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1.
High-quality LaCuO2, elaborated by solid-state reaction in sealed tube, crystallizes in the delafossite structure. The thermal analysis under reducing atmosphere (H2/N2: 1/9) revealed a stoichiometric composition LaCuO2.00. The oxide is a direct band-gap semiconductor with a forbidden band of 2.77 eV. The magnetic susceptibility follows a Curie-Weiss law from which a Cu2+ concentration of 1% has been determined. The oxygen insertion in the layered crystal lattice induces p-type conductivity. The electrical conduction occurs predominantly by small polaron hopping between mixed valences Cu+/2+ with an activation energy of 0.28 eV and a hole mobility (μ300 K=3.5×10−7 cm2 V−1 s−1), thermally activated. Most holes are trapped in surface-polaron states upon gap excitation. The photoelectrochemical study, reported for the first time, confirms the p-type conduction. The flat band potential (Vfb=0.15 VSCE) and the hole density (NA=5.8×1017 cm−3) were determined, respectively, by extrapolating the curve C−2 versus the potential to their intersection with C−2=0 and from the slope of the linear part in the Mott-Schottky plot. The valence band is made up of Cu-3d orbital, positioned at 4.9 eV below vacuum. An energy band diagram has been established predicting the possibility of the oxide to be used as hydrogen photocathode.  相似文献   

2.
Highly oriented (100) thin films of LaVO3 and La1−xSrxVO3 have been fabricated by pulsed laser deposition in a reducing atmosphere. The films show a transition from insulating to metallic behaviour in the composition region of x, 0.175<x<0.200. In the single crystals of the antiferromagnetic insulating phase, a first-order structural phase transition is observed few degrees below the magnetic transition, which manifests itself as a kink in the temperature dependence of resistivity. In the highly oriented thin films of LaVO3 and La1−xSrxVO3 fabricated on lattice matched substrates in this study, the structural phase transformation in the insulating phase has been suppressed. The electrical conduction is found to take place via hopping through localized states at low temperatures. The metallic compositions show a non-linear (T1.5) behaviour in the temperature dependence of resistivity. V (2p) core level spectra of these films show a gradual change in the relative intensities of V3+ and V4+ ions as the value of x increases.  相似文献   

3.
The oxygen nonstoichiometry of La0.6Sr0.4FeO3 − δ was measured at intermediate temperatures (773 to 1173 K) between 1 bar and the decomposition oxygen partial pressure by thermogravimetry and coulometric titration. The decomposition of the ABO3 perovskite phase was found to occur at low oxygen partial pressures (below 10− 20 bar). Using an atmosphere-controlled high-temperature XRD setup, the rhombohedral lattice parameters were obtained between 10− 4 and 1 bar at 773 to 1173 K. A phase transition from rhombohedral to cubic might be expected to occur at high temperatures and for δ near the plateau at δ = [Sr] / 2. The lattice expansion was separated into “pure” thermal and chemically induced expansion by combining the lattice parameters with the oxygen nonstoichiometry data. The linear thermal expansion was formulated with a “pure” thermal expansion coefficient of αth = 11.052 · 10− 6 K− 1 and a chemical expansion coefficient of αchem = 1.994 · 10− 2.The results were compared with previous data obtained for La0.6Sr0.4Co1 − yFeyO3 − δ with y = 0.2-0.8. La0.6Sr0.4FeO3 − δ was confirmed to show the highest thermo-chemical stability. While the chemical expansion of La0.6Sr0.4Co1 − yFeyO3 − δ seems little affected by the iron content, the thermal expansion coefficient was the lowest for La0.6Sr0.4FeO3 − δ.  相似文献   

4.
Heat capacities of the electron acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its radical-ion salt NH4-TCNQ have been measured at temperatures in the 12-350 K range by adiabatic calorimetry. A λ-type heat capacity anomaly arising from a spin-Peierls (SP) transition was found at 301.3 K in NH4-TCNQ. The enthalpy and entropy of transition are ΔtrsH=(667±7) J mol−1 and ΔtrsS=(2.19±0.02) J K−1 mol−1, respectively. The SP transition is characterized by a cooperative coupling between the spin and the phonon systems. By assuming a uniform one-dimensional antiferromagnetic (AF) Heisenberg chains consisting of quantum spin (S=1/2) in the high-temperature phase and an alternating AF nonuniform chains in the low-temperature phase, we estimated the magnetic contribution to the entropy as ΔtrsSmag=0.61 J K−1 mol−1 and the lattice contribution as ΔtrsSlat=1.58 J K−1 mol−1. Although the total magnetic entropy expected for the present compound is R ln 2 (=5.76 J K−1 mol−1), a majority of the magnetic entropy (∼4.6 J K−1 mol−1) persists in the high-temperature phase as a short-range-order effect. The present thermodynamic investigation quantitatively revealed the roles played by the spin and the phonon at the SP transition. Standard thermodynamic functions of both compounds have also been determined.  相似文献   

