Assembly of a high-dielectric constant thin TiOX layer directly on H-terminated semiconductor diamond

A high-dielectric constant (high-k) TiOx thin layer was fabricated on hydrogen-terminated diamond (H-diamond) surface by low temperature oxidation of a thin titanium layer in ambient air. The metallic titanium layer was deposited by sputter deposition. The dielectric constant of the resultant TiOx was calculated to be around 12. The capacitance density of the metal-oxide-semiconductor (MOS) based on the TiOx/H-diamond was as high as 0.75 µF/cm2 contributed from the high-k value and the very thin thickness of the TiOx layer. The leakage current was lower than 10-13 A at reverse biases and 10-7A at the forward bias of -2 V. The MOS field-effect transistor based on the high-k TiOx/H-diamond was demonstrated. The utilization of the high-k TiOx with a very thin thickness brought forward the features of an ideally low subthreshold swing slope of 65 mV per decade and improved drain current at low gate voltages. The advantages of the utilization high-k dielectric for diamond MOSFETs are anticipated.

Hopping transport on a fractal: ac conductivity of porous silicon

We have measured the frequency dependence of the conductivity and the dielectric constant of various samples of porous Si in the regime 1 Hz-100 kHz at different temperatures. The conductivity data exhibit a strong frequency dependence. When normalized to the dc conductivity, our data obey a universal scaling law, with a well-defined crossover, in which the real part of the conductivity sigma' changes from an sqrt(omega) dependence to being proportional to omega. We explain this in terms of activated hopping in a fractal network. The low-frequency regime is governed by the fractal properties of porous Si, whereas the high-frequency dispersion comes from a broad distribution of activation energies. Calculations using the effective-medium approximation for activated hopping on a percolating lattice give fair agreement with the data.

Piezoelectric and dielectric properties of Ce substituted La2Ti2O7 ceramics

The ferroelectric and dielectric properties of cerium (Ce) substituted La2Ti2O7 (LTO) have been investigated. Single phase, dense La2-xCexTi2O7 (x=0.15, 0.25, 0.35) ceramics were prepared by spark plasma sintering. The solubility limit of Ce in La2-xCexTi2O7 was found to be between 0.35 and 0.5. The a-, b- and c-axes of the unit cell decrease with increasing Ce substitution. The Curie point (Tc) of La2-xCexTi2O7 (x=0, 0.15, 0.25, 0.35) decreases and dielectric constant and loss increase with increasing Ce substitution. Cerium can increase the d33 of La2Ti2O7. The highest d33 was 3.9±0.1pC/N for La1.85Ce0.15Ti2O7 textured ceramic. © 2012 Elsevier Ltd.

Interplay between the charge transport phenomena and the charge-transfer phase transition in RbxMn[Fe(CN)6]y.zH2O

Charge transport and dielectric measurements were carried out on compacted powder and single-crystal samples of bistable RbxMn[Fe(CN)6]y·zH2O in the two valence-tautomeric forms (MnIIFeIII and MnIIIFeII) as a function of temperature (120-350 K) and frequency (10-2-106 Hz). The complex conductivity data reveal universal conductivity behavior and obey the Barton-Nakajima-Namikawa relationship. The charge transport is accompanied by dielectric relaxation that displays the same thermal activation energy as the conductivity. Surprisingly, the activation energy of the conductivity was found very similar in the two valence-tautomeric forms (0.55 eV), and the conductivity change between the two phases is governed mainly by the variation of the preexponential factor in each sample. The phase transition is accompanied by a large thermal hysteresis of the conductivity and the dielectric constant. In the hysteresis region, however, a crossover occurs in the charge transport mechanism at T < 220 K from an Arrhenius-type to a varying activation energy behavior, conferring an unusual “double-loop” shape to the hysteresis.

