First principles analysis of the MgAl2O4:Ni absorption spectrum

Analysis of the energy-level scheme and absorption spectrum of the Ni²⁺ ion in MgAl₂O₄ was performed. The recently developed first-principles approach to the analysis of the absorption spectra of impurity ions in crystals based on the discrete variational multi-electron (DV-ME) method [K. Ogasawara, et al., Phys. Rev. B 64 (2001) 115413) was used in the calculations. The method is based on the numerical solution of the Dirac equation; no phenomenological parameters are used in the calculations. As a result, complete energy-level scheme of Ni²⁺ and its absorption spectra were calculated, assigned and compared with experimental data on the ground and excited state absorption spectra. Numerical contributions of all possible electron configurations into the calculated energy states were determined. By performing analysis of the molecular orbitals population, numerical contributions of the oxygen 2p- and 2s-orbitals into the 3d molecular orbitals were determined.     

Effect of cation distribution on the properties of Mn0.2ZnxNi0.8−xFe2O4

Mn_0.2Zn_xNi_0.8−xFe₂O₄ (x=0.2, 0.3, 0.4, 0.5, 0.6) are synthesized by the citrate precursor method. Effects of zinc substitution on DC resistivity, dielectric relaxation intensity, initial permeability, saturation magnetization and Curie temperature have been investigated. It is observed that resistivity increases with increase in zinc concentration up to x=0.5 and then decreases. The observed behaviour is explained in terms of hopping and site preference of ions in the lattice. The main contribution to dielectric relaxation intensity is observed to be due to space charge polarization. Initial permeability is observed to increase with increase in zinc concentration. Saturation magnetization increases up to x=0.4 and then starts decreasing. Canting effect is observed for higher zinc concentrations.     

Crystal-field hamiltonian and spin-orbit interaction for d and d ions at low C3 symmetry sites: V:Al2O3 and Ni:LiNbO3

The experimental studies have provided evidence of the occurrence of transitions from the ³T_1g(³F) ground state to the crystal-field levels ³T_2g(³F), ³T_1g(³P) and ³A_2g(³F) for the V³⁺ centres in Al₂O₃ crystal; and from the ³A_2g(³F) ground state to the crystal-field levels ³T_2g(³F), ³T_1g(³F) and ³T_1g(³P) for the Ni²⁺ centres in LiNbO₃ crystal (levels are assigned to irreps of the O_h point symmetry group). Using the experimental spectroscopic data, theoretical calculations of the crystal-field levels of V³⁺:Al₂O₃ and Ni²⁺:LiNbO₃ are carried out based on the Racah theory. The observed crystalline-field splittings of the V³⁺ and Ni²⁺ terms were accounted for using a C₃ symmetry Hamiltonian. The spin-orbit interaction was taken into account in this work. The Racah, crystal-field and spin-orbit parameters, which fit experimental and theoretical energy levels, have been reliably obtained. A good agreement between the theoretical and experimental results for the energy levels of V³⁺:Al₂O₃ and Ni²⁺:LiNbO₃ has been obtained.     

Crystal-field analysis for d ions at D4h symmetry sites: Electronic states in trans-NiCl2(H2O)4 complex

The polarized absorption spectra of trans-NiCl₂(H₂O)₄ complex were measured by Bussière et al. [Coord. Chem. Rev. 219-221 (2001) 509-543] at low-temperature. Using the experimental spectroscopic data, semiempirical calculations of the crystal-field levels of trans-NiCl₂(H₂O)₄ chromophore are carried out, based on the Racah theory. We used idealized D_4h point group symmetry to analyse the observed crystalline-field splitting of this chromophore. As a result, Racah and crystal-field parameters have been reliably obtained. A good agreement between the theoretical and experimental energy levels of trans-NiCl₂(H₂O)₄ complex has been obtained. The region of ³T_1g/¹E_g(O_h) bands is of great interest and it is useful to use the tetragonal symmetry to understand the features of this spectral region.     