5.
New fluorophosphate glasses based on MnF2, NaPO3 and MFn (M=Zn2+, Sr2+, Mg2+, Ba2+, Li+, Na+ and K+) have been synthesised and characterized. Large vitreous areas were observed. Samples of 4 mm in thickness have been obtained. These glasses are easy to prepare and stable in ambient air. Depending on the composition and the nature of the M cation, glass transition temperature, Tg, lies between 230 and 314 °C, crystallisation temperature, Tx is between 320 and 475 °C. These glasses are pink coloured, and infrared transmission extends up to 4.5 μm with extrinsic OH absorption band at 3200 cm−1 and other bands around 2200 and 1600 cm−1 that relate to PO4 tetrahedron vibration. Other physical properties including density, microhardness, Young modulus, thermal expansion and refractive index were investigated and correlated to composition.  相似文献   

6.
Electron paramagnetic resonance (EPR) investigations has been carried out on the new family of molybdenum doped vanadium sesquioxides (V1−xMox)2−δO3. The oxidation effects were monitored from the rate of paramagnetic V4+ created when the sample is exposed to the air. The effects of the oxidation time, sample temperature, and annealing at 1000 °C under a diluted hydrogen atmosphere on the EPR signal features are analyzed. The V4+ concentration in the oxidized samples is determined and the relaxation effects driven by the conduction electrons are pointed out from the thermal behaviour of the EPR line features. EPR spectra of all the oxidized samples also reveal a small ferromagnetic contribution strongly correlated with the V4+ content.  相似文献   

7.
The equilibrium p(O2)-T-δ diagrams of perovskite-type La1 − xSrxCoO3 − δ (x = 0.3-0.7), collected at 873-1223 K in the oxygen partial pressure range 10− 5-1 atm by coulometric titration and thermogravimetric analysis, were analyzed in order to appraise the effects of the point-defect interactions. The nonstoichiometry variations were adequately described combining the rigid-band approach for delocalized holes and the pair-cluster formation reaction involving oxygen vacancies and Co2+ cations, whilst coulombic repulsion between the positively charged vacancies can be neglected. The resultant relationships between the oxygen chemical potential and mobile vacancy concentration were used for numerical regression analysis of the steady-state oxygen permeation through dense La1 − xSrxCoO3 − δ membranes, affected by the surface exchange kinetics when Sr2+ content is higher than 40-50%. The calculated ionic conductivity is strongly influenced by the defect association processes, and decreases with decreasing concentration of the mobile vacancies as clustering starts to prevail on reduction. The Mössbauer spectroscopy studies of La1 − xSrxCoO3 − δ, doped with 1 mol% 57Fe isotope and moderately reduced at p(O2) ≈ 105 atm, show no long-range vacancy ordering at x ≤ 0.5.  相似文献   

8.
We present results on the Hall coefficient RH in the normal state for a GdBa2Cu3O7−δ/La0.75Sr0.25MnO3 bilayer and a La0.75Sr0.25MnO3 film grown by dc magnetron sputtering on (1 0 0) SrTiO3. We find that the electric transport on the bilayer can be qualitatively described using a simple parallel layers model. The GdBa2Cu3O7−δ layer presents a carrier density approximately equal to that reported for 7 − δ = 6.85 oxygen doping. Also we observe an unexpected presence of two Hall resistivity regimes, effects that may be associated with the internal magnetic field induced on the superconducting layer by the ferromagnetic layer.  相似文献   

9.
Crystal structure, thermogravimetry (TG), thermal expansion coefficient (TEC), electrical conductivity and AC impedance of (Ba0.5Sr0.5)1-xLaxCo0.8Fe0.2O3-δ (BSLCF; 0.05?x?0.20) were studied in relation to their potential use as intermediate temperature solid oxide fuel cell (IT-SOFC) cathode. A single cubic pervoskite was observed by X-ray diffraction (XRD). The TEC of BSLCF was increasing slightly with the increasing content of La, and all the compounds showed abnormal expansion at high temperature. Proved by the TG result, it was associated with the loss of lattice oxygen. The electrical conductivity, which is the main defect of Ba0.5Sr0.5 Co0.8Fe0.2O3-δ (BSCF), was improved by La doping, e.g., the compound of x=0.20 demonstrated a conductivity of σ=376 S cm−1 at 392 °C. The increase of electrical conductivity resulted from the increased concentration of charge carrier induced by La doping. In addition, the AC impedance revealed the better electrochemical performance of BSLCF. For example, at 500 °C, the sample with composition x=0.15 yielded the resistance values of 2.12 Ω cm2, which was only 46% of BSCF.  相似文献   

