Optical properties of Nb doped SrTiO3 from first principles study

The electronic and optical properties of Nb doped SrTiO₃ are studied by ab initio linear muffin-tin orbital method in the atomic sphere approximation. The equilibrium lattice constants of SrTi_1−xNb_xO₃ with x=0.0, 0.25 and 0.5 are found by minimization of the total energy curves. The computated lattice constants are in good agreement with experimental data. Our electronic band calculation shows that the Fermi level of SrTi_1−xNb_xO₃ with x≥0.125 moves into the conduction bands and the system shows metallic behavior. The numerical results indicate that the Nb impurity atoms would lead to the distortion of the band edges. The complex dielectric function of SrTiO₃ and Nb doped SrTiO₃ are calculated using the random-phase approximation. The doping effect on the optical properties of SrTi_1−xNb_xO₃ is discussed.     

Magnetic properties and electronic structure of the LaGaO3 perovskite doped with nickel

Solid solutions of the composition LaGa_{1 ? x} Ni _x O₃ (0.01 ≤ x ≤ 0.10) are synthesized, and their magnetic and electrical properties are investigated. It is established that the ground state of the Ni(III) atoms is the low-spin state ² E _g ; however, in the temperature range under investigation, there occurs the ² E _g ? ⁴ T _1g spin equilibrium. An increase in the nickel concentration leads to an increase in the electron conduction of the solid solutions. The band structure of the LaGa_0.5Ni_0.5O₃ model compound is calculated using the ab initio full-potential linearized augmented-plane-wave method within the generalized gradient approximation (FLAPWGGA). It is shown that the dominant role in the variations observed in the magnetic and electrical properties of the nonmagnetic semiconductor LaGaO₃ upon doping with nickel is played by the Ni 3d(e _g ↑, ↓) states.     

XRD, microstructural and EPR susceptibility characterization of combustion synthesized nanoscale Mg1−xNixO solid solutions

The lattice parameter a(x) of the stoichiometric Mg_1−xNi_xO (0?x?1) solid solutions prepared by urea-based combustion synthesis with fuel to oxidizer ratio (ψ=1) was determined by X-ray diffraction. It was found that the dependence of the lattice parameter a(x) on the composition deviated more from the linear Vegard's model (VM) when compared to Kuzmin-Mironova (KM) model. a(x) in the Mg_1−xNi_xO system differs nontrivially from the predictions of both VM and KM models. For x=0.4 (Mg_0.6Ni_0.4O), the maximum deviation was about 2 and 1.7 pm, respectively. The increase in the intensity of (1 1 1) peak in XRD with increase of nickel concentration confirms that the substitution induces changes at the unit cell level. Nelson-Riley function (NRF) and Williamson-Hall plots are used to calculate micro strain in the solid solution. This analysis indicates that the micro strain is maximum for the compositions 60-40 (Mg_0.6Ni_0.4O), 50-50 (Mg_0.5Ni_0.5O) and 40-60 (Mg_0.4Ni_0.6O). The crystallite size was estimated using Williamson-Hall plot. We conclude that almost similar sized crystallite is formed in all the compositions studied. Porosity determined using XRD increases with a raise in the nickel concentration. The SEM morphology provides corroborative evidence. EPR susceptibilities of solid solution Mg_1−xNi_xO are determined at room temperature. Variable temperature of EPR allowed to check the Curie-Weiss law for solid solution. The linearity of C_M(x) and Θ(x) with concentration of nickel has ruled out chemical clustering in the samples.     

Neutron diffraction investigation of structural and magnetic states of lithium-doped antiferromagnet NiO

The elastic neutron scattering in polycrystalline samples of the (Ni_1−x Li_x)O solid solutions (x<0.1) is investigated by neutron diffraction technique. It is shown for the first time that the doping of nickel monoxide by lithium is accompanied by the formation of vacancies in the anionic sublattice, and the vacancy concentration is equal to the lithium content in the solid solution. The neutral lithium atoms are randomly arranged over sites of the cationic sublattice with possible spatial polarization of a valence electron toward an oxygen vacancy. In the composition range studied, the diamagnetic dilution of nickel monoxide by lithium turns out to be magnetically similar to the dilution with magnesium. In both cases, the Néel temperature and the mean magnetic moment per atom linearly decrease with an increase in concentration of the diamagnetic dopant.     

