Experimental evidence of Ga-vacancy induced room temperature ferromagnetic behavior in GaN films

We have grown Ga deficient GaN epitaxial films on (0001) sapphire substrate by plasma-assisted molecular beam epitaxy and report the experimental evidence of room temperature ferromagnetic behavior. The observed yellow emission peak in room temperature photoluminescence spectra and the peak positioning at 300 cm(-1) in Raman spectra confirms the existence of Ga vacancies. The x-ray photoelectron spectroscopic measurements further confirmed the formation of Ga vacancies; since the N/Ga is found to be >1. The ferromagnetism is believed to originate from the polarization of the unpaired 2p electrons of N surrounding the Ga vacancy. (C) 2011 American Institute of Physics. [doi:10.1063/1.3654151]

Sulphur potential measurements with a two phase sulphide oxide electrolyte

The open circuit potentials of the galvanic cell,Pt (or Au)¦(Ar + H2S + H2)primeparCaS + ZrO2(CaO)par (Ar + H2S+ H2)Prime£t (or Au) has been measured in the temperature range 1000 to 1660 K and PH2S:PH 2 ratios from 1.73×10–5 to 2.65×10–1. The solid electrolyte consists of a dispersion of calcium sulphide in a matrix of calcia-stabilized zirconia. The surface of the electrolyte is coated with a thin layer of calcium sulphide to prevent the formation of water vapour by reaction of hydrogen sulphide with calcium oxide or zirconia present in the electrolyte. The use of a lsquopoint electrodersquo with a catalytically active tip was necessary to obtain steady emfs. At low temperatures and high sulphur potentials the emfs agreed with the Nernst equation. Deviations were observed at high temperatures and low sulphur potentials, probably due to the onset of significant electronic conduction in the oxide matrix of the electrolyte. The values of oxygen and sulphur potentials at which the electronic conductivity is equal to ionic conductivity in the two-phase electrolyte have been evaluated from the emf response of the cell. The sulphide-oxide electrolyte is unsuitable for sulphur potential measurements in atmospheres with high oxygen potentials, where oxidation of calcium sulphide may be expected.

Carbon potential measurements on some actinide carbides

Uranium-Plutonium mixed carbide with a Pu/(U+Pu) ratio of 0.55 is to be used as the fuel in the Fast Breeder Test Reaotor - (PBTRj at Kalpakkam, India. carbur ization of the stainlese steel clad by this fuel is determined by its carbon potential. - i. Because the carbon potential of this fuel composition is not 1 available in the literature, it was meadured by the methanehydrogen gas equilibration technique. The sample was equilibrated with purified hydrogen and the equilibrium methane-tohydrogen ratio in the gas phase was measured with a flame ionization detector. The carbon potential of the ThC-ThCz as well as Mo-Mo2C system,whiah is an important binary in the aotinide-fission product-carbon systems, were also measured by this technique, in the temperature range 973 K to 1173 K. The data for ! the Mo-MozC system are in agreement with values reported in the literature. The results for the ThC-ThC2 system are different from estimated values with large unaertainty limits given in the literature. The data on (U,Pu) mixed carbide indicates possibility of stainlesss steel clad attack under isothermal equilibrium conditions.

Application of composition gradient solid electrolytes in sensors and thermodynamic measurements

New compos~tiong radient solid electrolytes are developed which have application in high temperature solid state galvanic sensors and provide a new tool for thermodynamic measurements. The electrolyte consists oi a solid solution between two ionic conductors with a common mobile ion and spatial variation in composition of otber coxup nents. Incorporation of the composite electrolyte in sensors permits the use oi dissimilar gas electrodes. It is demonsuated, both experimentall y and theoretically, that the composition gradient of the relativeiy immobile species does not give rise to a diffusion potential.The emi of a cell is determined by the activity of the mobile species at the two eiectrodes. The thermodynamic properties of solid solutions can be measured using the gradient solid electrolyte. The experimental stuay is based on model systems A?(COj)x(S04)l-x (A=Na,K),where S \.aria across the electrolyte. The functionally gradient solid electrolytes used for activity measurements consist of pure carbonate at one ena and the solid solution under stuav at the other. The identical vaiues of activity, obtained h m t hree different modes of operation of the ceil. indicate unit transport number for the ddi metal ion in the graciient electrolyte. Tlle activities in the solid solutions exhibit moderate positive deviations from Raoult 's law.

