Novel oxidative electrophilic coupling reactions of phenoxazine derivatives with MBTH and their applications to spectrophotometric determination of residual chlorine in drinking water and environmental water samples

Novel, sensitive and rapid spectrophotometric methods, using phenoxazine (PNZ), 2-chlorophe-noxazine (CPN) and 2-trifluoromethylphenoxazine (TPN) as chromogenic reagents for the determination of residual chlorine are proposed. The methods are based on the reduction of chlorine by an electrophilic coupling reagent, 3-methyl-2-benzothiazoline hydrazono hydrochloride hydrate (MBTH) in mild hydrochloric acid medium and subsequent coupling with PNZ, CPN or TPN. The blue color formed in the reaction showed maximum absorbance at 680–690 nm and obeyed Beer's law over the range 0.1–2.2 μg ml⁻¹. The molar absorptivity values with PNZ, CPN and TPN were 2.80 × 10⁴, 2.67 × 10⁴ and 1.91 × 10⁴ l mol⁻¹ cm⁻¹ and Sandell's sensitivity values were 0.028, 0.027 and 0.028 μg cm⁻² respectively. The proposed methods were successfully applied in the determination of residual chlorine in drinking water and environmental water samples. The performance of proposed methods was evaluated in terms of Student's t-test and variance ratio F-test which indicated the significance of proposed methods over the standard spectrophotometric method.     

Electrical and optical properties of 12CaO·7Al2O3 electride doped indium tin oxide thin film deposited by RF magnetron co-sputtering

12CaO·7Al₂O₃ electride (C12A7:e⁻) doped indium tin oxide (ITO) (ITO:C12A7:e⁻) thin films were fabricated on a glass substrate by an RF magnetron co-sputtering system with increasing number of C12A7:e⁻ chips (from 1 to 7) and at various oxygen partial pressure ratios. The optical transmittance of the ITO:C12A7:e⁻ thin film was higher than 70% in the visible wavelength region. In the electrical properties of the thin film, a decrease of the carrier concentration from 2.6 × 10²⁰ cm^− 3 to 2.1 × 10¹⁸ cm^− 3 and increase of the resistivity from 1.4 × 10^− 3 Ω cm to 4.1 × 10^− 1 Ω cm were observed with increasing number of C12A7:e⁻ chips and oxygen partial pressure ratios. It was also observed that the Hall mobility was decreased from 17.27 cm²·V^− 1·s^− 1 to 5.13 cm²·V^− 1·s^− 1. The work function of the ITO thin film was reduced by doping it with C12A7:e⁻.     

Fast silicon p doped low temperature bolometer

The construction of a fast silicon p doped low temperature bolometer is described. It is a 5 × 5 × 0.3 mm Si <100 > n-type chip whose surface has been implanted with p doses of the order of 10¹⁸cm⁻³. The bolometer has a response time better than 1 μs, a responsivity of 10⁴VW⁻¹ and a NEP of .     

Impedance spectroscopy measurements of charge carrier mobility in 4,4'-N,N'-dicarbazole-biphenyl thin films doped with tris(2-phenylpyridine) iridium

The charge carrier mobility of green phosphorescent emissive layers, tris(2-phenylpyridine) iridium [Ir(ppy)₃]-doped 4,4'-N,N'-dicarbazole-biphenyl (CBP) thin films, has been determined using impedance spectroscopy (IS) measurements. The theoretical basis of mobility measurement by IS rests on a theory for single-injection space-charge limited current. The hole mobilities of the Ir(ppy)₃-doped CBP thin films were measured to be 10^− 10–10^− 8 cm²V^− 1 s^− 1 in the 2–7 wt.% Ir(ppy)₃-doped CBP from the frequency dependence of both conductance and capacitance. These hole mobility values are much lower than those of the undoped CBP thin films (~ 10^− 3 cm²V^− 1 s^− 1) because the Ir(ppy)₃ molecules act as trapping centers in the CBP host matrix. These mobility measurements in the Ir(ppy)₃-doped CBP thin films provide insight into the hole injection process.     