Phase formation in the BaCO<Subscript>3</Subscript>–PbO–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Features of the formation of lead-ferroniobate compounds in the xBaCO₃–(1 – x)PbO–Fe₂O₃–Nb₂O₅ system by solid-phase synthesis are investigated. For perovskite-type lead-ferroniobate solid solution, a single-phase concentration region is revealed at 1233 K. The crystalline structures of the synthesized compounds are refined using Rietveld analysis and the Pm3?m and R3m space groups. Ceramic samples of lead ferroniobate are studied by scanning electron microscopy.     

Raman scattering and room temperature ferromagnetism in Co-doped SrTiO3 particles

Raman scattering has been used to study the influence of cobalt, an effective dopant to obtain SrTiO₃ magnetic oxide, on the lattice dynamics of SrTiO₃. It is found that Co doping increases the lattice defects and induces a Raman vibration mode of 690 cm⁻¹. On the other hand, the ferromagnetism dependence on the x and annealing temperature was clearly and coherently observed in SrTi_1−xCo_xO₃ (x = 0, 0.01, 0.03 and 0.05) nanoparticles. It is found that the ferromagnetism of SrTi_1−xCo_xO₃ nanoparticles is weakly related to crystal deformation and oxygen vacancies in SrTiO₃. So, F-center model can explain the origin of the ferromagnetism in the prepared Co-doped SrTiO₃ samples. At the same time, the finding of large room-temperature ferromagnetism (1.6 emu/g) in this system would stimulate further interest in the area of more complicated ternary oxides.     

Oxygen non-stoichiometry, redox thermodynamics, and structure of LaFe1 − x Co x O3 − δ

The oxygen non-stoichiometry and redox thermodynamic properties of the LaFe_{1 ? x} Co _x O_{3 ? δ} system (x?=?0.25 and 0.75) are studied. At low temperatures, the LaCoO₃ and LaFeO₃ systems show partial solid solubility. At 1,273 K (in air), both compounds are single phases and are orthorhombic and rhombohedral for x?=?0.25 and 0.75, respectively. Thermogravimetry has been used to measure the oxygen non-stoichiometry versus oxygen partial pressure at three temperatures, 1,223, 1,273, and 1,323 K. Redox thermodynamic quantities are extracted directly from the oxygen non-stoichiometry curves. The extracted enthalpies of oxidation do not vary significantly with stoichiometry, and for x?=?0.25 and 0.75, they are ?640?±?60 and ?440?±?60 kJ (mol O₂)^?1, respectively. Ideal solid solution thermodynamic models are used to analyze the redox mechanisms.     

Effect of nickel on the magnetic state of dysprosium in Dy<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript>x</Subscript>-Ni bilayer films

This paper reports on the results of investigations into the temperature and spectral dependences of the magnetic circular dichroism in Dy_1?xNi_x-Ni bilayer films prepared through thermal sputter deposition of components under ultrahigh vacuum. The distribution of the components over the layer thickness is examined by Auger spectroscopy. The nickel content x in Dy_1?xNi_x layers varies from 0.005 to 0.06. It is shown that, in the temperature range 80–300 K, the contribution made to the magnetic circular dichroism by a Dy_1?xNi_x layer in a bilayer film with a nickel content higher than the threshold value is approximately equal to the magnetic circular dichroism observed in an isolated Dy_1?xNi_x film at temperatures below the temperature of the phase transition to a ferromagnetic state (～100 K). This phenomenon is explained by magnetic ordering in the Dy_1?xNi_x layer of the bilayer film due to the combined effect of two factors, namely, the incorporation of nickel into a dysprosium layer and the presence of a continuous nickel sublayer in the film.     

