Electrical switching studies on Ge-Te-Tl chalcogenide glasses: Effect of thallium on the composition dependence of switching voltages

Bulk Ge(17)Te83_,JI glasses (05x.5_13), have been found to exhibit memory type electrical switching. The switching voltages (also known as threshold voltage V-th) of Ge17Te83-xTlx glasses are found to decrease with increasing thallium content. The rate of decrease of Vtry is greater at lower concentrations and \textbackslashid, falls at a slower rate for higher thallium concentrations (x 6). The addition of thallium to the Ge-Te network fragments the covalent network and introduces ionic nature to it; the reduction in network connectivity leads to the decrease in switching voltages with thallium content. The decrease in the glass transition temperatures of Ge17Te83-xTlx glasses with increasing thallium concentration supports the idea of decrease in network connectivity with TI addition. The more metallic nature of TI also contributes to the observed reduction in the switching voltages of Ge17Te83-xTlx glasses with TI content. Further, there is an interesting correlation seen between the threshold voltage V-th and the average bond energy, as a function of TI content. In addition, the switching voltages of Ge17Te83-xTlx glasses have been found to decrease with sample thickness almost linearly. The set-reset studies indicate that the Ge17Te83-xTl2 sample can be switched for more than 10 cycles, whereas other glasses could not be reset beyond two switching cycles. (C) 2010 Elsevier B.V. All rights reserved.

Phase relations and gibbs energies in the system Mn-Rh-O

Phase relations in the system Mn-Rh-O are established at 1273 K by equilibrating different compositions either in evacuated quartz ampules or in pure oxygen at a pressure of 1.01 x 10(5) Pa. The quenched samples are examined by optical microscopy, X-ray diffraction, and energy-dispersive X-ray analysis (EDAX). The alloys and intermetallics in the binary Mn-Rh system are found to be in equilibrium with MnO. There is only one ternary compound, MnRh2O4, with normal spinel structure in the system. The compound Mn3O4 has a tetragonal structure at 1273 K. A solid solution is formed between MnRh2O4 and Mn3O4. The solid solution has the cubic structure over a large range of composition and coexists with metallic rhodium. The partial pressure of oxygen corresponding to this two-phase equilibrium is measured as a function of the composition of the spinel solid solution and temperature. A new solid-state cell, with three separate electrode compartments, is designed to measure accurately the chemical potential of oxygen in the two-phase mixture, Rh + Mn3-2xRh2xO4, which has 1 degree of freedom at constant temperature. From the electromotive force (emf), thermodynamic mixing properties of the Mn3O4-MnRh2O4 solid solution and Gibbs energy of formation of MnRh2O4 are deduced. The activities exhibit negative deviations from Raoult's law for most of the composition range, except near Mn3O4, where a two-phase region exists. In the cubic phase, the entropy of mixing of the two Rh3+ and Mn3+ ions on the octahedral site of the spinel is ideal, and the enthalpy of mixing is positive and symmetric with respect to composition. For the formation of the spinel (sp) from component oxides with rock salt (rs) and orthorhombic (orth) structures according to the reaction, MnO (rs) + Rh2O3 (orth) --> MnRh2O4 (sp), DELTAG-degrees = -49,680 + 1.56T (+/-500) J mol-1. The oxygen potentials corresponding to MnO + Mn3O4 and Rh + Rh2O3 equilibria are also obtained from potentiometric measurements on galvanic cells incorporating yttria-stabilized zirconia as the solid electrolyte. From these results, an oxygen potential diagram for the ternary system is developed.

Self-assembled molecular squares containing metal-based donor: synthesis and application in the sensing of nitro-aromatics

Self-assemblies between a linear Pt-based donor and ferrocene- chelated metallic acceptors produced novel heterometallic squares 4 and 5, which show fluorescence quenching upon the addition of nitro-aromatics.

