Synthesis and electrical characterisation of the perovskite niobate-titanates,Sr1−x/2Ti1−xNbxO3−δ

The synthesis and electrical characterisation over a range of oxygen partial pressures (10⁻²⁰ to 1 atm) are reported for the cubic perovskite niobate-titanates Sr_1−x/2Ti_1−xNb_xO_3−δ, which are proposed as potential anode materials for solid oxide fuel cells. Single phase samples were observed for 0≤x≤0.4, and phase purity was retained on annealing at both high and low oxygen partial pressures. Good electrical conductivity was observed on reduction in low oxygen partial pressures, with a maximum for the sample with 25% Nb (x=0.25), σ=5.6 Scm⁻¹ at 930°C (P (O₂)=10⁻¹⁸ atm). For dense samples the higher the Nb content the more resistant the reduced sample was to reoxidation as the oxygen partial pressure was increased. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Photocrystallization in amorphous thin films of Se70Te30−xCdx

Summary The present paper reports a study of photocrystallization in a-Se₇₀Te_30−xCd_x films (0≤x≤4). The photocrystallization is achieved by shining white light at room temperature for different exposure times. The results indicate that the photocrystallization is suppressed on addition of Cd in binary Se₇₀Te₃₀ system. This is explained in terms of the structure of Se-Te-Cd system. Work supported by University Grants Commission. The authors of this paper have agreed to not receive the proofs for correction.     

Electrical switching studies on As<Subscript>40</Subscript>Te<Subscript>60-x</Subscript>Se<Subscript>x</Subscript> and As<Subscript>35</Subscript>Te<Subscript>65-x</Subscript>Se<Subscript>x</Subscript> glasses

The I–V characteristics of bulk As₄₀Te_60-xSe_x and As₃₅Te_65-xSe_x glasses have been studied with a current sweep of 0–18 mA-0, over a wide range of compositions (4≤x≤22). All the glasses studied showed a threshold electrical switching behaviour. The number of switching cycles withstood by the samples has been found to depend on the ON-state current. It is seen that the switching voltages increase with increase in selenium content. Further, the switching voltages are found to be almost independent of the thickness of the sample (d), in the range 0.18–0.3 mm. Also, the switching voltages and the number of switching cycles withstood by the samples are found to decrease with temperature. Received: 6 November 2002 / Accepted: 8 November 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. Fax: +91-80/360-0135, E-mail: sasokan@isu.iisc.ernet.in     

Synthesis and electrical characterisation of different doped magnesium titanates

The synthesis and characterization are reported for the cubic spinel titanate Mg_(2−x)Ni_xTiO₄ (x≤0.25) and Mg_(2−x)Mn_xTiO₄ (x≤1). Single phase samples were observed for Mg_(2−x)Ni_xTiO₄ and with x≤0.4 for Mg_(2−x)Mn_xTiO₄. AC measurements were carried out on four different compositions (x=0.01, 0.03, 0.04 and 0.15) in the Mg_(2−x)Ni_xTiO₄ series and for Mg_1.9Mn_0.1TiO₄. For all these compounds, increasing conductivity with temperature and Arrhenius conductivity dependence are observed, the activation energy is around 0.28 eV for the Ni compounds and is 0.184 eV for Mg_1.9Mn_0.1TiO₄. The DC conductivity was recorded over a range of oxygen partial pressures (10⁻¹⁹ to 1 atm) at 930 °C. The Mg_(2−x)Ni_xTiO₄ compounds show a n-type behaviour whereas the Mg_(2−x)Mn_xTiO₄ show a p-type behaviour at high p(O₂) and n-type at low p(O₂). The stability under reduced conditions was checked and discussed for the different synthesized compounds. Paper presented at the 5th Euroconference onSolid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Phase equilibria in the La-Me-Co-O (Me=Ca, Sr, Ba) systems