Living cationic polymerization of isobutene

The polymerization of isobutene initiated by 1-chloro-1-phenylethane has been investigated, and molecular weight studies conducted using size exclusion chromatography. Polymerizations carried out in a 40/60 (v/v) mixture of dichloromethaneIcyclohexane, using titanium (IV) chloride as a catalyst in the presence of pyridine at -30 °C were found to be controlled and living. The number average molecular weights of the polymers increased linearly with monomer conversion, and the molecular weight distributions were between 1.15 and 1.20. Efficiencies of initiation were between 80 and 100%, and evidence was found to suggest that backbiting to the initiator had occurred, resulting in the formation of cyclic oligomers during the early stages of polymerization. The kinetics of polymerization can be explained in terms of active species in. equilibrium with dormant species. The effects of temperature. and dielectric constant on this equilibrium were studied and a model based upon the Fuoss equation was developed. Pyridine was found to behave as proton trap in the system, and when it was used in excess the rate of polymerization was retarded. By assuming that the catalyst and pyridine formed a one to one complex, it was possible to show that the reaction was second order with respect to the catalyst. The synthesis of low molecular weight polyisobutenes was studied. When the concentration of initiator was increased relative to that of the isobutene, such that the theoretical degree of polymerization was 20 or less, the rate of initiation was slow compared to propagation. The efficiency of initiation in these polymerizations was typically between 30 and 40 %. Optimal conditions of temperature. and.catalyst concentration were established, leading to a 60 % efficiency of initiation. A one-pot synthesis of phenol end-capped polyisobutene was attempted by adding phenol at the end of a living polymerization. Evidence to substantiate the existence of capped polymer chains in the resultant product was inconclusive. Block copolymerizations of oxetane and isobutene were conducted using 1-chloro-1phenylethane/TiCl4, but no copolymer or oxetane homopolymer could be isolated.

Studies on the thermal decomposition behaviour, kinetics and electrical conductivity of the non-isothermal decomposition of pyridine mono carboxylic acids and some of their transition metal complexes

The thesis is divided into four chapters. They are: introduction, experimental, results and discussion about the free ligands and results and discussion about the complexes. The First Chapter, the introductory chapter, is a general introduction to the study of solid state reactions. The Second Chapter is devoted to the materials and experimental methods that have been used for carrying out tile experiments. TIle Third Chapter is concerned with the characterisations of free ligands (Picolinic acid, nicotinic acid, and isonicotinic acid) by using elemental analysis, IR spectra, X-ray diffraction, and mass spectra. Additionally, the thermal behaviour of free ligands in air has been studied by means of thermogravimetry (TG), derivative thermogravimetry (DTG), and differential scanning calorimetry (DSC) measurements. The behaviour of thermal decomposition of the three free ligands was not identical Finally, a computer program has been used for kinetic evaluation of non-isothermal differential scanning calorimetry data according to a composite and single heating rate methods in comparison with the methods due to Ozawa and Kissinger methods. The most probable reaction mechanism for the free ligands was the Avrami-Erofeev equation (A) that described the solid-state nucleation-growth mechanism. The activation parameters of the decomposition reaction for free ligands were calculated and the results of different methods of data analysis were compared and discussed. The Fourth Chapter, the final chapter, deals with the preparation of cobalt, nickel, and copper with mono-pyridine carboxylic acids in aqueous solution. The prepared complexes have been characterised by analyses, IR spectra, X-ray diffraction, magnetic moments, and electronic spectra. The stoichiometry of these compounds was ML2x(H20), (where M = metal ion, L = organic ligand and x = water molecule). The environments of cobalt, nickel, and copper nicotinates and the environments of cobalt and nickel picolinates were octahedral, whereas the environment of copper picolinate [Cu(PA)2] was tetragonal. However, the environments of cobalt, nickel, and copper isonicotinates were polymeric octahedral structures. The morphological changes that occurred throughout the decomposition were followed by SEM observation. TG, DTG, and DSC measurements have studied the thermal behaviour of the prepared complexes in air. During the degradation processes of the hydrated complexes, the crystallisation water molecules were lost in one or two steps. This was also followed by loss of organic ligands and the metal oxides remained. Comparison between the DTG temperatures of the first and second steps of the dehydration suggested that the water of crystallisation was more strongly bonded with anion in Ni(II) complexes than in the complexes of Co(II) and Cu(II). The intermediate products of decomposition were not identified. The most probable reaction mechanism for the prepared complexes was also Avrami-Erofeev equation (A) characteristic of solid-state nucleation-growth mechanism. The tempemture dependence of conductivity using direct current was determined for cobalt, nickel, Cl.nd copper isonicotinates. An activation energy (ΔΕ), the activation energy (ΔΕ ) were calculated.The ternperature and frequency dependence of conductivity, the frequency dependence of dielectric constant, and the dielectric loss for nickel isonicotinate were determined by using altemating current. The value of s paralneter and the value of'density of state [N(Ef)] were calculated. Keyword Thermal decomposition, kinetic, electrical conduclion, pyridine rnono~ carboxylic acid, cOlnplex, transition metal compJex.

