enantiopure cis-dihydrodiols 9, 16, 18, 21 and 25 as major metabolites and cis-dihydrodiol sulfoxides 14, 22 and 26 as minor metabolites, resulting from a tandem trioxygenation of substrates 7, 19 and 23 respectively. Chemical oxidation, of the enantiopure cis-dihydrodiol sulfides 9, 16, 18 and 21 with dimethyldioxirane (DMD), gave separable mixtures of the corresponding pairs of cis-dihydrodiol sulfoxide diastereoisomers 14 and 27, 28 and 29, 30 and 31, 22 and 32. While dialkyl sulfoxide bioproducts 3, 6, 20 and 24 were of variable enantiopurity (27-greater than or equal to 98% ee), alkyl aryl monosulfoxides 2 and 5, cis-dihydrodiols 9, 16, 18, 21 and 25 and cis-dihydrodiol sulfoxide bioproducts 14, 22 and 26 were all single enantiomers (greater than or equal to 98% ee). The absolute configurations of the products, obtained from enzyme-catalysed (TDO and NDO) and chemical (DMD) oxidation methods, were determined by stereochemical correlation, circular dichroism, and X-ray crystallographic methods.

Speciation of Chlorometallate Ionic Liquids Based on Gallium(III) and Indium(III)

A range of ionic liquids was prepared by mixing 1-alkyl-3-methylimidazolium chloride with gallium(III) chloride or indium(III) chloride in various ratios, producing both acidic and basic compositions. Their speciation was investigated using Ga-71 NMR or In-115 NMR spectroscopy, as well as extended X-ray absorption fine structure. Polynuclear Lewis acidic anions, [MxCl3x+1](-), were found in chlorogallate(III) ionic liquids, but not in chloroindate(III) systems.

Toluene and naphthalene dioxygenase-catalysed sulfoxidation of alkyl aryl sulfides

A series of alkyl aryl sulfides were metabolised, using selected strains of the soil bacterium Pseudomonas putida containing either toluene dioxygenase (TDO) or naphthalene dioxygenase (NDO), to give chiral sulfoxides. Alkyl aryl sulfoxides 2a-2k, 4a-4j and 4l, having enantiomeric excess (ee) values of >90%, were obtained by use of the appropriate strain of P. putida (UV4 or NCIMB 8859), Enantiocomplimentarity was observed for the formation of sulfoxides 2a, 2b, 2d, 2j, 4a, 4b and 4d, with TDO-catalysed (UV4) oxidation favouring the (R) enantiomer and NDO-catalysed oxidation (NCIMB 8859) the (S) enantiomer. Evidence of involvement of the TDO enzyme was obtained using a recombinant strain of Escherichia coli (pKST 11), The marked degree of stereoselectivity appears to be mainly due to enzyme-catalysed asymmetric sulfoxidation, however the possibility of a minor contribution from kinetic resolution, in some cases, cannot be excluded.

The electronic band structure of indium selenide:Photoemission and theory

The electronic band structure of vacuum cleaved single-crystal indium selenide has been investigated by X-ray and ultraviolet photoelectron spectroscopy. The valence band consists of three well separated groups, one derived from the Se 4s levels, and two derived from p-like wavefunctions. The band structure and valence band density of states has been calculated using a tight-binding single-layer approximation and all the major features in the experimental spectra are well accounted for. The spin-orbit splitting and electron loss structure associated with the In 4d core level is also reported.