The phase equilibria of the La-Me-Co-O systems (Me = Ca, Sr and Ba) were studied in air at 1100 °C. Two types of solid solution of general composition La_1−xMe_xCoO_3−δ and (La_1−y Me_y)₂CoO₄ were found to exist in the systems. The limiting composition of La_1−xMe_xCoO_3−δ lies at x=0.8 for Me = Sr, Ba and between 0.3–0.5 for Me = Ca. It is shown that the rhombohedral distortion of the perovskite type La_1−xMe_xCoO_3−y decreases while x increases. La_1−xMe_xCoO_3−δ (Me = Sr, Ba) shows an ideal cubic structure at x=0.5. The stability range of (La_1−yMe_y)₂CoO₄ was found to be 0.25≤y≤0.35 for Me = Ca, 0.3≤y≤0.55 for Me = Sr and 0.3≤y≤0.375 for Me = Ba. All phases have tetragonal K₂NiF₄-type crystal structure. Based on the XRD and neutron diffraction patterns of quenched samples, the phase diagrams (Gibbs triangles) are constructed for all systems. The phase equilibrium at low oxygen pressure is shown for the example of the La-Sr-Co-O system. The decomposition mechanism of La_1−xSr_xCoO_3−δ at 1100 °C for the samples with 0.5<x<0.8 within the oxygen pressure range −0.678>log(Po₂)>−2.25 can be written as follows: La_1−x′ Sr_x′CoO_3−δ′=n La_1−x″Sr_x″CoO_3−δ″+m SrCoO_2.5+q/2 O₂ where x′>x″. The decomposition mechanism of La_1−xSr_xCoO_3−δ for the samples with x < 0.5 within the oxygen pressure range −2.25>log(Po₂)>−3.55 changes and can be written as follows: La_1−xSr_xCoO_3−δ′=r La_1−x′Sr_x′CoO_3−δ″+w (La_1−y′Sr_y′)₂CoO₄+v CoO+f/2 O₂. The results are shown in “logPo₂-composition” diagrams. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Synthesis and properties of In2(Se1-xTex)3 thin films: a new semiconductor compound

In₂(Se_1-xTe_x)₃ polycrystalline films were prepared by a dual-source thermal evaporation technique. The depositions onto glass and SnO₂-coated glass substrates were carried out in a vacuum chamber and followed by an annealing in neutral ambient (Ar or N₂). The structural, morphological and compositional studies of the films were made by X-ray diffraction, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, Raman scattering and optical transmission. Optimum conditions are investigated for the formation of the ternary compound In₂(Se_1-xTe_x)₃ in order to tune the band gap by changing the Te concentration. The film properties as a function of Te amount are discussed. It is shown that single-phase, textured and homogeneous layers of In₂(Se_1-xTe_x)₃ can be grown with x≤0.2 at optimal deposition and heat treatment conditions. For x≅0.17 these films showed an energy band gap of about 1.45 eV and an electrical conductivity at room temperature six orders of magnitude higher than that of the binary γ-In₂Se₃ thin films. Received: 9 July 1999 / Accepted: 25 November 1999 / Published online: 13 July 2000     

Investigation of impurity effects in La2?xSrxCu1?yMyO4 (M=Ga,Zn) by electronic specific heat

The electronic specific heat C_el was studied at T≤10K on Ga- and Zn-doped La_2−xSr_xCuO₄ (0.16≤x≤0.22). In pure La_2−xSr_xCuO₄ (0.16≤x≤0.22), the C_el at T<T_c contains only a T² component but no T-linear one, which is peculiar to a clean d-wave superconductor. Partial substitution of Ga or Zn for Cu changes the T²-term of C_el into a quite different one described by the sum of a T-linear and a nearly T³ term. The coefficient of the T-linear term, γ, markedly increases with Zn-or Ga-content. The λ/λ_N vs. T_c/T_co relation for Zn-doped samples with x≥0.2 is in good agreement with the theoretical curve for resonant impurity scattering in a d-wave superconductor, while those for Ga-doped samples and for Zn-doped samples with x<0.2 deviate slightly from the theoretical curve. Such a deviation will be discussed in relation to the change in the magnetic properties of the present system caused by impurity-doping.     

Anomalous electrical behavior in ferromagnetic La1−xBaxCoO3−δ materials (0<x≤0.50)

We prepared in this work La_1−xBa_xCoO_3−δ (0<x≤0.50) compounds using the nitrate decomposition method, and focus in the study of the transport properties of the ferromagnetic compounds (x>0.15, T_c≈200 K) in the temperature range 77 K≤T≤300 K. We find that while for x<0.20 these materials show semiconducting behavior, their electrical conduction being dominated by small-polaron holes, for x>0.20 they show metallic behavior for T>100 K, with a transition to semiconducting behavior being observed for T ≤ 100 K. For x=0.20, small changes in the oxygen stoichiometry of the samples - due to slight variations in the thermal treatments - greatly affect the transport properties of the materials that can show either two metal-insulator transitions as the temperature increases or a semiconducting behavior. Very interestingly all these ferromagnetic samples are very sensitive to the polarity of the applied electrical current, and display peculiar “diodic” behaviors. All these observations are explained on the basis of an inhomogeneous electronic structure in the Ba-doped cobalt perovskites. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