Studies of molecular interactions using physical techniques

The investigations described in this thesis concern the molecular interactions between polar solute molecules and various aromatic compounds in solution. Three different physical methods were employed. Nuclear magnetic resonance (n.m.r.) spectroscopy was used to determine the nature and strength of the interactions and the geometry of the transient complexes formed. Cryoscopic studies were used to provide information on the stoichiometry of the complexes. Dielectric constant studies were conducted in an attempt to confirm and supplement the spectroscopic investigations. The systems studied were those between nitromethane, chloroform, acetonitrile (solutes) and various methyl substituted benzenes. In the n.m.r. work the dependence of the solute chemical shift upon the compositions of the solutions was determined. From this the equilibrium quotients (K) for the formation of each complex and the shift induced in the solute proton by the aromatic in the complex were evaluated. The thermodynamic parameters for the interactions were obtained from the determination of K at several temperatures. The stoichiometries of the complexes obtained from cryoscopic studies were found to agree with those deduced from spectroscopic investigations. For most systems it is suggested that only one type of complex, of 1:1 stiochiometry, predominates except that for the acetonitrile-benzene system a 1:2 complex is formed. Two sets of dielectric studies were conducted, the first to show that the nature of the interaction is dipole-induced dipole and the second to calculate K. The equilibrium quotients obtained from spectroscopic and dielectric studies are compared. Time-averaged geometries of the complexes are proposed. The orientation of solute, with respect to the aromatic for the 1:1 complexes, appears to be the one in which the solute lies symmetrically about the aromatic six-fold axis whereas for the 1:2 complex, a sandwich structure is proposed. It is suggested that the complexes are formed through a dipole-induced dipole interaction and steric factors play some part in the complex formation.

The stability and formulation of topical analgesics

High-performance liquid chromatographic methods are developed for the simultaneous determination of various salicylates, their p-hydroxy isomers and nicotinic acid esters. The method is sensitive enough to detect trace amounts (~µM/L)of the product generated from cross reactivity between the drugs and the vehicle. The developed method also allows analysis of various topical products containing salicylate and nicotinate esters in their formulations. Applying this method, the degradation profiles of salicylates, nicotinates, p-hydroxy benzoate, o-methoxy benzoate and aspirin prodrugs in alkaline media are determined. The profile for alkyl salicylate degradation is found to be first order (A---? B) When the alcoholic radical is similar to that of the ester. In alcohol having a radical different from that of the ester function, the degradation is found to proceed through competitive transesterification and hydrolysis. The intermediates are identified following synthesis and isolation. The rate and extent of transesterification depends on the proportion of alcohol present in the system. Equations are presented to model the time profiles of reactant and product concentration. The reactions are base catalysed and the predominant pathway involves a concerted solvent attack upon the salicylate anion. Competitive hydrolysis of both ester components also follows this mechanism at moderate pH values but rates increase under strongly alkaline conditions as direct hydroxide attack becomes significant. In contrast, transesterification is independent of base concentration once full ionization is accomplished. The competitive hydrolysis is modelled using equations involving the dielectric constant of the medium. A range of other esters are also shown to undergo base-catalysed transesterification. In non-alcoholic solution phenyl salicylate undergoes a concentration-dependent oligomerisation which yields salsalate among the products. Competitive transesterification and hydrolysis also occur in products for topical use which have vehicles based upon alcohol, glycol or glycol polymers. Such reactions may compromise stability assessments, pharmaceutical integrity and delivery profiles.