Defect structure of the Spinel,Ni2.44Ti0.77O4

Cation-excess spinels with composition Ni_2(1+x)Ti_(1?x)O₄ (0.16 ≤ x ≤ 1) form a limited solid solution between the rocksalt (NiO) and the hypothetical spinel (Ni₂TiO₄) structure types at temperatures above 1375°C. A quenched product of this series, Ni_2.44Ti_0.77O₄ ($\text{Fd3m;}\text{Z}\text{= 8; ρ}{}_{\mathrm{<mtext>calc</mtext>}}\text{= 5.6}\text{g}\text{/}\text{cm}{}^3\text{; a = 8.339}\text{A}\text{?}$), has been refined with X-ray intensity data in three models. Results indicate partial occupancy of the tetrahedral site (8a) and a second octahedral site (16c). Substitution of one tetrahedral metal atom for two octahedral atoms in random units of the NiO structure accounts for the additional metal atoms over the M₃O₄ stoichiometry. The best agreement with the model is obtained when all Ti₄₊ partially occupies the tetrahedral site.     

Concentration-phase transitions in solid solutions Li x Na1 − x Ta0.1Nb0.9O3, Li0.12Na0.88Ta y Nb1 − y O3, and NaTa y Nb1 − y O3 and their manifestations in Raman spectra

Using the Raman-spectroscopy method, we have studied concentration-phase transitions in the solid solutions Li _x Na_{1 ? x} Ta_0.1Nb_0.9O₃, Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, and NaTa _y Nb_{1 ? y} O₃ (x = 0?0.16, y = 0–1). It has been revealed that, for the solid solutions Li _x Na_{1 ? x} Ta_0.1Nb_0.9O₃ and Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, the concentration-phase transition is a transition between the ferroelectric and antiferroelectric states. It is accompanied by the disappearance from the spectrum of a line that corresponds to stretching bridge vibrations of oxygen atoms along the polar axis, which is forbidden by selection rules in the centrosymmetric phase, and by splitting into two components of a line that corresponds to librational vibrations of oxygen octahedra as a whole, which can be caused by doubling of the unit cell in the antiferroelectric phase. Manifestation and variation of intensities of lines with frequencies 860–873 and 900–905 cm^?1 upon variation of the concentration of tantalum for solid solutions Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, and NaTa _y Nb_{1 ? y} O₃ is caused by the formation of polar clusters in the medium, which is centrosymmetric in general due to disordering in the sublattice of niobium and tantalum.     

Influence of doping concentration on room-temperature ferromagnetism for Fe-doped BaTiO3 ceramics

Ba(Ti_1−xFe_x)O₃ ceramics (x=7, 30 and 70 at%) were prepared by solid-state reaction. All samples are single-phase with 6H-BaTiO₃-type hexagonal perovskite structure. Mössbauer spectra show all Fe atoms to be present as Fe³⁺ in BaTiO₃ lattice, occupying M1 octahedral and pentahedral sites. Room-temperature ferromagnetism is exhibited and saturation magnetization gradually decreases with increasing Fe content. The observed ferromagnetism is considered to be an intrinsic property of Ba(Ti_1−xFe_x)O₃, originating from super-exchange interactions between Fe³⁺ in different occupational sites associated with oxygen vacancies. The variation in magnetization with Fe content is related to the ratio of pentahedral to octahedral sites and oxygen vacancies.     

Concerning the structural mechanism of oxygen inclusion into the lattice of titanium carbide

Variations in the unit cell occupancy of TiC_xO_y phase are considered in terms of successive oxygen inclusion into the lattice of defect carbides TiC_0.5 ? TiC_0.9. A classification of TiC_xO_y solid solutions formed and the concentration limits of their existence are presented. Three types of cubic ternary solid solutions are shown to occur in the system TiCO: solid solutions of interstitial oxygen inclusion into the initial carbide; solid solutions of oxygen inclusion—carbon and metal exclusion; and solid solutions of oxygen inclusion—oxygen substitution for carbon-carbon and metal exclusion.Specific points (inflection and breaks) on the plots where n_i is the number of atoms per unit cell, n_i = f(y) for TiC_xO_y, are accounted for by both variations in the type of solid solution and the possibility of atomic arrangement in the vicinity of these points. On the basis of the above scheme some experimental peculiarities of Ti carbide phase oxydation are explained.     