Thermoelectric properties of the Bi2−xYxRu2O7 (x=0-2) pyrochlores

Electrical conductivity and Seebeck coefficient for the Bi_2−xY_xRu₂O₇ pyrochlores with x=0.0,0.5,1.0,1.5,2.0 were measured in the temperature range of 473-1073 K in air. With increasing Bi content, the temperature dependence of the electrical conductivity changed from semiconducting to metallic. The signs of the Seebeck coefficient were positive in the measured temperature range for all the samples, indicating that the major carriers were holes. The temperature dependence of the Seebeck coefficient for the Y₂Ru₂O₇ indicated the thermal activation-type behavior of the holes, while that for the Bi_2−xY_xRu₂O₇ with x=0.0-1.5 indicated the itinerant behavior of the holes. The change in the conduction behavior from semiconductor to metal with increasing Bi content is consistent with the increase in the overlap between the Ru4d t_2g and O2p orbitals, but the mixing of Bi6s, 6p states at E_F may not be ruled out. The thermoelectric power factors for the Bi_2−xY_xRu₂O₇ with x=1.5 and 2.0 were lower than 10⁻⁵ W m⁻¹ K⁻² and those with x=0.0,0.5,1.0 were around 1-3×10⁻⁵ W m⁻¹ K⁻².     

Chemical pressure effect on the magnetic order of the La1.4Sr1.6Mn2O7 bilayered manganite

In this paper we have studied, by means of high-resolution neutron powder diffraction, the structural and magnetic feature of pure La_1.4Sr_1.6Mn₂O₇ and Sr-doped (25%) La_1.4Sr_1.6Mn₂O₇.Our data reveal the stabilization of the A-type AFM long-range order for the La_1.4Sr_1.6Mn₂O₇ bilayered manganites induced by the partial replacement of the Sr with the smaller Ca, keeping constant the hole doping. This can be in turn due to the change in the orbital character of the e_g electrons as a function of Ca-doping.     

Anomalous magnetism in three-dimensional orthogonal dimer lattice system: (Ba1−xSrx)2Ru3O9 (x≈0.35)

The magnetic and transport properties of a new cubic KSbO₃-type ruthenate, (Ba_1−xSr_x)₂Ru₃O₉ (x≈0.35), have been investigated. The crystal structure has a singular geometry in which ruthenium atoms form an ideal three-dimensional orthogonal dimer lattice. The magnetic susceptibility is Pauli-paramagnetic but exhibits an anomalous temperature dependence reminiscent of a gap-like behavior. The resistivity exhibits a metallic behavior, except for a rise at low temperature.     

Crystal growth, spectroscopic and crystal field studies of [N(CH3)4]2MnCl4 and [N(CH3)4]2CoCl4 single crystals in the paraelectric phase

Single crystals [N(CH₃)₄]₂MnCl₄ and [N(CH₃)₄]₂CoCl₄ were grown by the slow evaporation technique from the super-saturated solutions. The samples obtained were undergone the X-ray and spectroscopic studies. Absorption spectra in the paraelectric phase at T=303 K have been recorded using the Shimadzu 160A double beam automatic scanning spectrophotometers. On the basis of the exchange charge model and Racah theory the crystal field parameters and Racah parameters have been calculated; all absorption bands for both crystals were given an assignment.     

Enhancement of the anomalous Hall effect and spin glass behavior in the bilayered manganite La2−2xSr1+2xMn2O7

The Hall resistivity and magnetization have been investigated in the ferromagnetic state of the bilayered manganite La_2−2xSr_1+2xMn₂O₇ (x=0.36). The Hall resistivity shows an increase in both the ordinary and anomalous Hall coefficients at low temperatures below 50 K, a region in which experimental evidence for the spin glass state has been found in a low magnetic field of 1 mT. The origin of the anomalous behavior of the Hall resistivity relevant to magnetic states may lie in the intrinsic microscopic inhomogeneity in a quasi-two-dimensional electron system.     

Magnetic structure and collective Jahn-Teller distortions in nanostructured particles of CuFe2O4

The aim of the present work is to compare the structural, the composition and chemical state of the surface and magnetic properties of different nanosized CuFe₂O₄ powders exhibiting collective Jahn-Teller effect. The samples under examination consist of edged nanosized particles (needle like) with average length 1300 ± 20 nm and diameter 300 ± 20 nm obtained after high temperature synthesis, and superparamagnetic (at room temperature) spherical particles (d = 6 ± 2 nm), obtained by soft chemistry techniques. The surface composition of the particles was investigated by X-ray photoelectron spectroscopy (XPS). Mössbauer spectroscopy (MöS), including at high magnetic field up to 5 T and 4.2 K, was used for characterization of cation distribution in the samples. The data yielded by the XPS and MöS analyses for spherical nanosized particles led us to the assumption for the existence of a Jahn-Teller effect gradient—from the B-sublattice on the surface to a compensation of the tetragonal distortion in the two sublattices in the core. The analysis of the contribution of the anisotropy energy in edged and spherical nanoparticles shows that it must be considered as an effective value reflecting the influence of the individual factors depending on the particle shape and surface.     