Formulation of topical non-steroidal anti-inflammatory agents

Reversed-pahse high-performance liquid chromatographic (HPLC) methods were developed for the assay of indomethacin, its decomposition products, ibuprofen and its (tetrahydro-2-furanyl)methyl-, (tetrahydro-2-(2H)pyranyl)methyl- and cyclohexylmethyl esters. The development and application of these HPLC systems were studied. A number of physico-chemical parameters that affect percutaneous absorption were investigated. The pKa values of indomethacin and ibuprofen were determined using the solubility method. Potentiometric titration and the Taft equation were also used for ibuprofen. The incorporation of ethanol or propylene glycol in the solvent resulted in an improvement in the aqueous solubility of these compounds. The partition coefficients were evaluated in order to establish the affinity of these drugs towards the stratum corneum. The stability of indomethacin and of ibuprofen esters were investigated and the effect of temperature and pH on the decomposition rates were studied. The effect of cetyltrimethylammonium bromide on the alkaline degradation of indomethacin was also followed. In the presence of alcohol, indomethacin alcoholysis was observed and the kinetics of decomposition were subjected to non-linear regression analysis and the rate constants for the various pathways were quantified. The non-isothermal, sufactant non-isoconcentration and non-isopH degradation of indomethacin were investigated. The analysis of the data was undertaken using NONISO, a BASIC computer program. The degradation profiles obtained from both non-iso and iso-kinetic studies show that there is close concordance in the results. The metabolic biotransformation of ibuprofen esters was followed using esterases from hog liver and rat skin homogenates. The results showed that the esters were very labile under these conditions. The presence of propylene glycol affected the rates of enzymic hydrolysis of the ester. The hydrolysis is modelled using an equation involving the dielectric constant of the medium. The percutaneous absorption of indomethacin and of ibuprofen and its esters was followed from solutions using an in vitro excised human skin model. The absorption profiles followed first order kinetics. The diffusion process was related to their solubility and to the human skin/solvent partition coefficient. The percutaneous absorption of two ibuprofen esters from suspensions in 20% propylene glycol-water were also followed through rat skin with only ibuprofen being detected in the receiver phase. The sensitivity of ibuprofen esters to enzymic hydrolysis compared to the chemical hydrolysis may prove valuable in the formulation of topical delivery systems.

Strategic development and physicochemical analysis of oral preparations for unstable drugs

Oral liquid formulations are ideal dosage forms for paediatric, geriatric and patient with dysphagia. Dysphagia is prominent among patients suffering from stroke, motor neurone disease, advanced Alzheimer’s and Parkinson’s disease. However oral liquid preparations are particularly difficult to formulate for hydrophobic and unstable drugs. Therefore current methods employed in solving this issue include the use of ‘specials’ or extemporaneous preparations. In order to challenge this, the government has encouraged research into the field of oral liquid formulations, with the EMEA and MHRA publishing list of drugs of interest. The current work investigates strategic formulation development and characterisation of select API’s (captopril, gliclazide, melatonin, L-arginine and lansoprazole), each with unique obstacles to overcome during solubilisation, stabilisation and when developing a palatable dosage from. By preparing a validated calibration protocol for each of the drug candidates, the oral liquid formulations were assessed for stability, according to the ICH guidelines along with thorough physiochemical characterisation. The results showed that pH and polarity of the solvent had the greatest influence on the extent of drug solubilisation, with inclusion of antioxidants and molecular steric hindrance influencing the extent of drug stability. Captopril, a hydrophilic ACE inhibitor (160 mg.mL-1), undergoes dimerisation with another captopril molecule. It was found that with the addition of EDTA and HP-β-CD, the drug molecule was stabilised and prevented from initiating a thiol induced first order free radical oxidation. The cyclodextrin provided further steric hindrance (1:1 molar ratio) resulting in complete reduction of the intensity of sulphur like smell associated with captopril. Palatability is a crucial factor in patient compliance, particularly when developing a dosage form targeted towards paediatrics. L-arginine is extremely bitter in solution (148.7 g.L-1). The addition of tartaric acid into the 100 mg.mL-1 formulation was sufficient to mask the bitterness associated with its guanidium ions. The hydrophobicity of gliclazide (55 mg.L-1) was strategically challenged using a binary system of a co-solvent and surfactant to reduce the polarity of the medium and ultimately increase the solubility of the drug. A second simpler method was developed using pH modification with L-arginine. Melatonin has two major obstacles in formulation: solubility (100 μg.mL-1) and photosensitivity, which were both overcome by lowering the dielectric constant of the medium and by reversibly binding the drug within the cyclodextrin cup (1:1 ratio). The cyclodextrin acts by preventing UV rays from reaching the drug molecule and initiated the degradation pathway. Lansoprazole is an acid labile drug that could only be delivered orally via a delivery vehicle. In oral liquid preparations this involved nanoparticulate vesicles. The extent of drug loading was found to be influenced by the type of polymer, concentration of polymer, and the molecular weight. All of the formulations achieved relatively long shelf-lives with good preservative efficacy.