Effect of preparation conditions on the physical and hydrophobic properties of two step processed ambient pressure dried silica aerogels

The experimental results on the physical and hydrophobic properties of the ambient pressure dried silica aerogels as a function of sol-gel and drying conditions, are reported.The aerogels have been produced by a two stage (acidic and basic) catalytic sol-gel process using tetraethylorthosilicate (TEOS) precursor, oxalic acid (OXA) and ammonium hydroxide (NH₄OH) catalysts, ethanol (EtOH) solvent and hexamethyldisilazane (HMDZ) silylating agent at 200^∘C.The molar ratios of HMDZ/TEOS (M), OXA/TEOS (A) NH₄OH/TEOS (B), acidic H₂O/TEOS (Wa) basic H₂O/TEOS (Wb), EtOH/TEOS (S) were varied from 0.09 to 0.9, 3.115 × 10^{− 5} to 3.115 × 10⁻³, 4 × 10^{− 3} to 8 × 10^{− 2}, 2 to 9, 1.25 to 5 and 1 to 16 respectively. The physical properties such as the percentage (%) of volume shrinkage, density, thermal conductivity, percentage of porosity, the percentage of optical transmission and contact angle have been found to be strongly dependent on the sol-gel parameters. It was found from the FTIR spectra of the aerogels that with the increase of M, the bands at 3500 and 1600 cm^{− 1} corresponding to H-OH and Si-OH respectively decreased and the bands at 840 and 1250 cm^{− 1} due to Si-C and 2900 and 1450 cm⁻¹ due to C-H increased. The best quality silica aerogels in terms of low density, low volume shrinkage, low thermal conductivity, high hydrophobicity and high optical transmission have been obtained with the molar ratio of TEOS:EtOH:acidicH₂O:basicH₂O:OXA:NH₄OH:HMDZ at 1:8:3.75:2.25:6.23 × 10^{− 5}: 4 × 10^{− 2}:0.36 respectively, by ambient pressure dried method.     

Structural and electrical characterization of AgInS<Subscript>2</Subscript> thin films grown by single-source thermal evaporation method

Structural and electrical properties of AgInS₂ (AIS) thin films grown by single-source thermal evaporation method were studied. The X-ray diffraction spectra indicated that the AIS single phase was successfully grown by annealing above 400∘C in air. The grain size of the AIS crystals was above 2.5 μm from the surface photograph. Furthermore, the AIS grain sizes became large with increasing the annealing temperatures. All the samples indicated n-type conduction by the Van der Pauw technique. The carrier concentrations and the resistivities of the AIS films at room temperature were in the range of 10¹⁹–10²² cm⁻³ and 10⁻¹–10⁻³ Ωcm, respectively. Therefore the mobilities increased from 0.6 to 6.0 cm²/Vs with increasing the grain sizes.     

A study of very thin DLC foils as a gas barrier

Measurements of vacuum tightness and mechanical strength of diamond-like carbon (DLC) foils in the thickness range of 1–7 μg cm⁻² have been performed with a purpose to evaluate suitability of foils as a gas barrier. Hydrogen and argon at pressures from 10⁻² Pa to 20 kPa were used as test gases. The permeation rate specified as conductance density was found for the best sample of self-supporting foil to be around 1.5×10⁻³ l and 3.3×10⁻⁴ l s⁻¹ cm⁻² for H₂ and Ar, respectively. Conductance density of the same foils mounted on the frames with a mesh along the apertures as support was about twice higher than that for the self-supporting ones, likely due to the mechanical imperfections of the foil assemblies of the first ones. On the other hand, mesh-supported foils as thin as 3 μg cm⁻² and of 5 mm in diameter were withstanding the pressure of up to 18 kPa, while self-supporting foils of the same thickness ruptured at around 1.2 kPa. There was no observed relation between thickness of the foil and its mechanical properties and permeation rate. This suggests that rather tears and pinholes present in foils are the limiting factors of the foil–vacuum tightness and strength. Results obtained in the studies, presented in this work, demonstrate the ability of very thin DLC to isolate a high vacuum beam line from a gas cell in a variety of applications and ability to withstand the gas pressure relevant, in particular, to some gas-filled ionization chambers.     