Crystal field analysis of energy level structure of the Cr2O3 antiferromagnet

A detailed analysis of the energy level structure of the six-fold coordinated Cr³⁺ ion in the chromium oxide Cr₂O₃ is performed using the exchange charge model of the crystal field theory. Parameters of the crystal field acting on the Cr³⁺ optical electrons are calculated from the crystal structure data for the [CrO₆]⁹⁻ impurity center. The energy levels obtained are compared with the experimental absorption spectra for the considered crystal; a good agreement with experimental data is demonstrated. One possible explanation for the ultraviolet p₁ absorption band is proposed based on the results of crystal field calculations.     

Electrochemical studies on mixtures of LiNi0.8Co0.17Al0.03O2 and LiCoO2 cathode materials for lithium ion batteries

Detailed electrochemical investigations have been carried out on LiNi_0.8Co_0.17Al_0.03O₂ as cathode materials for lithium ion batteries in the potential range of 2.8-4.3 V. This sample showed an initial discharge capacity of 186 mAh/g which corresponds to 67% of its theoretical capacity. The effect of addition of LiCoO₂ to LiNi_0.8Co_0.17Al_0.03O₂ in the ratio 10:90, 30:70, 50:50 has been studied. The results showed that the addition of LiCoO₂ has improved the working voltage of the cell. In addition, the percentage retention (95%) of the cell is significantly increased in the composition ratio 50:50.     

Analysis of exchange bias effect of NiO+NiFe2O4 composites

Exchange bias (EB) and magnetic properties of ferrimagnetic (FI) NiFe₂O₄ and antiferromagnetic (AFM) NiO bulk composites, prepared by a chemical co-precipitation and post-thermal decomposition method from Fe-doped NiO matrix, have been investigated. Enhanced coercivities and shifted hysteresis loops are still observed for these samples after field cooling. But the vertical magnetization shifts are not observed. In comparison with the bulk samples, a NiO/10% NiFe₂O₄ nanocomposite was also prepared via direct mixture, in which both the horizontal and vertical shift in the hysteresis loops are observed at 10 K. The observed phenomena are explained in terms of interfacial exchange interaction between the two phases and the finite-size effect, respectively.     

Experimental and theoretical studies of polaron optical properties in KNbO3 perovskite

Time-resolved absorption and luminescence spectra have been measured in KNbO₃ perovskite crystals after pulsed band-gap excitation by 200 fs laser pulses and 10 ns electron pulses. Quantum chemical calculations using the large unit cell periodic model support the interpretation of the observed transient absorption bands at 0.8 and 1.1 eV as the self-trapped electron polarons and bound hole polarons, respectively. The activation energy for the 2.2 eV green luminescence quenching is 0.05 eV. We suggest that the short lifetime (<15 ns) of the luminescence at RT is caused by the radiative recombination of nearest electron and hole polarons.     

Transient differential reflectivity of ferromagnetic and paramagnetic phases in the bilayered manganite La1.24Sr1.76Mn2O7

Photoinduced effects in a single crystal of bilayered manganites, La_2−2xSr_1+2xMn₂O₇ (x=0.38), were investigated in a wide range of temperatures by pump-probe measurement at a photon energy of 1.6 eV. In a ferromagnetic metallic state, significant enhancement of positive rise in differential reflectivity with a slow relaxing time of 100 ps was observed just below T_C=127 K, indicating that the reflectivity change with the slow relaxation time constant is induced by laser heating. We have also observed an unconventional fast relaxing component that has a time constant of the order of 10 ps. This fast relaxing component, whose absolute value has an asymmetric peak at T_C, is presumably due to short-range correlation of Jahn-Teller distortion.     

