The structural and multiferroic properties of (Bi1−xLax)(Fe0.95Co0.05)O3 ceramics

La and Co co-doped BiFeO₃ ((Bi_1−xLa_x)(Fe_0.95Co_0.05)O₃ (x=0, 0.10, 0.20, 0.30)) ceramics were prepared by tartaric acid modified sol–gel method. The X-ray diffraction patterns indicate a transition from rhombohedral structure to tetragonal structure at x=0.20, which has been confirmed by the Raman measurements. The band gap increases with increasing x to 0.20, and then decreases with further increasing x to 0.30. The structural transition has significant effects on the multiferroic properties. The remnant magnetization and saturate ferromagnetic magnetization decrease abruptly with increasing x to 0.10, and then gradually increase with further increasing x up to 0.30. The coercivity is significantly reduced with increasing La doping concentration. The ferroelectricity has been improved by La doping, and the polarization increases with increasing x to 0.10, then decreases with further increasing x up to 0.30. The simultaneous coexistence of soft ferromagnetism and ferroelectricity at room temperature in tetragonal Bi_0.70La_0.30Fe_0.95Co_0.05O₃ indicates the potential multiferroic applications.     

The multiferroic properties of Bi(Fe0.95Co0.05)O3 films

Bi(Fe_0.95Co_0.05)O₃ films were prepared on conductive indium tin oxide (ITO)/glass substrates by chemical solution deposition. Well saturated polarization hysteresis loop has been observed with a remnant polarization value of about 22 μC/cm² at room temperature. Weak ferromagnetism with saturation magnetization of about 3 emu/cm³ was observed at room temperature. The clear observation of both room temperature ferroelectric and ferromagnetic properties suggests the potential multiferroic applications of Bi(Fe_0.95Co_0.05)O₃.     

Conductivity and sintering property of LaNi1 − xFexO3 ceramics prepared by Pechini method

Preparation of LaNi_1 − xFe_xO₃, which is one of the candidate materials of solid oxide fuel cell cathode, current collecting layer and interconnect coating was examined with Pechini method and solid state reaction method. Single phase LaNi_1 − xFe_xO₃ with large Ni content has successfully been prepared by low temperature sintering as 750 °C with Pechini method, whereas large amount of raw materials has remained with solid state reaction method by sintering at the same temperature. It can be ascribed to more homogenous cation distribution in raw powder material prior to sintering with Pechini method. It has also been revealed that LaNi_1 − xFe_xO₃ with x lower than 0.3 is thermodynamically unstable in air above 1000 °C. LaNi_0.6Fe_0.4O₃ showed superior property as cathode material with high electrical conductivity, thermodynamic stability and appropriate sintering property.     

Microstructures and multiferroic properties of textured Bi0.8La0.2FeO3 thin films

La-substituted BiFeO₃, Bi_0.8La_0.2FeO₃, thin films were fabricated on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition. X-ray diffraction and high-resolution transmission electron microscope were used to analyze the structures of the films. The results show the films fabricated under optimized growth condition are (0 1 2) textured. X-ray photoemission spectroscopy results indicate that the oxidation state of Fe ion is Fe³⁺ in the films without detectable Fe²⁺. The films show low leakage current and excellent dielectric characters. Multiferroic properties with a remnant ferroelectric polarization of 5.2 μC/cm² and a remanent magnetization of 0.02 μ_B/Fe were established. These results have some implications for further research.     

Luminescent properties of HTP AgGd1−xW2O8:Eux and AgGd1−x(W1−yMoy)2O8:Eux phosphor for white LED