A study of the microstructure of La1 − x Ca x MnO3 (x = 0.5, 0.8) solid solutions

HREM and XPD methods are used to study the microstructure of La_{1 − x} Ca _x MnO₃ perovskite-like oxides synthesized by pyrolysis of polymer-salt compositions. The XPD data show that the samples studied are single-phase solid solutions. Morphological transitions are observed in series of samples depending on the substitution parameter x. At 0 ≤ x ≤ 0.4 the samples can be characterized by rhombic symmetry (space group Pnmb); at 0.5 ≤ x ≤ 0.8 the symmetry increases to the tetragonal space group I4/mmm; at 0.9 ≤ x ≤ 1 the symmetry lowers to the monoclinic space group P1121. Heating of samples with x = 0.5 and 0.8 up to 1200°C in air does not lead to noticeable changes in the sample structure, which indicates their high thermal stability. When the La_0.2Ca_0.8MnO₃ sample is heated to 1100°C in vacuum nanocrystalline states with particle disintegration into microphases of different structures form because of a partial decomposition of the solid solution. As a result, a system of Mn₃O₄ nanoparticles appears, which is coherently bound with the perovskite phase of a defective structure.     

A study of iso- and alio-valent cation doped Ag2SO4 solid electrolyte

2 SO₄. The solid solubility limits up to x≤3 mole% for monovalent, x≤5.27 mole% for divalent and x≤3.63 mole% for trivalent cation doped Ag₂SO₄ are set with XRD, SEM, IR and DSC techniques. A predominant dependence of conductivity on the ionic size of iso- and alio-valent cations is observed. In particular, the conductivity enhances in both α and β phases, despite having a lower ionic-size dopant cation (relative to that of Ag⁺) in the transition element cation doped Ag₂SO₄. Ca²⁺, Ba²⁺, Y³⁺ and Dy³⁺ doped samples show depature from the regular behaviour in the β-phase. The conductivity behaviour is discussed considering ionic size, valence and electronic structure of the guest cations. Received: 3 February 1997/Accepted: 27 May 1997     

Structural and optical properties of Ge20SbxSe80-x films

20 Sb_xSe_80-x (where 10≤x≤40 at.%) thin films. The optical absorption results indicate that the absorption mechanism is due to non-direct transition. The optical gap of the as-deposited films was found to decrease monotonically with increasing antimony content, a result which was interpreted on the basis of the chemical-bond approach proposed by Bicerno and Ovshinsky. Annealing of the Ge₂₀Sb₄₀Se₄₀ films at temperatures higher than 450 K was found to decrease the optical gap and increase the refractive index of the investigated film. Increasing the amount of crystalline GeSe₂ and Sb₂Se₃ phases while increasing the annealing temperature could be responsible for the continuous decrease of the optical gap of the Ge₂₀Sb₄₀Se₄₀ film. Received: 4 November 1997/Accepted: 16 December 1997     

The study of lithium fast ion conductors of Li3xLa0.67−xScyTi1−2yNbyO3 system

Perovskite-type lithium fast ion conductors of Li_3xLa_0.67−xSc_yTi_1−2yNb_yO₃ system were prepared by solid state reaction. X-Ray powder diffraction shows that perovskite solid solution form in the ranges of x=0.10, y≤0.10. AC impedance measurements indicate that the bulk conductivities and the total conductivities are of the order of 10⁻⁴ S·cm⁻¹ and 10⁻⁵ S·cm⁻¹ at 25 °C respectively. The compositions have low bulk activation energies of about 17 kJ/mol in the temperature ranges of 298 – 523 K and total activation energies of about 37 kJ/mol in the temperature ranges of 298 – 523 K.     