Investigations of the reduction behavior of Iron-impregnated alumina gels (Fe/AlOOH) and the formation of Fe0-Al2O3 metal-ceramic composites

Fe/AlOOH gels calcined and reduced at different temperatures have been investigated by a combined use of Mossbauer spectroscopy, x-ray diffraction, and electron microscopy in order to obtain information on the nature of the iron species formed as well as the various reduction processes. Calcination at or below 1070 K mainly gives reducible Fe3+ while calcination at higher temperatures gives substitutional Fe3+ in the form of Al2-xFexO3. The Fe3+ species in the calcined samples are, by and large, present in the form of small superparamagnetic particles. Crystallization of Al2O3 from the gels is catalyzed by Fe2O3 as well as FeAl2O4. Fe (20 wt. %)/AlOOH gels calcined at or below 870 K give FeAl2O4 when reduced in hydrogen at 1070 K or lower and a ferromagnetic Fe0-Al2O3 composite (with the metallic Fe particles >100 angstrom) when reduced at 1270 K. Samples calcined at 1220 K or higher give the Fe0-Al2O3 composite when reduced in the 870-12,70 K range, but a substantial proportion of Fe3+ remains unreduced in the form of Al2-xFexO3, showing thereby the extraordinary stability of substitutional Fe3+ to reduction even at high temperatures. Besides the ferromagnetic Fe0-Al2O3 composite, high-temperature reduction of Al2-xFexO3 yields a small proportion of superparamagnetic Fe0-Al2O3 wherein small metallic particles (<100 angstrom) are embedded in the ceramic matrix. In order to preferentially obtain the Fe0-Al2O3 composite on reduction, Fe/AlOOH gels should be calcined at low temperatures (less-than-or-equal-to 1100 K); high-temperature calcination results in Al2-xFexO3. Several modes of formation of FeAl2O4 are found possible during reduction of the gels, but a novel one is that involving the reaction, 2Fe3+ + Fe0 --> 3Fe2+.

Multifractal analysis, a method to investigate the morphology of materials

Using the multifractal formalism, we discuss the results obtained to characterized the morphology of polymer alloys and granular discontinuous metallic thin films. In the first case we have found a correlation between the multifractality and the mechanical properties of the alloys. In the second case, we have found that it is possible to measure the differences between the morphology of thin films induced by a growth process on a subtrate and that of percolation clusters of the classical theory of percolation.

Giant magnetoresistance phenomenon in manganates

The discovery of giant magnetoresistance (GMR) in rare earth manganates of the general formula Ln(1-x)A(x)MnO(3) (Ln = rare earth, A = divalent cation) has aroused much interest not only because of its technological implications, but also due to the fascinating features and mechanism of the phenomemon in these oxides. GMR is observed in these manganates when they become ferromagnetic and transform from an insulating state to a metallic state close to the Curie temperature. The essential features of magnetoresistance in the manganates can be understood on the basis of the double-exchange mechanism, but this is too simplistic to account for all the observed data. The most curious property of the manganates relates to the high resistivity exhibited in the so-called metallic state. Charge ordering competes with the double-exchange interaction responsible for ferromagnetism and GMR in these materials. The charge-ordered (charge-crystal) insulating state in the rare earth manganates can be melted into a metallic and ferromagnetic charge-liquid state by applying a magnetic field, thus providing a unique case of charge and spin separation in solids. The observation of GMR in Tl2Mn2O7 shows that there can be causes other than double-exchange for the phenomenon.

High pressure electrical measurements on Ge-Te-Se glasses

Electrical resistivity measurements have been carried out on bulk Ge-Te-Se glasses in a Bridgman anvil System. The resistivity of the Ge-Te-Se samples is found to decrease continuously with increasing pressure, with the metallization occurring around 8 GPa. Ge20TexSe80-x glasses (10 less than or equal to x less than or equal to 50) with the mean co-ordination number Z(av) = 2.4 exhibit a plateau in resistivity up to about 4 GPa pressure, followed by a continuous decrease to metallic values. On the other hand, Ge10TexSe90-x glasses (10 less than or equal to x less than or equal to 40) having Z(av) = 2.2, exhibit a smaller plateau (only up to 1 GPa), followed by a decrease in resistivity with pressure. This subtle difference in the high pressure resistivity of Ge-Te-Se glasses with Z(av) < 2.4 and Z(av) greater than or equal to 2.4 can be associated with the changes in the local structure of the chalcogenide glasses with composition.