Intense red phosphors, AgGd_1−xEu_x(W_1−yMo_y)₂O₈ (x=0.0-1.0, y=0.0-1.0), have been synthesized through traditional solid-state reaction and characterized by X-ray diffraction (XRD) and photoluminescence (PL). XRD results reveal that AgGd_1−xEu_xW₂O₈ synthesized at 1000 °C has a tetragonal crystal structure, which is named as high temperature phase (HTP) AgGdW₂O₈. All phosphors compositions with Eu³⁺ show red and green emission on excitation either in the charge-transfer or Eu³⁺ levels. Analysis of the emission spectra with different Eu³⁺ concentrations reveal that the optimum dopant concentration for Eu³⁺ is x=0.6 in the HTP AgGd_1−xEu_xW₂O₈ (x=0.0-1.0). Studies on the AgGd_0.4Eu_0.6(W_1−yMo_y)₂O₈ (y=0.0-1.0) and AgGd_1−xEu_x(W_0.7Mo_0.3)₂O₈ (x=0.0-1.0) show that the emission intensity is maximum for compositions with y=0.3 and x=0.5, respectively, and a decrease in emission intensity is observed for higher y or x values. The Mo⁶⁺ and Eu³⁺ co-doped AgGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped AgGd(WO₄)₂ in UV region. The intense emission of the tungstate/molybdate phosphors under 394 and 465 nm excitations, respectively, suggests that these materials are promising candidates as red-emitting phosphors for near-UV/blue GaN-based white LED for white light generation.     

Magnetic characterization of Bi(Fe1 − xMnx)O3

Bi(Fe_1 − xMn_x)O₃ ceramics (x up to 0.3) were prepared by rapid sintering. Weak ferromagnetism with two magnetic anomalies at low temperatures was observed for Bi(Fe_0.95Mn_0.05)O₃ and Bi(Fe_0.9Mn_0.1)O₃. From temperature-dependent magnetic relaxation measurements, the anomalies at 20 K and 100 K are related to the freezing of cluster spin glass.     

Influence of substrate temperature in BiFeO3-CoFe2O4 nanocomposites deposited on SrTiO3 (0 0 1)

BiFeO₃-CoFe₂O₄ epitaxial nanocomposites have been deposited on SrTiO₃ (0 0 1) substrates by pulsed laser deposition. We present here a study of the influence of the deposition temperature (T_S), in the 550-800 °C range, on the film composition, morphology and microstructure. Electron-probe microanalysis shows strong reduction of the Bi content in the films when increasing T_S. Films prepared at T_S=750 °C and above are virtually Bi-free. X-ray diffraction (XRD) data show that, due to the volatility of Bi, there is a progressive reduction in the amount of BiFeO₃. The deposition temperature and the concomitant presence of Fe_xO_y spurious phases in the nanocomposites grown at high temperature promote radical changes in film morphology and magnetization. It thus follows that a temperature range suitable for controlled modification of nanocomposites morphology would be extremely narrow.     

The structure and luminescence properties of long afterglow phosphor Y3−xMnxAl5−xSixO12

A series of phosphors with the composition Y_3−xMn_xAl_5−xSi_xO₁₂ (x=0, 0.025, 0.050, 0.075, 0.150, 0.225, 0.300) were prepared with solid state reactions. The X-ray powder diffraction analysis of samples shows that the substitution of Mn²⁺ and Si⁴⁺ does not change the garnet structure of phosphors, but makes the interplanar distance decrease to a certain extent. The emission spectra show that Mn²⁺ in Y₃Al₅O₁₂ emits yellow-orange light in a broad band. With the increment of substitution content, the emission intensity of the phosphors increases firstly then decreases subsequently, and the emission peak moves to longer wavelength. Afterglow spectra and decay curves show that all the Mn²⁺ and Si⁴⁺ co-doped samples emit yellow-orange light with long afterglow after the irradiation of ultraviolet light. The longest afterglow time is 18 min. Thermoluminescence measurement shows that there exist two kinds of traps with different depth of energy level and their depth decreases with the increment of substitution content.     

Magnetic properties of Ni-substituted BiFeO3

BiFe_1−xNi_xO₃ ceramic powders with x up to 0.10 have been prepared by the sol-gel technique. The band gap of BiFeO₃ is 2.23 eV, and decreases to 2.09 eV for BiFe_0.95Ni_0.05O₃ and BiFe_0.90Ni_0.10O₃. The Mössbauer spectra show sextet at room temperature, indicating the magnetic ordering and the presence of only Fe³⁺ ions. Superparamagnetism with blocking temperature of 31 K for BiFe_0.95Ni_0.05O₃ and 100 K for BiFe_0.90Ni_0.10O₃ was observed. Enhanced magnetization at room temperature have been observed (1.0 emu/g for BiFe_0.95Ni_0.05O₃ and 2.9 emu/g for BiFe_0.90Ni_0.10O₃ under magnetic field of 10,000 Oe), which is one order larger than that of BiFeO₃ (0.1 emu/g under magnetic field of 10,000 Oe). The enhanced magnetization was attributed to the suppression of the cycloidal spin structure by Ni³⁺ substitution and the ferrimagnetic interaction between Fe³⁺ and Ni³⁺ ions.     