10.
Antiferromagnetic phase transition in two vanadium garnets AgCa2Co2V3O12 and AgCa2Ni2V3O12 has been found and investigated extensively. The heat capacity exhibits sharp peak due to the antiferromagnetic order with the Néel temperature TN=6.39 K for AgCa2Co2V3O12 and 7.21 K for AgCa2Ni2V3O12, respectively. The magnetic susceptibilities exhibit broad maximum, and these TN correspond to the inflection points of the magnetic susceptibility χ a little lower than T(χmax). The magnetic entropy changes from zero to 20 K per mol Co2+ and Ni2+ ions are 5.31 J K−1 mol-Co2+-ion−1 and 6.85 J K−1 mol-Ni2+-ion−1, indicating S=1/2 for Co2+ ion and S=1 for Ni2+ ion. The magnetic susceptibility of AgCa2Ni2V3O12 shows the Curie-Weiss behavior between 20 and 350 K with the effective magnetic moment μeff=3.23 μB Ni2+-ion−1 and the Weiss constant θ=−16.4 K (antiferromagnetic sign). Nevertheless, the simple Curie-Weiss law cannot be applicable for AgCa2Co2V3O12. The complex temperature dependence of magnetic susceptibility has been interpreted within the framework of Tanabe-Sugano energy diagram, which is analyzed on the basis of crystalline electric field. The ground state is the spin doublet state 2E(t26e) and the first excited state is spin quartet state 4T1(t25e2) which locates extremely close to the ground state. The low spin state S=1/2 for Co2+ ion is verified experimentally at least below 20 K which is in agreement with the result of the heat capacity.  相似文献   

11.
The conductivity and dielectric permittivity spectra of single-crystalline La1.87Sr0.13CuO4 are directly measured with the electric field polarized perpendicular to the CuO planes (Ec) covering the frequency range 10-40 cm−1 and temperatures 5-300 K. We observe in the superconducting state a well pronounced excitation with strongly temperature dependent parameters. We suggest that the excitation is caused by the transverse Josephson plasma mode that appears due to the different strengths of Josephson coupling between the superconducting charge stripes in the neighboring and next-nearest neighboring copper-oxygen planes of La1.87Sr0.13CuO4. A strongly enhanced low-frequency (below 15 cm−1) absorption is seen in the superconducting state that is assigned to delocalized quasiparticles of as yet unknown origin.  相似文献   

12.
Y-doped La0.7Sr0.3CrO3−δ is a promising anode catalyst for solid oxygen fuel cell (SOFC). The performances of chemical and physical are measured by SEM, XRD and FT-IR. The conductivities of catalyst are measured by DC four-probe method in 20% H2S-N2, 3% H2-N2 and air from 573 K to 1173 K, respectively. The results show that Y-doped La0.7Sr0.3CrO3−δ powders have perfect perovskite phase structure with no extra peaks and exhibit good chemical compatibility with Ce0.8Sm0.2O1.9 (as electrolyte) in air. Through XRD and FT-IR analysis no sulfur-containing species is detected after exposure to the 20% H2S at 1173 K for 5 h. Meanwhile, Y-doped La0.7Sr0.3CrO3−δ shows that the highest conductivity is 0.21 S/cm at 1173 K in H2S. The open circuit voltages are 0.85 V at 1173 K in H2S and 1.04 V at 823 K in H2. The maximal power densities are 12.4 mW/cm2 in H2S and 1.59 W/cm2 in H2 for cells comprising Y-doped La0.7Sr0.3CrO3−δ-Sm0.2Ce0.8O1.9/Sm0.2Ce0.8O1.9/Ag.  相似文献   