Investigation of the influence of solid ionic conductor admixtures on the performance of gas sensors based on tin oxide

Tin oxide is a well-known and widely used gas sensitive material for detection of toxic and hazardous gas components in air. Different admixtures such as catalysts, aliovalent ions and solid ionic conductors were added to improve the sensitivity, selectivity and stability of these sensors. For material preparation a sol-gel route is usually used and catalysts are added before sintering to improve the sensitivity and to favour the sensors to specific gas components. In this work we investigated the influence of added solid ionic conductors on the gas sensitivity of tin oxide based ceramic admixtures dependent on the relative parts of the oxidic sodium ionic conductor, the ionic conductivity and the grain size in relation to the tin oxide grains. Almost ideal model substances for these studies are solid electrolytes with the NASICON (Na_1+xZr₂Si_xP_3−xO₁₂) structure. They can be prepared in the sol-gel route and in a solid state reaction as well resulting in different powder grain sizes. The sodium ionic conductivity of the solid electrolytes in the composition range 0≤×≤3 varies by several orders of magnitude. Both materials, the NASICON and the tin oxide, were characterized with respect to morphology and structure by BET and XRD measurements. Powders of tin oxide were homogeneously mixed with different NASICON powders, pressed as discs, sintered, and contacted with gold electrodes for measurements of the conductivity in air at various temperatures (200°C≤T≤400 °C). For preparation of sensor layers the powder mixtures were transferred to a paste, screen printed on an alumina substrate with interdigital gold electrodes and sintered for gas sensitivity measurements. A dramatic sensitivity enhancement of the composite to alcohol and significant sensitivity reduction to other gases like CO, H₂, NH₃, CH₄, C₃H₈ was found. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Structural assessment of the electrochemical performance of LixCoO2 membrane electrodes by X-ray diffraction and absorption refinements

Li_xCoO₂ samples with different nominal load x were prepared submitting HT-LiCoO₂ membrane electrodes to electrochemical polarisation, followed by aging in open circuit conditions. Care was taken to obtain samples for both positive and negative overcharge beyond the canonical regime (0.6≤x≤1) of the Li_xCoO₂ electrode. For 11 samples in the range 0.37≤x≤1.43, Rietveld refinements of X-ray diffraction data were performed, with Li at 3a, Co at 3b and O at 6c in the space group R-3m as starting model. In the range 0.37≤x≤1, results show a continuous variation of theac unit cell and structural parameters such as the lithium site occupancy and the Li-O and Co-O interatomic distances. For samples in the range 1≤x≤1.43, Li₂CO₃ was detected as an impurity which might be due to decomposition of the electrolyte, and, if the negative overcharge was high enough, an abnormally high electron density at the 3a site indicates some Li→Co substitution. Results from Co-K edge X-ray absorption spectroscopy for the samples with x=0.37, 0.89, 1 and 1.43 show a clear shift of the absorption maximum with the oxidation state of Co and support the conclusions from Rietveld refinement. GNXAS refinement of EXAFS spectra for the samples with x=0.37 and 1 suggest that cation disordering may occur also for deep lithium deintercalation (positive overcharge), a fact which was not detectable from diffraction data.     

Co-precipitation synthesis and performance of multi-doped LiCrxNixMn2-2xO4-zFz cathode materials for lithium ion batteries

Multiple ion-doped lithium manganese oxides LiCr_xNi_xMn_2-2xO_4-zF_z (0 < x ≤ 0.25, z =  0.05, 0.1) with a spinel structure and space group Fd m were prepared by using the co-precipitation procedure carried out in water–alcohol solvent using adipic acid as the chelating agent. The electrochemical measurements indicated that the charge/discharge capacities of the samples prepared at 600 °C are higher than that of the treatment at 800 °C or microwave heating. The capacitance-voltage (CV) curves of LiCr_xNi_xMn_2-2xO_4-zF_z (0 < x ≤ 0.25, z = 0.05, 0.1) showed that when x ≤ 0.1, the samples had two reduction–oxidation peaks at 4.0 to 4.2-V region, whereas when x > 0.1, the samples had only one reduction–oxidation peak at 4.0- to 4.2-V region in CV measurements and could offer more stable voltage plateau in a 4-V region and also had stable electrical conductivity after 20 cycles. Another reduction–oxidation peak appeared in 4.6-4.8-V region (Ni²⁺–Ni⁴⁺ reduction–oxidation peaks); this suggests that the LiCr_xNi_xMn_2-2xO_4-zF_z (0.1 < x≤ 0.25, z = 0.05, 0.1) cathode material could offer 4.6 to 4.8-V charge/discharge plateaus, and its specific capacity increases with increasing Ni²⁺. The impedance measurements of the cell proved that the F⁻ anion doped can not only prevent Mn³⁺ from disproportion but also can prevent the passivation film from forming and can help keep stable the cell’s electrical properties. The LiCr_0.05Ni_0.05Mn_1.9O_3.9F_0.1 sintered at 600 °C shows the best cycle performance and the largest capacity in all prepared samples; its first discharge capacity is 120 mAh/g, and the discharge capacity loses only 1.78% after 20 cycles. After 100 cycles, it still remains in the spinel structure.     