Biosensor enhanced by glucose oxidase biomimetic membrane containing the platinum and silica nanoparticles

In this paper, glucose biosensor is fabricated with immobilization of glucose oxidase (GOx) in platinum and silica sol. The glucose biosensor combined with Pt and SiO₂ nanoparticles could make full use of the properties of nanoparticles. A set of experimental results indicates that the current response for the enzyme electrode containing platinum and silica nanoparticles increases from 0.32 µA cm^− 2 to 33 µA cm^− 2 in the solution of 10 mM β-D-glucose. The linear range is 3 × 10^− 5 to 3.8 × 10^− 3 M with a detection limit of 2 × 10^− 5 M at 3σ. The effects of the various volume ratios of Pt and SiO₂ sols with respect to the current response and the stability of the enzyme electrodes are studied.     

Improvement of semiconductor detector characteristics during supercurrent proton irradiation

Volt-ampère characteristics of Si p-type detectors are established to improve after pulse supercurrent irradiation with low energy protons. Appreciable improvement of energy resolution is observed for detectors irradiatied with the supercurrent proton beam within a dose interval from 10¹¹ to 5×10¹² proton cm⁻². Radiational resource of operation increases from 2.3 × 10¹⁰ to 3.7×10 ¹¹ proton cm⁻² for detectors which were pre-irradiated by the supercurrent proton beam.     