13.
Lanthanum based mixed valence manganite system La1−xCax−0.08Sr0.04Ba0.04MnO3 (LCSBMO; x=0.15, 0.24 and 0.33) synthesized through the sol-gel route is systematically investigated in this paper. The electronic transport and magnetic susceptibility properties are analyzed and compared, apart from the study of unit cell structure, microstructure and composition. Second order phase transition is observed in all the samples and significant difference is observed between the insulator to metal transition temperature (TMI) and paramagnetic (PM) to ferromagnetic (FM) transition temperature (TC). In contrast to the insulating FM behaviour usually observed in La1−xCaxMnO3 (LCMO) for x=0.15, a clear insulator to metal transition is observed for LCSBMO for the same percentage of lanthanum. The temperature dependent resistivity of polycrystalline pellets, when obeying the well studied law ρ=ρo+ρ2T2 for T<TMI, is observed to differ significantly in the values of ρo and ρ2, with the electrical conductivity increasing with x. The variable range hopping model has been found to fit resistivity data better than the small polaron model for T>TMI. AC magnetic susceptibility study of the polycrystalline powders of the manganite system shows the highest PM to FM transition of 285 K for x=0.33.  相似文献   

14.
A new compound, K4(SO4)(HSO4)2(H3AsO4) was synthesized from water solution of KHSO4/K3H(SO4)2/H3AsO4. This compound crystallizes in the triclinic system with space group P1¯ and cell parameters: a=8.9076(2) Å, b=10.1258(2) Å, c=10.6785(3) Å; α=72.5250(14)°, β=66.3990(13)°, γ=65.5159(13)°, V=792.74(3) Å3, Z=2 and ρcal=2.466 g cm−3. The refinement of 3760 observed reflections (I>2σ(I)) leads to R1=0.0394 and wR2=0.0755. The structure is characterized by SO42−, HSO4 and H3AsO4 tetrahedra connected by hydrogen bridge to form two types of dimer (H(16)S(3)O4?S(1)O42− and H(12)S(2)O4?H3AsO4). These dimers are interconnected along the [1¯ 1 0] direction by the hydrogen bonds O(3)-H(3)?O(6). They are also linked by the hydrogen bridge assured by the hydrogen atoms H(2), H(3) and H(4) of the H3AsO4 group to build the chain S(1)O4?H3AsO4 which are parallel to the “a” direction. The potassium cations are coordinated by eight oxygen atoms with K-O distance ranging from 2.678(2) to 3.354(2) Å.Crystals of K4(SO4)(HSO4)2(H3AsO4) undergo one endothermic peak at 436 K. This transition detected by differential scanning calorimetry (DSC) is also analyzed by dielectric and conductivity measurements using the impedance spectroscopy techniques. The obtained results show that this transition is protonic by nature.  相似文献   

15.
Submicron-sized polyhedral Li4Ti5−xSnxO12 (x=0.0, 0.05, and 0.1) materials were successfully prepared by a single-step molten salt method. The structural, morphological, transport and electrochemical properties of the Li4Ti5−xSnxO12 were studied. X-ray diffraction patterns showed the formation of a cubic structure with a lattice constant of 8.31 Å, and the addition of dopants follows Vegard's law. Furthermore, FT-IR spectra revealed symmetric stretching vibrations of octahedral groups of MO6 lattice in Li4Ti5O12. The formation of polyhedral submicron Li4Ti5−xSnxO12 particles was inferred from FE-SEM images, and a particle size reduction was observed for Sn-doped Li4Ti5O12. The chemical composition of Ti, O and Sn was verified by EDAX. The DC electrical conductivity was found to increase with increasing temperature, and a maximum conductivity of 8.96×10−6 S cm−1 was observed at 200 °C for Li4Ti5O12. The galvanostatic charge–discharge behavior indicates that the Sn-doped Li4Ti5O12 could be used as an anode for Li-ion batteries due to its enhanced electrochemical properties.  相似文献   

16.
The oxygen deficiency of perovskite-type Pr0.5Sr0.5FeO3−δ, studied by coulometric titration, thermogravimetry and Mössbauer spectroscopy, is significantly higher than that in La0.5Sr0.5FeO3−δ at 973-1223 K. The variations of hole mobility and Seebeck coefficient in oxidizing atmospheres, where the total conductivity of praseodymium-strontium ferrite is predominantly p-type electronic, suggest progressive delocalization of the p-type charge carriers on increasing oxygen chemical potential. As for other perovskite-type ferrites, reduction leads to the co-existence of vacancy-ordered and disordered domains. The n-type electronic conductivity of Pr0.5Sr0.5FeO3−δ at reduced p(O2) and the hole transport under oxidizing conditions are both lower compared to the La-containing analogue. Analogous conclusion was drawn for the ionic conductivity, calculated from the steady-state oxygen permeation data under oxidizing conditions and from the p(O2)-dependencies of total conductivity in the vicinity of electron-hole equilibrium points where the average iron oxidation state is 3+. The similar activation energies for partial ionic and electronic conductivities in Ln0.5Sr0.5FeO3−δ (Ln=La, Pr) indicate that the presence of praseodymium does not alter any of the conduction mechanisms but decreases the charge-carrier mobility due to the smaller radius of Pr3+ cations stabilized in the perovskite lattice.  相似文献   