Metal-insulator transition and giant magnetoresistance in La1-xMnO3-delta thin films and superlattices

The first fabrication of self-doped La1-xMnO3-delta films which are unique among the other La(1-x)M(x)MnO(3) (M = Ca, Ba and Pb) thin films showing giant magnetoresistance is reported. Ag-doped La0.7MnO3-delta films were grown on LaAlO3[100] substrates. These films show ferromagnetic and metal-insulator transition at 220 K and exhibit giant magnetoresistance (GMR) with Delta R/R(o) = 85% and Delta R/R(H) > 550%. Without silver addition these self-doped films are non-magnetic, Enhancement in GMR up to 8% has been observed in superlattices having alternate magnetic and non-magnetic La1-xMnO3-delta layers.

Quantum corrections to the conductivity in a perovskite oxide: A low-temperature study of LaNi1-xCoxO3 (0?x?0.75)

In this paper we propose to study the evolution of the quantum corrections to the conductivity in an oxide system as we approach the metal-insulator (M-I) transition from the metallic side. We report here the measurement of the low-temperature (0.1 Kmetallic for x?0.65. For all x, at low temperatures, the conductivity (?) rises with temperature (T). Below 2 K, ? follows a power-law behavior, ?(T)=?(0)+?Tm. For samples in the metallic regime, away from the metal-insulator transition (x?0.4), m?0.3�0.4. As the transition is approached [i.e., ?(0)?0], m increases rapidly; and at the transition [?(0)=0, xc?0.65], m?1. On the insulating side (x>0.65), m takes on large values and ?(0)=0. We explain the temperature dependence of ?(T), for T<2 K, on the metallic side (x?0.4), as arising predominantly from electron-electron interactions, taking into account the diffusion-channel contribution (which gives m=0.5) as well as the Cooper-channel contribution. In this regime, the correction to conductivity, ??(T), is a small fraction of ?(T). However, as the M-I transition is approached (x?xc), ??(T) starts to dominate ?(T) and the above theories fail to explain the observed ?(T).

Synthesis, structure and IR absorption studies of LnBaCuCoO(5) (Ln equal earth) oxides

A series of oxides LnBaCuCoO(5) (Ln = Pr, Nd, Sm, Dy, Gd, Ho and Er) have been synthesized by ceramic method. The oxides crystallize in a tetragonal structure, isostructural to YBaCuCoO5. All the oxides in the series are semiconducting. IR spectra of these oxides show distinct absorption bands at 630 cm(-1), 550 cm(-1) and 330 cm(-1) which are assigned to E, A(2) and A(1) modes respectively. Doping of holes in these oxides, by calcium substitution in Er1-xCaxBaCuCoO5-x (up to x similar or equal to 0.3) was done but, these oxides did not show metallic behaviour.

Microstructural stability and nanoindentation of an electrodeposited nanocrystalline Ni-1.5wt.%P alloy

Microstructural stability of nanocrystalline Ni-1.5wt.%P alloy with an initial grain size of 3 nm processed by pulsed electrodeposition was studied using differential scanning calorimetry (DSC) and annealing. Microstructural characterization suggests that the observed exothermic peak during heating in DSC is related to both concurrent grain growth and Ni3P formation. Nanoindentation on samples with grain sizes from 3 to 50 nm revealed a breakdown in Hall-Petch strengthening in nano Ni-P alloy at grain sizes <= 10 nm, consistent with some previous observations. It is concluded that there is a grain boundary weakening regime for grain sizes < 10 nm, based on analysis which show that the data cannot be rationalized in terms of microstrain relaxation, variation in elastic modulus, texture evolution and duplex structure formation.