Phase relations in the system Sr–Ir–O and thermodynamic measurements on SrIrO3, Sr2IrO4 and Sr4IrO6 using solid-state cells with buffer electrodes

The standard Gibbs energies of formation of SrIrO3, Sr2IrO4 and Sr4IrO6 have been determined in the temperature range from 975 to 1400 K using solid-state cells with (Y2O3) ZrO2 as the electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode. For the design of appropriate working electrodes, phase relations in the ternary system Sr–Ir–O were investigated at 1350 K. The only stable oxide detected along the binary Ir–O was IrO2. Three ternary oxides, SrIrO3, Sr2IrO4 and Sr4IrO6, compositions of which fall on the join SrO–IrO2, were found to be stable. Each of the oxides coexisted with pure metal Ir. Therefore, three working electrodes were prepared consisting of mixtures of Ir+SrO+Sr4IrO6, Ir+Sr4IrO6+Sr2IrO4, and Ir+Sr2IrO4+SrIrO3. These mixtures unambiguously define unique oxygen chemical potentials under isothermal and isobaric conditions. Used for the measurements was a novel apparatus, in which a buffer electrode was introduced between reference and working electrodes to absorb the electrochemical flux of oxygen through the solid electrolyte. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. The standard Gibbs energies of formation of the compounds, obtained from the emf of the cells, can be represented by the following equations: View the MathML sourcem View the MathML source View the MathML source where Δf (ox)Go represents the standard Gibbs energy of formation of the ternary compound from its component binary oxides SrO and IrO2. Based on the thermodynamic information, chemical potential diagrams for the system Sr–Ir–O were developed.

An advanced design of the solid-state cell for accurate thermodynamic measurements on ternary oxides: system Sm–Pd–O

An advanced design of the solid-state cell incorporating a buffer electrode has been developed for high temperature thermodynamic measurements. The function of the buffer electrode, placed between reference and working electrodes, was to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. The application of the novel design and its advantages have been demonstrated by measuring the standard Gibbs energies of formation of ternary oxides of the system Sm–Pd–O. Yttria-stabilized zirconia was used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode. For the design of appropriate working electrodes, phase relations in the ternary system Sm–Pd–O were investigated at 1273 K. The two ternary oxides, Sm4PdO7 and Sm2Pd2O5, compositions of which fall on the Sm2O3–PdO join, were found to coexist with pure metal Pd. The thermodynamic properties of the ternary oxides were measured using three-phase electrodes in the temperature range 950–1425 K. During electrochemical measurements a third ternary oxide, Sm2PdO4, was found to be stable at low temperature. The standard Gibbs energies of formation (Δf(ox)Go) of the compounds from their component binary oxides Sm2O3 and PdO, can be represented by the equations: Sm4PdO7: Δf(ox)Go (J mol−1)=−34,220+0.84T(K) (±280); Sm2PdO4: Δf(ox)Go (J mol−1)=−33,350+2.49T(K) (±230); Sm2Pd2O5: Δf(ox)Go (J mol−1)=−59,955+1.80T(K) (±320). Based on the thermodynamic information, three-dimensional P–T–C and chemical potential diagrams for the system Sm–Pd–O were developed.

Solid-state cells with buffer electrodes for accurate thermodynamic measurements: system Nd-Ir-O

A new design for the solid-state cell incorporating a buffer electrode for high-temperature thermodynamic measurements is presented. The function of the buffer electrode, placed between the reference and working electrodes, is to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevents polarization of the measuring electrode and ensures accurate data. The application of this novel design and its advantages are demonstrated by measurement of the standard Gibbs energies of formation of Nd6Ir2O13 (low-temperature form) and Nd2Ir2O7 in the temperature range from 975 to 1450 K. Yttria-stabilized zirconia is used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode. For the design of appropriate working electrodes, phase relations in the ternary system NdIrO were investigated at 1350 K. The two ternary oxides, Nd6Ir2O13 and Nd2Ir2O7, compositions of which fall on the join Nd2O3IrO2, were found to coexist with pure metal Ir. Therefore, two working electrodes were prepared consisting of mixtures of Ir+Nd2O3+Nd6Ir2O13 and Ir+Nd6Ir2O13+ Nd2Ir2O7. These mixtures unambiguously define unique oxygen chemical potentials under isothermal and isobaric conditions. The standard Gibbs energies of formation (ΔG°f (ox)) of the compounds from their component binary oxides Nd2O3 and IrO2, obtained from the emf of the cells, can be represented by the equations:View the MathML source View the MathML source Based on the thermodynamic information, chemical potential diagrams for the system NdIrO are developed.