17.
The conducting oxides solid solutions of Cd1+xIn2−2xSnxO4 (x=0.1, 0.3, 0.5, 0.7, 1.0) were prepared via a solid state reaction method. The band gaps were estimated to be 2.4 eV for x=1.0, 2.5 eV for x=0.7, 2.6 eV for x=0.5, 2.7 eV for x=0.3 and 2.8 eV for x=0.1. Oxygen could be evolved over Cd2SnO4 under the irradiation of Xe-lamp or even visible light (λ>420 nm), while the others could only work in the UV-light range. Raman showed the cation distribution in Cd2SnO4 is ordered, while that in the others is disordered. The cations distribution was proposed to be the cause of the difference in photocatalytic O2-evolution activities.  相似文献   

18.
The oxygen hyperstoichiometry of K2NiF4-type La2Ni0.9Fe0.1O4+δ, studied by thermogravimetric analysis and coulometric titration in the oxygen partial pressure range 6×10−5-0.7 atm at 923-1223 K, is considerably higher than that of undoped lanthanum nickelate. The p(O2)-T-δ diagram of iron-doped lanthanum nickelate can be adequately described by introducing point-defect interaction energy in the concentration-dependent part of defect chemical potentials and accounting for the site-exclusion effects. The critical factors affecting the equilibrium oxygen incorporation process include coulombic repulsion of interstitial anions, trapping of the p-type electronic charge carriers by iron, and interaction between Fe3+ and holes localized on nickel cations. Due to low chemical expansion of La2Ni0.9Fe0.1O4+δ lattice, the thermodynamic functions governing oxygen intercalation, site-blocking factors and hole mobility are all independent of the defect concentrations. The predominant 3+ state of iron cations under oxidizing conditions was confirmed by the Mössbauer spectroscopy. The stability of La2NiO4-based phase in reducing atmospheres is essentially unaffected by doping.  相似文献   

19.
Ag-network was successfully deposited by VA-EP (vacuum assisted electroless plating) method on Pr1.6Sr0.4NiO4-YSZ cathode to form (1−x) wt% Pr1.6Sr0.4NiO4wt% YSZ-Ag (x=0, 10, 20, 30, 40) (abbr. PYx-Ag) composite cathode. XRD results suggested that there was a good chemical stability between Pr1.6Sr0.4NiO4 and YSZ at temperatures below 1050 °C. PY20-Ag cathode exhibited higher exchange current density, lower overpotential and ASR (Area Specific Resistance) than PY20 cathode. At 650 °C, the ASR of PY20-Ag cathode was 2.5 Ω cm2, which was only about 42% of that of PY20, 5.9 Ω cm2. PY20-Ag can be a promising candidate for SOFC cathode.  相似文献   

20.
Transparent conducting thin films of fluorine-doped tin oxide (FTO) have been deposited onto the preheated glass substrates of different thickness by spray pyrolysis process using SnCl4·5H2O and NH4F precursors. Substrate thickness is varied from 1 to 6 mm. The films are grown using mixed solvent with propane-2-ol as organic solvent and distilled water at optimized substrate temperature of 475 °C. Films of thickness up to 1525 nm are grown by a fine spray of the source solution using compressed air as a carrier gas. The films have been characterized by the techniques such as X-ray diffraction, optical absorption, van der Pauw technique, and Hall effect. The as-deposited films are preferentially oriented along the (2 0 0) plane and are of polycrystalline SnO2 with a tetragonal crystal structure having the texture coefficient of 6.19 for the films deposited on 4 mm thick substrate. The lattice parameter values remain unchanged with the substrate thickness. The grain size varies between 38 and 48 nm. The films exhibit moderate optical transmission up to 70% at 550 nm. The figure of merit (φ) varies from 1.36×10−4 to 1.93×10−3 Ω−1. The films are heavily doped, therefore degenerate and exhibit n-type electrical conductivity. The lowest sheet resistance (Rs) of 7.5 Ω is obtained for a typical sample deposited on 4 mm thick substrate. The resistivity (ρ) and carrier concentration (nD) vary over 8.38×10−4 to 2.95×10−3 Ω cm and 4.03×1020 to 2.69×1021 cm−3, respectively.  相似文献   

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