Superconducting properties of Tl1?yPbyCaSr2Cu2O7: Role of Pb and oxygen stoichiometry

In the Tl1-yPbyCaSr2Cu2O7 system, monophasic superconducting compositions are formed in the range 0.25 < y < 0.60 and the minimum Pb content required to stabilize the tetragonal 1122 phase is about 25%. Maximum Tc is found when y = 0.5, at which composition the hole concentration is optimal. Metallic compositions of Tl1?yPbyCaSr2Cu2O7 (y = 0.25) and Tl0.75Pb0.25Y1?xCaxSr2Cu2O7 (0.80 less-than-or-equals, slant X less-than-or-equals, slant 1.0) become superconducting on decreasing the oxygen content by vacuum annealing.

Oriented films of LaNiO3 and other members of the Lan+1NinO3n+1 series, LaCuO3−δ and Pb(Zr0.52Ti0.48)O3, obtained by nebulized spray pyrolysis

The technique of nebulized spray pyrolysis has been explored to find out whether oriented films of certain important oxides can be produced on single-crystal substrates by this relatively gentle method. Starting with acetylacetonate precursors, oriented films of metallic LaNiO3 containing nearly spherical grains (30 nm) have been obtained. Films of near-stoichiometric La4Ni3O10 and La3Ni2O7 showing metallic conductivity have been obtained by this method. This is indeed gratifying since it is difficult to prepare monophasic and stoichiometric bulk samples of these materials. Films of La2NiO4 show the expected semiconducting behavior. In the La-Cu-O system, starting with acetylacetonates, we have obtained films mainly comprising semiconducting La2Cu2O5, which is generally difficult to prepare in bulk form. More interestingly, nebulized spray pyrolysis gives excellent stoichiometric films of Pb(Zr0.52Ti0.48)O-3 consisting of nearly spherical grains (30 nm) which show ferroelectric behavior. The present investigation demonstrates that nebulized spray pyrolysis provides a useful and desirable route to deposite oriented films of complex oxide materials on single-crystal substrates.

LaNiO3: a promising material for contact with YBa2 Cu3O7-x thin films

Epitaxial LaNiO3 metallic oxide thin films have been grown on c-axis oriented YBa2Cu3O7-delta thin films on LaAlO3 substrates by pulsed laser deposition technique and the interface formed between the two films has been examined by measuring the contact conductance of the same. The specific contact conductance of the interface measured using a modified four probe method was found to be 1.4 to 6 x 10(4) ohm(-1) cm(-2) at 77 K, There are indications that contact conductance can be brought closer to that obtained for noble metal-YBCO interface.

Charge-ordering in manganates

Ordering of Mn3+ and Mn4+ ions occurs in the rare earth manganates of the general composition Ln(1-x)A(x)MnO(3) (Ln rare earth, A = Ca, Sr). Such charge-ordering is associated with antiferromagnetic and insulating properties. This phenomenon is to be contrasted with the ferromagnetic metallic behavior that occurs when double-exchange between the Mn3+ and Mn4+ ions predominates. Two distinct types of charge-ordering can be delineated. In one, a ferromagnetic metallic (FMM) state transforms to the charge-ordered (CO) state on cooling. In the other scenario, the CO state is found in the paramagnetic ground stale and there is no ferromagnetism down to the lowest temperatures. Magnetic fields transform the CO state to the FMM state, when the average radius of the A-site cations is sufficiently large ([r(A)] > 1.17 Angstrom). Chemical melting of the CO state by Cr3+ substitution in the Mn site is also found only when [r(A)] greater than or similar to 1.17 Angstrom. The effect of the size of the A-cations on the Mn-O-Mn angle is not enough to explain the observed variations of the charge-ordering temperature as well as the ferromagnetic Curie temperature T-c. An explanation based on a competition between the Mn and A-cation orbitals for sigma-bonding with the oxygen rho(sigma) orbitals is considered to account for the large changes in T-c and hence the true bandwidth, with [r(A]). Effects of radiation, electric field, and other factors on the CO state are discussed along with charge-ordering in other manganate systems. Complex phase transitions, accompanied by changes in electronic and magnetic properties, occur in manganates with critical values of(rA) Or bandwidth. Charge-ordering is found in layered manganates, BixCa1-xMnO3 and CaMnO3-delta.