Informational masking of monaural target speech by a single contralateral formant

Recent research suggests that the ability of an extraneous formant to impair intelligibility depends on the variation of its frequency contour. This idea was explored using a method that ensures interference cannot occur through energetic masking. Three-formant (F1+F2+F3) analogues of natural sentences were synthesized using a monotonous periodic source. Target formants were presented monaurally, with the target ear assigned randomly on each trial. A competitor for F2 (F2C) was presented contralaterally; listeners must reject F2C to optimize recognition. In experiment 1, F2Cs with various frequency and amplitude contours were used. F2Cs with time-varying frequency contours were effective competitors; constant-frequency F2Cs had far less impact. To a lesser extent, amplitude contour also influenced competitor impact; this effect was additive. In experiment 2, F2Cs were created by inverting the F2 frequency contour about its geometric mean and varying its depth of variation over a range from constant to twice the original (0%-200%). The impact on intelligibility was least for constant F2Cs and increased up to ∼100% depth, but little thereafter. The effect of an extraneous formant depends primarily on its frequency contour; interference increases as the depth of variation is increased until the range exceeds that typical for F2 in natural speech.

Informational masking of monaural target speech by a single contralateral formant

Recent research suggests that the ability of an extraneous formant to impair intelligibility depends on the variation of its frequency contour. This idea was explored using a method that ensures interference occurs only through informational masking. Three-formant analogues of sentences were synthesized using a monotonous periodic source (F0 = 140 Hz). Target formants were presented monaurally; the target ear was assigned randomly on each trial. A competitor for F2 (F2C) was presented contralaterally; listeners must reject F2C to optimize recognition. In experiment 1, F2Cs with various frequency and amplitude contours were used. F2Cs with time-varying frequency contours were effective competitors; constant-frequency F2Cs had far less impact. Amplitude contour also influenced competitor impact; this effect was additive. In experiment 2, F2Cs were created by inverting the F2 frequency contour about its geometric mean and varying its depth of variation over a range from constant to twice the original (0–200%). The impact on intelligibility was least for constant F2Cs and increased up to ~100% depth, but little thereafter. The effect of an extraneous formant depends primarily on its frequency contour; interference increases as the depth of variation is increased until the range exceeds that typical for F2 in natural speech.

Dielectric and electro-optical properties of some cyanobiphenyl liquid-crystals

A variety of methods have been reviewed for obtaining parallel or perpendicular alignment in liquid-crystal cells. Some of these methods have been selected and developed and were used in polarised spectroscopy, dielectric and electro-optic studies. Also, novel dielectric and electro-optic cells were constructed for use over a range of temperature. Dielectric response of thin layers of E7 and E8 (eutectic mixture liquid-crystals) have been measured in the frequency range (12 Hz-100 kHz) and over a range of temperature (183-337K). Dielectric spectra were also obtained for supercooled E7 and E8 in the Hz and kHz range. When the measuring electric field was parallel to the nematic director, one loss peak (low-frequency relaxation process) was observed for E7 and for E8, that exhibits a Debye-type behaviour in the supercooled systems. When the measuring electric field was perpendicular to the nematic director, two resolved dielectric processes have been observed. The phase transitions, effective molecular polarisabilities, anisotropy of polarisabilities and order parameters of three liquid crystal homologs (5CB, 6CB, and 7CB), 60CB and three eutectic nematic mixtures E7, E8, and E607 were calculated using optical and density data measured at several temperatures. The order parameters calculated using the different methods of Vuks, Neugebauer, Saupe-Maier, and Palffy-Muhoray are nearly the same for the liquid crystals considered in the present study. Also, the interrelationship between density and refractive index and the molecular structure of these liquid crystals were established. Accurate dielectric and dipole results of a range of liquid-crystal forming molecules at several temperatures have reported. The role of the cyano-end group, biphenyl core, and flexible tail in molecular association, were investigated using the dielectric method for some molecules which have a structural relationship to the nematogens. Analysis of the dielectric data for solution of the liquid-crystals indicated a high molecular association, comparable to that observed in the nematic or isotropic phases. Electro-optic Kerr effect were investigated for some alkyl cyanobiphenyls, their nematic mixtures and the eutectic mixture liquid-crystals E7 and E8 in the isotropic phase and solution. The Kerr constant of these liquid crystals found to be very high at the nematic-isotropic transition temperatures as the molecules are expected to be highly ordered close to phase transition temperatures. Dynamic Kerr effect behaviour and transient molecular reorientation were also observed in thin layers of some alkyl cyanobiphenyls. Dichroic ratio R and order parameters of solutions containing some azo and anthraquinone dyes in the nematic solvent (E7 and E8), were investigated by the measurement of the intensity of the absorption bands in the visible region of parallel aligned samples. The effective factors on the dichroic ratio of the dyes dissolved in the nematic solvents were determined and discussed.