Comprehensive characterization of hydride VPE grown GaN layers and templates

GaN community has recently recognized that it is imperative that the extended, and point defects in GaN and related materials, and the mechanisms for their formation are understood. This is a first and an important step, which must be followed by defect reduction before full implementation of this material and its allied binaries/ternaries in devices. This review is based on a recent concerted effort to establish benchmarks as far as defects are concerned, and identify the basic issues involved. Samples were analyzed for extended defects by TEM and chemical etches, for polarity by electric force microscopy and convergent beam electron diffraction (CBED), for point defects by DLTS, for optical quality and deep defects by photoluminescence (PL), for vacancies by positron annihilation, for donor and acceptor like states within the gap by ODMR and EPR, and for carrier transport targeted for defects and impurities by variable temperature and magnetic field-dependent Hall measurements.Hydride VPE samples grown at Lincoln Laboratories with 1.5, 5.5 and 55 μm thicknesses were investigated for defects by TEM, and their polarity was found to be Ga-polarity, as expected, by CBDE combined with simulations. The density of misfit dislocations at the substrate/EPI interface was determined to be on the order of 10¹³ cm⁻² based on high-resolution electron microscopy images. The threading dislocation density decreased gradually with distance from the interface, reaching a value of about 10⁸ cm⁻² at the surface of a 55 μm film. A 200 μm thick laser separated and free-standing HVPE grown GaN template grown at Samsung was also characterized similarly. The free surface and substrate sides were confirmed to be Ga- and N-polarity, respectively. The density of dislocations near the N-face was determined to be, in order, (3±1)×10⁷ and (4±1)×10⁷ by cross-sectional TEM and plan-view TEM, respectively. Identical observations on the Ga-face revealed the defect concentration to be less than 1×10⁷ cm⁻² by plan-view TEM and 5×10⁵ cm⁻² by cross-sectional TEM.Defects in a 10 μm thick GaN layer grown by HVPE at Lincoln Laboratory have been investigated by photo electrochemical (PEC) etching, and by wet etching in hot H₃PO₄ acid and molten KOH. Threading vertical wires (i.e. whiskers) and hexagonal-shaped etch pits are formed on the etched sample surfaces by PEC and wet etching, respectively. Using atomic force microscopy, one finds the density of “whisker-like” features to be 2×10⁹ cm⁻², the same value found for the etch-pit density on samples etched with both H₃PO₄ and molten KOH. Values agree well with TEM results.A free standing GaN template has been characterized for its structural and optical properties using X-ray diffraction, defect delineation etch followed by imaging with atomic force microscopy (AFM). The Ga-face and the N-face of the c-plane GaN exhibited a wide variation in terms of the defect density. The defect concentrations on Ga- and N-faces were about 5×10⁵ cm⁻² for the former and about 1×10⁷ cm⁻² for the latter, again in good agreement with TEM results mentioned above.High resolution X-ray rocking curves (omega scans) were measured. The [0 0 2] symmetric and [1 0 4] asymmetric peaks in 10 μm thick HVPE films had FWHM values between 5.8 and 7.9 arcmin, and 3.9 and 5.2 arcmin, respectively. The Samsung template investigated had wide diffraction peaks (20.6 and 24 arcmin for [0 0 2] and [1 0 4] diffractions, respectively) on the Ga-face, similar for the N-face, when a 2 mm slit size was used. When the slit size was reduced to 0.02 mm, the Ga- and N-face [0 0 2] peaks reduced to 69 and 160 arcsec. A bowing radius of 1.2 m was calculated to account for increased broadening with wider slits.In the HVPE layer studied, SIMS investigations indicate that both O and Si concentrations drop rapidly away from the surface into the sample — mainly due in part to the artifact of the technique and in part due to condensates on the surface of the sample, down to about 10¹⁷ cm⁻³ for Si and high 10¹⁶ cm⁻³ for O. The Ga-face profile in the Samsung template indicated levels below mid-10¹⁶ cm⁻³ for all three of the impurities. The picture is different for the N-side, however, as it was juxtaposed to the substrate during growth and was mechanically polished after laser separation. The impurity concentration on this face, depending on the species, is some 1–3 orders of magnitude higher than the case for the Ga-face.Transport properties as a function of the layer thickness, ranging from about 1 to 68 μm, while all the other parameters being the same, as they evolve from the sapphire/GaN interface and up were determined in epitaxial layers. A strong dependence on distance from the interface was observed with the averaged mobility figures increasing from 190 cm²/V s in the 5 μm film to 740 cm²/V s in the 68 μm film. The preliminary differential Hall measurements indicate that the mobility at the surface of the thick layer is about 1200 cm²/V s. Electron mobilities in free-standing template were 1425 cm²/V s at T=273 K and 7385 cm²/V s at T=48.2 K. By using the most recent unscreened acoustic deformation potential and allowing only the acceptor concentration to vary (2.4×10¹⁵ cm⁻³ for the best fit), one obtains an excellent fit to the measured mobility in the temperature range of 30–273 K by using an iterative BTE method. In addition, an excellent fit for the temperature-dependent electron concentration was also obtained utilizing the acceptor concentration determined from the fit to the Hall data, and the charge balance equation. This led to a donor concentration of 1.6×10¹⁶ cm⁻³, and activation energy of 26 meV, the latter being the highest reported in the literature for GaN.In the free-standing template, the Γ₅ and Γ₆ free excitons were identified from emission measurements by utilizing polarization geometries where the E field is perpendicular to the c-axis, favoring the Γ₅ exciton, and E field parallel to the c-axis (incident beam from the edge of the wafer) favoring the Γ₆ exciton. Focusing on the defect region of the PL spectrum, the N-face of the sample exhibited the usual yellow line. However, the Ga-face exhibited a broad band encompassing both yellow and green bands. The yellow luminescence in the free-standing template is weak and can be easily saturated. In contrast, the green luminescence is dominant and is attributed to the isolated defect involving gallium vacancy, whereas the yellow luminescence is related to the same defect bound to dislocation or surface-bound structural defect.Deep centers have been characterized by DLTS in HVPE-grown GaN epilayers of different thickness and dislocation densities, and templates. The main deep centers, such as A₁, B, and D, show higher concentrations in thinner samples, which suggests a correlation to the high dislocation densities. Based on the anti-correlation between A₁ and B, which is observed in thin HVPE-GaN layers, the defect B was tentatively attributed to N_Ga. Centers A₁ and E₁ found in thin HVPE-GaN are very similar to centers A₂ and E induced by electron-irradiation, indicating their point-defect