Crystallization-dependent magnetic properties of Mn1.56Co0.96Ni0.48O4 thin films

The effects of magnetic property dependence of the Mn_1.56Co_0.96Ni_0.48O₄ (MCN) films on crystallization are investigated in the growth temperature of 450-750 °C. With the growth temperature increase, both the crystalline quality and the grain size improve. The MCN films exhibit paramagnetic to ferromagnetic transition and the paramagnetic parts fit to the modified Curie-Weiss law. The ferromagnetic couplings of the magnetic ions in the MCN films enhance at elevated growth temperature. The saturation magnetization at 5 K increases with increasing growth temperature, but coercive field decreases monotonously. The magnetic properties of the MCN films strongly depend on their microstructures.     

Structural and transport properties of cubic spinel ZnCo2O4 thin films grown by reactive magnetron sputtering

We report on the growth of cubic spinel ZnCo₂O₄ thin films by reactive magnetron sputtering and bipolarity of their conduction type by tuning of oxygen partial pressure ratio in the sputtering gas mixture. Crystal structure of zinc cobalt oxide films sputtered in an oxygen partial pressure ratio of 90% was found to change from wurtzite Zn_1−xCo_xO to spinel ZnCo₂O₄ with an increase of the sputtering power ratio between the Co and Zn metal targets, D_Co/D_Zn, from 0.1 to 2.2. For a fixed D_Co/D_Zn of 2.0 yielding single-phase spinel ZnCo₂O₄ films, the conduction type was found to be dependent on the oxygen partial pressure ratio: n-type and p-type for the oxygen partial pressure ratio below ∼70% and above ∼85%, respectively. The electron and hole concentrations for the ZnCo₂O₄ films at 300 K were as high as 1.37×10²⁰ and 2.81×10²⁰ cm⁻³, respectively, with a mobility of more than 0.2 cm²/V s and a conductivity of more than 1.8 S cm⁻¹.     

Experimental and theoretical studies on dynamic properties of Li ions in LixMn2O4

In order to study the dynamic properties of Li_xMn₂O₄, potential relaxation techniques (PRT) is used to measure the chemical diffusion coefficient of Li_xMn₂O₄. Results are presented for x ranges from x=0.1 to 0.9. They show that the chemical diffusion coefficient at the two-phase coexistent stage near x=0.3 and 0.7 is higher than at the single-phase stage during the insertion and extraction process. Monte Carlo (MC) simulations are also used to simulate the ionic conductivity σ of Li ions in Li_xMn₂O₄ and its dependence as a function of lithium concentration x. The results show an M shaped curve in the plot of ionic conductivity σ versus x when the simulation temperature is 293 K, which confirms the experimental PRT results. The voltage profiles of Li_xMn₂O₄/Li cells were also simulated with different boundary conditions.     

Modified texture and high temperature transport properties of doubly substituted BaxAgyCa2.8Co4O9 thermoelectric oxide

Doubly substituted polycrystalline compound bulk samples of Ba_xAg_yCa_2.8Co₄O₉ were prepared via citrate acid sol-gel method followed by spark plasma sintering. The phase composition, orientation, texture and high temperature electrical properties were systematically investigated. The results showed that the orientation and the texture could be modified by altering ratio of Ba to Ag. The resistivity and the Seebeck coefficient of substituted samples were decreased by decreasing Ba/Ag ratio except for that of Ba_0.1Ag_0.1Ca_2.8Co₄O₉ sample with lowest electrical resistivity (7.2 mΩ cm at 973 K), moderately high Seebeck coefficient (172 μV/K at 973 K) and improved power factor (0.42 mW/mK² at 973 K).     

The great potential of coupled substitutions in In2O3 for the generation of bixbyite-type transparent conducting oxides, In2−2xMxSnxO3

The study of coupled substitution of In³⁺ by Sn⁴⁺/M²⁺ species in In₂O₃ has allowed In_2−2xSn_xM_xO₃ solid solutions with bixbyite structure to be synthesized for M=Ni, Mg, Zn, Cu and Ca. The latter exhibit a rather broad homogeneity range and are characterized by an ordered cationic distribution. More importantly, these novel oxides are transparent conductors, and among them the Zn and Cu phases show a great potential, since one observes a semi-metallic behavior with conductivity up to 3×10² and 3×10³ (Ω cm)⁻¹, respectively, to be compared to 2×10³ (Ω cm)⁻¹ for reduced ITO. Moreover, in contrast to the latter no reducing conditions are required for reaching such performances.