Structure of the Pyridine-Chloranil Complex in Solution: A Surprise from Depolarized Hyper-Rayleigh Scattering Measurements

In this article, we report the structure of a 1:1 charge transfer complex between pyridine (PYR) and chloranil (CHL) in solution (CHCl(3)) from the measurement of hyperpolarizability (beta(HRS)) and linear and circular depolarization ratios, D and D', respectively, by the hyper-Rayleigh scattering technique and state-of-the-art quantum chemical calculations. Using linearly (electric field vector along X) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D = I(X,X)(2 omega)/I(X,Z)(2 omega) and D' = I(X,C)(2 omega)/I(Z,C)(2 omega) in the laboratory fixed XYZ frame by detecting the second harmonic (SH) scattered light in a polarization resolved fashion. The stabilization energy and the optical gap calculated through the MP2/cc-pVDZ method using Gaussian09 were not significantly different to distinguish between the cofacial and T-shape structures. Only when the experimentally obtained beta(HRS) and the depolarization ratios, D and D', were matched with the theoretically computed values from single and double configuration interaction (SDCI) calculations performed using the ZINDO-SCRF technique, we concluded that the room temperature equilibrium structure of the complex is cofacial. This is in sharp contrast to an earlier theoretical prediction of the T-shape structure of the complex.

Aerodynamic Load Measurements at Hypersonic Speeds Using Internally Mounted Fiber-Optic Balance System

This paper describes the measurement of aerodynamic loads using fiber-optic strain gauge sensors and associated signal processors at hypersonic speeds in the 300mm hypersonic wind tunnel. at the Department of Aerospace Engineering, Indian Institute of Science. Fiber-optic sensors have been developed in USA since 1990, for variety of applications in experimental stress analysis, skin friction measurement in fluid flows, smart structures, smart materials, sensing of acoustic emission and more recently in the development of compact devices for measurement of displacement, stress/strain, pressure, temperature, acceleration etc. Our group at llSc has been playing a lead role in the use of these fiber - optic sensors for successful measurement of aerodynamic loads in wind tunnels and the first ever six-component wind tunnel strain gauge balance in the world based on fiber optic sensors was built at the Indian Institute of Science in the year 1999. We report here the results of our efforts in the development of an internal strain gauge balance for high-speed wind tunnel applications.

Temperature dependence of the energy gap and free carrier absorption in bulk InAs0.05Sb0.95 single crystals

Temperature dependence of the energy gap and free carrier absorption in a high-quality InAs0.05Sb0.95 single crystal was studied between 90 K and 430 K through the absorption spectra. At this alloy concentration, the room-temperature energy gap was measured to be 0.15 eV. Varshni- and the Bose–Einstein-type fit parameters were obtained from the measured temperature dependence of the energy gap, and the latter gave the zero-temperature gap to be 0.214 eV. It was found that although Weider’s empirical formula for the dependence of the energy gap on temperature and the alloy concentration agrees with the value of the gap at room temperature, it is inaccurate in describing its temperature dependence. From the free carrier absorption measurements, the phonon limited cross section of 7.35×10−16 cm2 at 15 μm was deduced at room temperature.

High room-temperature hole mobility in Ge0.7Si0.3/Ge/Ge0.7Si0.3 modulation-doped heterostructures

Modulation-doped two-dimensional hole gas structures consisting of a strained germanium channel on relaxed Ge0.7Si0.3 buffer layers were grown by molecular-beam epitaxy. Sample processing was optimized to substantially reduce the contribution from the parasitic conducting layers. Very high hall mobilities of 1700 cm2/V s for holes were observed at 295 K which are the highest reported to date for any kind of p-type silicon-based heterostructures. Hall measurements were carried out from 13 to 300 K to determine the temperature dependence of the mobility and carrier concentration. The carrier concentration at room temperature was 7.9×1011 cm−2 and decreased by only 26% at 13 K, indicating very little parallel conduction. The high-temperature mobility obeys a T−α behavior with α∼2, which can be attributed to intraband optical phonon scattering.