nature. Centers A, C, and D are not affected by 1 MeV electron-irradiation, thus ruling out the possibility of these centers being identical to any EI-induced centers; however, their nature remains unknown. As the layer thickness decreases, an increase of deep centers, both in species and concentrations, was clearly observed, which is believed to be closely associated with the significant increase of threading dislocations as revealed by TEM. Based on a comparison with EI-induced centers and an observation of anti-correlation, A₁ is tentatively assigned to N_I, and B to N_Ga. The template exhibited a new trap B′, with parameters E_T=0.53 eV and σ_T=1.5×10⁻¹⁵ cm² on the Ga-face, in addition to the four traps commonly observed in various epitaxial GaN layers. For the N-face, an N vacancy-related trap E₁, with E_T=0.18 eV and σ_T=4×10⁻¹⁷ cm², was observed. On the other hand, the Ga-face sample contained trap C, with E_T=0.35 eV and σ_T=1.6×10⁻¹⁵ cm². This trap may be related to surface damage caused by the RIE process employed.Electron beam and optical depth-profiling of thick (5.5–68 μm) n-type HVPE-GaN samples have been carried out using electron beam-induced current (EBIC) and micro-PL to determine the minority carrier diffusion length, L, and minority carrier lifetime. The minority carrier diffusion length increased linearly from 0.25 μm, at a distance of about 5 μm from the GaN/sapphire interface, to 0.63 μm at the GaN surface for a 36 μm thick sample. The increase in L was accompanied by a corresponding increase in PL band-to-band radiative transition intensity as a function of distance from the GaN/sapphire interface. These observations in PL intensity and minority carrier diffusion length have been attributed to a reduced carrier mobility and lifetime at the interface and to scattering at threading dislocations.Positron annihilation experiments have been conducted in HVPE films with varying thicknesses from 1 to 68 μm. Mg-doped samples and bulk GaN platelets have also been investigated and the behavior of positron annihilation in Mg-doped samples established. Unlike the Mg-doped samples, the positron lifetime in the HVPE samples increased with decreasing lattice temperature. This was interpreted as acceptors in these n-type samples being due to Ga vacancies as opposed to relatively shallow acceptor impurities. The similarities in the behavior of these samples and those investigated previously where the III/V ratio was changed also lend support to the Ga vacancy argument. Previous investigations established that as the III/V is lowered by increasing the ammonia flow during the growth, the Ga vacancy concentration increased. Using Mg-doped samples as a standard, the vacancy concentration was determined to be about 10¹⁷ cm⁻³ near the surface for the layer with a thickness greater than 30 μm. Assuming that the growth parameters in the set of layers with varying thicknesses that were investigated are the same, the Ga vacancy concentration increases to mid-10¹⁹ cm⁻³ near the interface. Since the interfacial region is n-type and highly conductive, this region must also contain even larger concentrations of O and/or N vacancies which lead to n-type material. SIMS results already indicate mid-10¹⁹ cm⁻³ levels of O being present in this region. This has been attributed to O out-diffusion from sapphire as previously reported.FTIR, ODMR and EPR measurements have been performed in GaN layers and templates. In FTIR measurements, two absorption bands corresponding to binding energies of 30.9 (Si) and 33.9 meV were found. Splitting of the binding energies with magnetic field is consistent with an effective mass of 0.22m₀. Angular rotation studies were performed with the magnetic field oriented perpendicular and parallel to the c-axis to provide symmetry information. The ODMR on the 2.2 eV peak in a 5–10 μm thick GaN layer, the notorious yellow emission, showed signatures of shallow donor (effective mass like) and deep defect centers with g-values of 1.95 and 1.99, respectively. The 3.27 eV peak with resolved LO phonon replicas, which is the blue peak observed in many GaN films grown by a variety of methods, is attributed to transitions involving shallow acceptors with g2.1 and g2.0. ODMR on the 2.4 eV “green” PL band in the free-standing template also revealed evidence for shallow donors with a g-value of 1.95 and other deeper centers. The larger line width of the shallow donor signal from the template, relative to that found for the epitaxial layers, is indicative of a lower concentration of this center, which leads to an increased hyperfine interaction. EPR studies confirmed the notable difference between the epilayers and the template, particularly the larger line widths in the template due to the lower concentration of shallow donors. Specifically, the free-standing sample has about 6×10¹⁵ cm⁻³ uncompensated donors while the epilayers have a concentration about a factor of four higher.Calculations indicate that incorporation of Si has a negligible effect on the lattice constant, but O and Mg can lead to an observable expansion of the lattice. Since values of the GaN lattice constant have often been based on bulk crystals that are now known to contain large concentrations of oxygen, the “true” GaN lattice constant is actually smaller than what has been measured for such crystals. Boron is an unintentional impurity that can be introduced during MBE growth. There has been speculation about whether B might act as an acceptor in GaN; this would require it to be incorporated on the nitrogen site. Computations indicate that incorporating B on the N site is energetically unfavorable. Even if it did incorporate there, it would act as a deep, rather than a shallow acceptor. Formation energies of H in AlN and GaN have also been calculated. The behavior of H in AlN is very similar to GaN: H⁺ dominates in p-type, H⁻ in n-type. Surprisingly, H in InN behaves exclusively as a donor, i.e. it is not amphoteric as in GaN and AlN, but actually contributes to the n-type conductivity of the material.Scanning thermal microscopy (SThM) has been applied to measure the local thermal conductivity of epitaxial GaN as it is affected to a large extent by phonon scattering, and a closer to the true value of this parameter can be obtained by a local measurement in areas of lower defect concentration such as those found in the wing regions of lateral epitaxially grown GaN. The method relies on a thermo-resistive tip forming one quadrant of a Winston bridge. The bridge is balanced with the tip heated followed by bringing the tip in contact with the sample under test which cools down due to thermal dissipation. However, the feedback circuit attempts to keep the thermo-resistance and thus the tip temperature the same. The square of the feedback voltage necessary for this is proportional to the thermal conductivity. Accurate values can be obtained with calibration using known substrates such as GaSb, GaAs, InP, Si and Al metal. Using SThM, thermal conductivity, κ, values of 2.0–2.1 W/cm K in the wing regions of lateral epitaxially grown GaN, 1.70–1.75 W/cm K in HVPE grown GaN, and 3.0–3.3 W/cm K for free-standing AlN have been measured.     