Electrical conductivity of pulverulent iron-cobalt molybdates Co1−xFexMoO4: evidence for hopping conduction

Different mixed iron-cobalt molybdates Co_1−xFe_xMoO₄ (0 < x ≤ 1) were prepared by means of a ceramic process. The influence of the isostructural substitution of Co²⁺ by Fe²⁺ and Fe³⁺ on the electrical conductivity of CoMoO₄ was studied in the temperature range (50–600°C). The results show that the iron substitution increases the electrical conductivity and changes the conduction mechanism of CoMoO₄. From a band conduction mechanism with an activation energy higher than 0.8 eV the conduction mode transforms into a hopping mechanism between the Fe²⁺ and Fe³⁺ ions in the octahedrally coordinated divalent cation sublattice. The activation energy is lower (0.4 eV) and does not alter around the polymorphic transition temperature. Owing to careful oxidations of the samples into cation deficient phases it was shown that the conductivity is proportional to the [Fe²⁺]/[Fe³⁺] ratio. These mild oxidations confirm the hopping mechanism. The presence of Co²⁺/Co³⁺ pairs has a minor contribution to the overall conductivity process. Paper presented at the 2nd Euroconference, Funchal, Madeira, Portugal, 10 – 16 Sept. 1995     

Ionic conductivity and chemical diffusion in LixCu2−xSe superionic alloys

Results of studies on the ionic conductivity and chemical diffusion coefficients of stoichiometric Li_xCu_2−xSe (0<x<0.20) ternary alloys in the temperature range 350–405 °C are presented. It is observed that in the stoichiometric copper selenide the substitution of part of copper by lithium leads to a strong change for the deterioration of ionic transport conditions.     

Photoluminescent analysis of Zn1-xCdxO alloys

The photoluminescent (PL) spectra of Zn_1-xCd_xO (0≤x≤0.53) alloy films were obtained successfully. A new explanation from the viewpoint of band structure is brought forward to comprehend the PL nature of the alloy films. According to this explanation, the near-band-energy emissions of the Zn_1-xCd_xO (x>0) films are caused by the radiative transitions between the Zn4s–Cd5s hybrid level and the O2p level, and the broadenings of the two levels are responsible for the gradually increased line width of the PL peak of the film; Zn3d and Cd4d orbital levels have great effects on the band-gap variations of the alloys. In addition, a quadratic equation is put forward to depict the relationship between the band gaps E_g of the alloys and their Cd contents x, i.e. E_g(x)=3.30-1.22x+1.26x² (0≤x≤0.53). PACS 78.55.-m; 78.55.Et; 81.15.Cd     

Study on structural, thermal, sintering and conductivity of Cu-Co doubly substituted Bi4V2O11

Doubly substitution of vanadium by Cu and Co in the limit of 10% in Bi₄V₂O₁₁, has led to the formation of the Bi₄V_1.8Cu_0.2−xCo_xO_10.7 solid solution. X-ray diffraction shows that all the compositions present a tetragonal symmetry. The thermal analysis has revealed that the polymorph γ' phase, which is formed by a partial ordering of oxygen ions in the γ high temperature form, is stabilized at room temperature. The influence of sintering temperature on the microstructure of the samples was investigated by the scanning electron microscopy (SEM). The ceramics sintered at 820 °C for more than 3 hours present micro-craks. The evolution of the electrical conductivity with temperature and the degree of substitution has been investigated by impedance spectroscopy. The sample with x=0.1 presents the highest value of the conductivity ≈4.6×10⁻² S·cm⁻¹ at 600 °C.     

Optical absorption edge of Cd1−x Mn x Ga2Se4 crystals

Summary We report the absorption edge spectra of the new family of diluted magnetic semiconductors Cd_1−x Mn _x Ga₂Se₄ (0≤x≤1), grown from the vapour phase by chemical transport. Absorption bands observed under the gap of CdGa₂Se₄ are attributed to intra-Mn²⁺ transitions involving excited states of the 3d ⁵ electrons, split by the crystal field. The authors of this paper have agreed to not receive the proofs for correction.