Ordered phases of lithium nickelite Li<Subscript>1−<Emphasis Type="Italic">x</Emphasis>−<Emphasis Type="Italic">z</Emphasis></Subscript>Ni<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>2</Subscript>

A symmetry analysis of ordering in lithium nickelite Li_1?x?zNi_1+xO₂ (Li_1?x?z□_yNi_1+xO₂) was performed with regard to the substitution of Li and Ni atoms and the occurrence of structural vacancies □ in the metal sublattice. For all the ordered phases, the k ₉ ⁽³⁾ ray of the Lifshitz {k₉} star is present in the order-disorder transition channel. This ray determines the consecutive alternation of atomic planes filled with only Ni atoms or only Li atoms and vacancies in the \([1\bar 11]_{B1} \) direction. It was shown that the rhombohedral ordered LiNiO₂ phase is formed in the defect-free lithium nickelite, whereas a family of three monoclinic Li₃□Ni₄O₈ (C2/m space group) and Li₂□Ni₃O₆ (C2/m and C2 space groups) superstructures arises as the concentration of structural vacancies increases. For all the superstructures, the order-disorder phase-transition channels were determined and the distribution functions of Li and Ni atoms have been calculated. The long-range order parameters describing each superstructure were found as functions of the Li_{1?x? z}Ni_1+xO₂ composition.     

Description of ferroelectric phase transitions in solid solutions of relaxors in the framework of the random-field theory

A model based on the random-field theory is proposed for calculating the properties of solid solutions of ferroelectric relaxors. The electric dipoles randomly distributed in the system are treated as sources of random fields. The random field distribution function is calculated taking into account the contribution of nonlinear and correlation effects and the differences in the dipole orientations for different solid solution components. The dependence of the phase transition temperature T _c on the concentration of solid solution components is analyzed. Numerical calculations are performed for the lead scandoniobate and lead scandotantalate solid solutions (PbSc_1/2Nb_1/2O₃)_1?x (PbSc_1/2Ta_1/2O₃)_x with different degrees of ordering and the lead magnoniobate and lead titanate solid solution (PbMg_1/3Nb_2/3O₃)_1?x (PbTiO₃)_x. It is shown that the higher transition temperature for more disordered solid solutions of the composition (PbSc_1/2Nb_1/2O₃)_1?x (PbSc_1/2Ta_1/2O₃)_x in the range 0≤x<0.5 is associated with the larger nonlinearity coefficient for PbSc_1/2Nb_1/2O₃ as compared to that for PbSc_1/2Ta_1/2O₃. The theory provides a means for calculating the region of the coexistence of the phases with different symmetry groups in the temperature-composition phase diagram of the (PbMg_1/3Nb_2/3O₃)_1?x (PbTiO₃) solid solution. Numerical calculations with the use of the fitting parameters obtained from the known transition temperatures T _c for the solid solution components adequately describe the experimental phase diagrams for the aforementioned solid solutions of ferroelectric relaxors.     

Chemical order and magnetic properties of the Ni2−xMnSb system

The results of extensive magnetisation, X-ray and neutron powder diffraction measurements on the intermetallic compound series Ni_2-xMnSb, for 0?x?1, are reported. For x ?0.4, a high degree in the C1_b structure is observed, but for x?0.3, some disorder is evident. The series is ferromagnetic, with Curie temperatures rising from 368 to 732 K with decreasing nickel concentration. The magnetic moments all lie in the range (4.0±0.3)μ_B, with a maximum at a composition near x=0.45. The magnetic moments are largely associated with the ordered manganese sites, but it is possible that a small negative moment ?0.25μ_B may be associated with the “nickel sites” for x?0.3. This latter moment may be accounted for by disordered Mn atoms antiferromagnetically aligned.     

Gd-doped SrTi<Subscript>0.5</Subscript>Fe<Subscript>0.5</Subscript>O<Subscript>3–δ</Subscript> mixed ionic-electronic conductors: structural,thermal, and electrical properties

The effect of Sr by Gd substitution on the structural, thermomechanical, electrical, and electrochemical properties of SrTi_0.5Fe_0.5O_3–δ was investigated in the present work. The powders were synthesized by a solid-state reaction method at 1150 °C with following sintering of the ceramic samples at 1350 °C. The unit cell parameters of the sintered Sr_1–x Gd _x Ti_0.5Fe_0.5O_3–δ (x = 0–0.4) ceramics were found to decrease with a gradual increase in Gd content, and a change in the crystal symmetry from cubic to tetragonal at x ≥ 0.1 was observed. It was found that the Gd doping enhanced the stability of the ceramic samples in a reducing atmosphere and reduced the thermal expansion coefficient value. Gd doping in the amount of 5 mol% can be used for long-term stabilization of the SrTi_0.5Fe_0.5O_3–δ material’s conductivity in reducing atmospheres with no significant alteration to the transport properties and oxygen permeability.     