Temperature variation of the grüneisen parameter in magnesium oxide

The thermal expansion of magnesium oxide has been measured below room temperature from 140°K to 284.5°K, using an interferometric method. The accuracy of measurement is better than 3% in the temperature range studied. The agreement of these results with Durand's is quite good, but consistently higher over most of the range by 2 or 3%, for the most part within the estimated experimental error. The Grüneisen parameter remains constant at about 1.51 over the present experimental range; but an isolated measurement of Durand at 85°K suggests that at lower temperatures it rises quite sharply above this value. This possibility is therefore investigated theoretically. With a non-central force model to represent MgO, γ(−3) and γ(2) are calculated and it is found that γ(−3) > γ(2), again suggesting that the Grüneisen parameter increases with falling temperature. Of the two reported experimental values for the infra-red absorption frequency, correlation with the heat capacity strongly indicates a wavelength of 25.26μm rather than 17.3μm. Thermal expansion measurements at still lower temperatures must be carried out to confirm definitely the rise in the Grüneisen parameter.

Evidence for low temperature glassy behavior in La0.5Sr0.5CoO3

We report the observed low temperature spin glass like feature in the optimally doped La0.5Sr0.5CoO3 ferromagnetic system. The characteristic of glassy behavior has been identified by noting (i) the frequency-dependent shift of the low temperature hump position in the out of phase ac susceptibility component; (ii) evolution of freezing temperature with dc biasing field that adheres to de Almeida-Thouless relation; (iii) memory effect; and (iv) sluggish magnetic relaxation. The results of magnetic measurements demonstrate that neither the inter-cluster interaction nor the spin disorder at the interface between ferromagnetic clusters is responsible for the manifestation of such collective glassy behavior. Rather, it is believed to arise from a distinct cluster glass like phase that possibly coexists with the dominant ferromagnetic phase. (C) 2012 American Institute of Physics. [doi:10.1063/1.3684610]

Temperature gradient induced phase transitions and morphological changes in diamond thin film

The diamond films were deposited onto a wurtzite gallium nitride (GaN) thin film substrate using hot-filament chemical vapor deposition (HFCVD). During the film deposition a lateral temperature gradient was imposed across the substrate by inclining the substrate. As grown films predominantly showed the hexagonal phase, when no inclination was applied to the substrate. Tilting the substrate with respect to the heating filament by 6 degrees imposed a lateral temperature gradient across the substrate, which induced the formation of a cubic diamond phase. Diamond grains were predominantly oriented in the (100) direction. However, a further increase in the substrate tilt angle to 12 degrees, resulted in grains oriented in the (111) direction. The growth rate and hence the morphology of diamond grains varied along the inclined substrate. The present study focuses on the measurements of dominant phase formation and crystal orientation with varying substrate inclination using orientation-imaging microscopy (OIM). This technique enables direct examination of individual diamond grains and their crystallographic orientation. (C) 2012 Elsevier B.V. All rights reserved.

Phonon anomalies and structural transition in spin ice Dy2Ti2O7: a simultaneous pressure-dependent and temperature-dependent Raman study

We revisit the assignment of Raman phonons of rare-earth titanates by performing Raman measurements on single crystals of O18 isotope-rich spin ice Dy2Ti2O718 and nonmagnetic Lu2Ti2O718 pyrochlores and compare the results with their O16 counterparts. We show that the low-wavenumber Raman modes below 250 cm-1 are not due to oxygen vibrations. A mode near 200 cm-1, commonly assigned as F2g phonon, which shows highly anomalous temperature dependence, is now assigned to a disorder-induced Raman active mode involving Ti4+ vibrations. Moreover, we address here the origin of the new Raman mode, observed below TC similar to 110 K in Dy2Ti2O7, through a simultaneous pressure-dependent and temperature-dependent Raman study. Our study confirms the new mode to be a phonon mode. We find that dTC/dP = + 5.9 K/GPa. Temperature dependence of other phonons has also been studied at various pressures up to similar to 8 GPa. We find that pressure suppresses the anomalous temperature dependence. The role of the inherent vacant sites present in the pyrochlore structure in the anomalous temperature dependence is also discussed. Copyright (c) 2012 John Wiley & Sons, Ltd.