Experimental comparison of different dead-time correction techniques in single-channel counting experiments

For single-channel counting, the dead-time correction method using transmission formulae was compared experimentally with the live-time technique. Agreement is within 4×10⁻⁴ for count rates up to 10⁴ s⁻¹ when the formulae for dead times in series are used and the dead-time value related to the analogue pulse width is adjusted for the BIPM modules. At higher count rates, a bias of 2×10⁻³ is observed. Two different live-time modules were compared and it was demonstrated that the live-time correction is also sensitive to the analogue pulse width and to the duration or rise time of the clock pulses. When these effects are taken into account, the two modules differ by only 5×10⁻⁴.     

Vapor growth of CdSe:Cr and CdS:Cr single crystals for mid-infrared lasers

Single crystals of CdSe:Cr and CdS:Cr with the doping level up to 10¹⁹ cm⁻³ were grown by a vapor phase contact-free technique. An efficient room-temperature pulsed and continuous wave (CW) lasing with the CdSe:Cr crystal was achieved. First a pulsed lasing with the CdS:Cr crystal was also demonstrated. The slope efficiency on the absorbed energy was as high as 46.5% for Cr²⁺:CdSe and 39% for Cr²⁺:CdS lasers. Using an intra-cavity prism, the Cr²⁺:CdSe laser wavelength was continuously tuned from 2.26 to 3.61 μm while the Cr²⁺:CdS laser from 2.2 to 3.3 μm. For the laser wavelength, the crystal passive loss coefficient was estimated to be smaller than 0.045 cm⁻¹ for CdSe:Cr crystals and 0.039 cm⁻¹ for CdS:Cr crystals. For the Cr²⁺:CdSe laser, the CW output power up to 1.07 W was achieved.     