Mossbauer study of ferrite systems Co x Mn1−x Fe2O4 and Ni x Mn1−x Fe2O4

Mössbauer spectra of Co _x Mn_1?x Fe₂O₄ and Ni _x Mn_1?x Fe₂O₄ ferrites withx values ranging from 0·1 to 0·8 in steps of 0·1 have been recorded at room temperature. All spectra exhibit well-defined Zeeman hyperfine patterns. It has been observed that hyperfine field at Fe³⁺ nucleus increases more rapidly by nickel substitution than by cobalt substitution. This has been explained in terms of exchange interactions and cation distribution in the spinels. Hyperfine fields, isomer shifts and quadrupole splittings have been determined.     

Effects of Al doping for Li[Li0.09Mn0.65*0.91Ni0.35*0.91]O2 cathode material

Li-rich Mn-based Li[Li_0.09Mn_{0.65*(0.91???x)} Ni_{0.35*(0.91???x)} Al _x ]O₂ cathode materials have been prepared by traditional solid-state reaction. The lattice parameters a, c, and V have decreased, but c/a increased with the increase of Al doping. All the samples show analogy morphology of a quasi-spherical shape. Li[Li_0.09Mn_0.591Ni_0.319]O₂ sample shows a higher initial discharge capacity of 239.4 mAh?g^?1 at 20 mA?g^?1, while Li[Li_0.09Mn_0.582Ni_0.314Al_0.015]O₂ sample presents a higher discharge capacity of 170.1 mAh?g^?1 and ratio of 72.0 % with 200 vs. 20 mA?g^?1. The solid electrolyte interface resistance (R _SEI) and charge transfer process resistance (R _ct ) values are relatively smaller for Al-doped samples than those of non-doped samples. Almost no reduction is observed after 24-time cycles in different discharge rates for the samples prepared.     

Jahn–Teller effect and superparamagnetism in zn substituted copper-gallate ferrite

Spinel ferrite CuFe₂O₄ and solid solution of Cu_1−xZn_xFe_2−yGa_yO₄ with 0.0?x?0.5 are synthesized through the usual ceramic method. X-ray diffraction measurements confirm the presence of single-phase tetragonal structure with c/a>1for CuFe₂O₄ and compositions with x?0.1. The formation of the tetragonal phase in these samples is attributed to the presence of the cooperative Jahn–Teller Cu ion at the octahedral B-site in the spinel lattice. At the compositional parameter x?0.2, tetragonal-to-cubic transformation occurred and the lattice parameter a for the cubic unit cell is found to decrease with increasing Zn content x. ⁵⁷Fe Mössbauer measurements at 293 K for these compounds reveal superparamagnetic phase for samples with 0.0?x?0.2. In contrast, Mössbauer spectra at 12 K for these materials show well ordered spectra where, the cation distribution and the hyperfine parameters are determined.     

Magnetic properties and specific heat of Dy1−xLaxNi2 compounds

Magnetic and specific heat measurements have been carried out on polycrystalline series of single-phase Dy_1−xLa_xNi₂ (0?x?1) solid solutions. The compounds have a Laves-phase superstructure (space group F4¯3m) with the lattice parameter gradually increasing with decreasing Dy content. The samples with x?0.8 are ferromagnetic with the Curie temperature below 22 K. At high temperatures, all solid solutions are Curie-Weiss paramagnets. The Debye temperature, phonon and conduction electron contributions as well as a magnetic contribution to the heat capacity have been determined from specific heat measurements. The magnetocaloric effect was estimated from specific heat measurements performed in a magnetic field of 0.42 and 4.2 T.