Build-up of auditory stream segregation induced by tone sequences of constant or alternating frequency and the resetting effects of single deviants

A sequence of constant-frequency tones can promote streaming in a subsequent sequence of alternating-frequency tones, but why this effect occurs is not fully understood and its time course has not been investigated. Experiment 1 used a 2.0-s-long constant-frequency inducer (10 repetitions of a low-frequency pure tone) to promote segregation in a subsequent, 1.2-s test sequence of alternating low- and high-frequency tones. Replacing the final inducer tone with silence substantially reduced reported test-sequence segregation. This reduction did not occur when either the 4th or 7th inducer was replaced with silence. This suggests that a change at the induction/test-sequence boundary actively resets build-up, rather than less segregation occurring simply because fewer inducer tones were presented. Furthermore, Experiment 2 found that a constant-frequency inducer produced its maximum segregation-promoting effect after only three tones—this contrasts with the more gradual build-up typically observed for alternating-frequency sequences. Experiment 3 required listeners to judge continuously the grouping of 20-s test sequences. Constant-frequency inducers were considerably more effective at promoting segregation than alternating ones; this difference persisted for ~10 s. In addition, resetting arising from a single deviant (longer tone) was associated only with constant-frequency inducers. Overall, the results suggest that constant-frequency inducers promote segregation by capturing one subset of test-sequence tones into an ongoing, preestablished stream, and that a deviant tone may reduce segregation by disrupting this capture. These findings offer new insight into the dynamics of stream segregation, and have implications for the neural basis of streaming and the role of attention in stream formation. (PsycINFO Database Record (c) 2013 APA, all rights reserved)

Build-up of auditory stream segregation induced by tone sequences of constant or alternating frequency and the resetting effects of single deviants

A sequence of constant-frequency tones can promote streaming in a subsequent sequence of alternating-frequency tones, but why this effect occurs is not fully understood and its time course has not been investigated. Experiment 1 used a 2.0-s-long constant-frequency inducer (10 repetitions of a low-frequency pure tone) to promote segregation in a subsequent, 1.2-s test sequence of alternating low- and high-frequency tones. Replacing the final inducer tone with silence substantially reduced reported test-sequence segregation. This reduction did not occur when either the 4th or 7th inducer was replaced with silence. This suggests that a change at the induction/test-sequence boundary actively resets build-up, rather than less segregation occurring simply because fewer inducer tones were presented. Furthermore, Experiment 2 found that a constant-frequency inducer produced its maximum segregation-promoting effect after only three tones—this contrasts with the more gradual build-up typically observed for alternating-frequency sequences. Experiment 3 required listeners to judge continuously the grouping of 20-s test sequences. Constant-frequency inducers were considerably more effective at promoting segregation than alternating ones; this difference persisted for ~10 s. In addition, resetting arising from a single deviant (longer tone) was associated only with constant-frequency inducers. Overall, the results suggest that constant-frequency inducers promote segregation by capturing one subset of test-sequence tones into an ongoing, preestablished stream, and that a deviant tone may reduce segregation by disrupting this capture. These findings offer new insight into the dynamics of stream segregation, and have implications for the neural basis of streaming and the role of attention in stream formation. (PsycINFO Database Record (c) 2013 APA, all rights reserved)