Manifestation of Nd ions on the structure,Raman and IR spectra of (TeO<Subscript>2</Subscript>-MoO-Nd<Subscript>2</Subscript>O<Subscript>3</Subscript>) glasses

The structure of [80TeO₂ + (20–x)MoO + xNd₂O₃] glasses, with x = 0, 4, 6, 10 and 12 mol%, is studied in this work. Raman scattering in the spectral range (−2000 to 3500 cm⁻¹) and IR absorption spectra have been measured for crystalline TeO₂ and glasses, and their assignments were discussed and compared. Many vibrational modes were found active in both Raman and IR and their assignments for crystalline TeO₂ and for the glasses were discussed in relation to the tetragonal structure of crystalline α -TeO₂. Nd₂O₃ was found to completely eliminate diffuse scattering and enhance the Raman scattering intensity. Anti-stokes Raman bands in the range −1460 cm^{− 1} to −1975 cm^{− 1} were observed for both (30Li₂O + 70B₂O₃+ xNd₂O₃) glasses and [80TeO₂ + (20−x)MoO + xNd₂O₃] glasses and were attributed to some emission processes due to the doping of the glasses with Nd₂O₃.     

Alignment change of hexahexylthiotriphenylene in the helical columnar phase by infrared laser irradiation

Alignment change of discotic liquid crystal domains induced by infrared irradiation was investigated for the helical columnar phase of hexahexylthiotriphenylene. A uniform and anisotropic alignment change was observed when a linearly polarized infrared light was irradiated. It was found that the IR laser irradiation leads to a homogeneous planar alignment even in the helical columnar phase which is highly ordered mesophase. The in-plane order parameter of triphenylene ring was estimated to be 0.82 from the dichroic ratio obtained by polarized infrared absorption measurements. The results strongly imply that the infrared irradiation is a possible technique for device fabrication by use of the helical columnar phase which exhibits a high carrire mobility (~ 10^− 1 cm² V^− 1 s^− 1).     

Fluorescence and nonlinear optical properties of non-aggregating hexadeca-substituted phthalocyanine

Highly non-aggregating hexadeca-substituted phthalocyanine (Pc) complexes were prepared and their fluorescence and nonlinear optical properties were studied. Three visible fluorescence bands were observed when the Pc complexes were excited at 355 nm and found to be concentration dependent. They are attributed to the optical transitions S₂ → S₀ at 415 nm, T₂ → T₁ at 630 nm, and S₂ → S₁ at 755 nm. Nonlinear absorptive and refractive effects were measured with the help of Z-scan technique. Saturation absorption was observed at 632.8 nm where the nonlinear absorption coefficient is found to be very large (β = −2.8 × 10⁻² cm/W) and the refractive nonlinear coefficient γ = −9.5 × 10⁻¹¹ cm²/W. In the transparency domain at 532 nm, reverse absorption saturation is observed and β and γ are found to be 17.5 and 15.5 times smaller, respectively. Optical limiting performances are measured in the absorption and transparency domains. Purely refractive-based optical limiting at 632.8 nm is found to have a threshold of 0.16 kW/cm², lower than the reverse absorption saturation and refractive-based optical limiting of 0.90 kW/cm² at 532 nm.     

Luminescence properties of Ammonium Silicon Fluoride films prepared by vapour etching technique

Photoluminescence (PL) properties of Ammonium Silicon Fluoride samples prepared by vapour etching technique are investigated with respect to excitation energy, excitation intensity and temperature. Ageing effect at ambient conditions is also examined by Fourier Transform Infrared Spectroscopy. PL peak maximum blue shifts as the excitation intensity increases and saturates at 2.106 eV. Temperature-dependent variations in PL peak energies and intensities cannot be thoroughly elucidated via Quantum Confinement model alone and require consideration of recombination rates at Si–SiO_x interface. Temperature dependence of integrated PL intensity is treated by a three-component functional form.Infrared absorption bands at 1060 cm^− 1, 1113 cm^− 1 and 1230 cm^− 1 attain saturation with time. Agreement between the saturation time of SiO_x longitudinal optic mode at 1230 cm^− 1 and that deduced from PL measurements in literature is noted. It is shown that PL emissions are intrinsic in nature and have a significant excitonic contribution.     

A thermally actuated heat pump

A new kind of heat pump is described derived from the Vuilleumier process which has been known since 1918 but not applied until 1960 for small refrigerators down to 80 K. It consists of two oscillating displacers connected 90° out of phase and in parallel with thermal regenerators. It is pressurized by helium or hydrogen gas to 30–60 bars (3−6 × 10⁶ N m⁻²) and runs at 750 to 1500 rpm. The calculated heating power for a model of 1000 cm³ swept volume, taking heat in at 500°C and allowing for losses, will be 4 to 6 kW and a COP between 1.6 and 2.     

Oxidation of U(IV) in HNO<Subscript>3</Subscript> Solutions Containing Urea and Tc(VII)

The kinetics of U(IV) oxidation with nitric acid in aqueous solutions containing urea, catalyzed with technetium ions, were studied by sampling with subsequent colorimetric determination of the U(IV) concentration. At the constant ionic strength of the solution μ = 2 in the range of the initial concentrations of U(IV) from 2 × 10⁻³ to 1.28 × 10⁻², Tc(VII) from 5 × 10⁻⁵ to 1 × 10⁻³, urea from 0.01 to 0.1, and hydrogen ions from 0.4 to 1.96 M, the reaction rate is described by the equation -d[U(IV)]/dt = k ₁[U(IV)][Tc]^0.5[CO(NH₂)₂] × {[H⁺]² + β₁[H⁺] + β₂}⁻¹ - k ₂[U(IV)]₂[H⁺]^0.4[CO(NH₂)₂]^1.6{ [H⁺]² + β₁[H⁺]+ β₂}⁻², where k ₁ = 172 ± 10 mol^0.5 l^−0.5 min⁻¹ and k ₂ = (9.4±1.2)×10² mol l⁻¹ min⁻¹ at 25°C, β₁ and β₂ are the hydrolysis constants of U⁴⁺ ions. The activation energy is 63±2 kJ mol⁻¹. A reaction mechanism is proposed, in which in the slow stages the complex ion U(OH) ₂ ²⁺ ·CO(NH₂)₂ reacts with TcO²⁺ and TcO²⁺ · CO(NH₂)₂ ions.__________Translated from Radiokhimiya, Vol. 47, No. 1, 2005, pp. 61–66.Original Russian Text Copyright © 2005 by Dvoeglazov, Marchenko, Koltunov.     

The structural and electrical property of CuCr1 − xNixO2 delafossite compounds

A series of CuCr_1 − xNi_xO₂ (0 ≤ x ≤ 0.06) polycrystalline samples was prepared. The electrical conductivity was measured in the temperature range of 160–300 K. It was found that the electrical conductivity (σ) increases rapidly with the doping of Ni²⁺ ions. At room temperature, the σ is 0.047 S cm^− 1 for the sample with x = 0.06, which is two orders of magnitude larger than that of the CuCrO₂ sample (9.49E− 4 S cm^− 1). The Seebeck coefficients are positive for all samples, which indicate p-type conducting of the samples. The experimental results imply that it is possible to get higher electrical conductivity p-type transparent conducting oxides (TCO) from CuMO₂ by doping with divalent ions.     

Electrochemical determination of cadmium(II) at platinum electrode modified with kaolin by square wave voltammetry

In this work, determination of cadmium(II) using square wave voltammetry (SWV) was described. The method is based on accumulation of these metal ions on kaolin platinum electrode (K/Pt). The K/Pt performance was optimized with respect to the surface modification and operating conditions. The optimized conditions were obtained in pH of 5.0 and accumulation time of 25 min. Under the optimal conditions, the relationship between the peak current versus concentration was linear over the range of 9 × 10⁻⁸ to 8.3 × 10⁻⁶ mol L⁻¹. The detection limit (DL, 3σ) was 5.4 × 10⁻⁹ mol L⁻¹. The analytical methodology was successfully applied to monitor the Cd(II) content in natural water. Interferences were also evaluated.