BiFeO3/Zn1−xMnxO bilayered thin films

BiFeO₃/Zn_1−xMn_xO (x = 0-0.08) bilayered thin films were deposited on the SrRuO₃/Pt/TiO₂/SiO₂/Si(1 0 0) substrates by radio frequency sputtering. A highly (1 1 0) orientation was induced for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO thin films demonstrate diode-like and resistive hysteresis behavior. A remanent polarization in the range of 2P_r ∼ 121.0-130.6 μC/cm² was measured for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO (x = 0.04) bilayer exhibits a highest M_s value of ∼15.2 emu/cm³, owing to the presence of the magnetic Zn_0.96Mn_0.04O layer with an enhanced M_s value.     

The magnetic properties of oxide spinel Li0.5Fe2.5−2xAlxCrxO4 solid solutions

The exchange interactions (J_BB and J_AB are the intra and the inter-sublattice exchange interactions between neighbouring spins, respectively) are obtained by using the general expressions of canting angle and critical temperature obtained by mean field theory of Li_0.5Fe_2.5−2xAl_xCr_xO₄. The expression of magnetic energy of Li_0.5Fe_2.5−2xAl_xCr_xO₄ is obtained for different spin configurations and dilution x. The saturation magnetisation of Li_0.5Fe_2.5-2xAl_xCr_xO₄ is obtained with different values of dilution x. The magnetic phase diagram of Li_0.5Fe_2.5-2xAl_xCr_xO₄ materials is obtained by high temperature series expansions (HTSEs). The critical exponent associated with the magnetic susceptibility of Li_0.5Fe_2.5−2xAl_xCr_xO₄ is deduced.     

Soft-mode driven tetragonal-to-monoclinic phase transition in multiferroic BiFeO3

The phase transition of BiFeO₃ (BFO) from tetragonal to monoclinic induced by pressure was investigated by first-principles method. The sequential monoclinic phase, _Ma$M_{\mathrm{a}}$, which is favorable during low compression with respect to the tetragonal phase, was characterized. The order parameters were calculated in the vicinity of the phase transition, showing that phase transition has a second-order character. The results demonstrated that the pressure-induced tetragonal-to-monoclinic phase transition in BFO is related to the softening behavior of the E mode, which are very helpful in further investigations of the morphotropic phase boundary (MPB) in lead-free materials.     

Crystal structure and photoluminescence of (Y1−xCex)2Si3O3N4

Oxonitridosilicate phosphors with compositions of (Y_1−xCe_x)₂Si₃O₃N₄ (x=0−0.2) have been synthesized by solid state reaction method. The structures and photoluminescence properties have been investigated. Ce³⁺ ions have substituted for Y³⁺ ions in the lattice. The emission and excitation spectra of these phosphors show the characteristic photoluminescence spectra of Ce³⁺ ions. Based on the analyses of the diffuse reflection spectra and the PL spectra, a systematic energy diagram of Ce³⁺ ion in the forbidden band of sample with x=0.02 is given. The best doping Ce content in these phosphors is ∼2 mol%. The quenching temperature is ∼405 K for the 2 mol% Ce content sample. The luminescence decay properties were investigated. The primary studies indicate that these phosphors are potential candidates for application in three-phosphor-converted white LEDs.     

Sn1−xBixO2 and Sn1−xTaxO2 (0≤x≤0.75): A first-principles study

The structural, elastic, electronic and optical (x=0) properties of doped Sn_1−xBi_xO₂ and Sn_1−xTa_xO₂ (0≤x≤0.75) are studied using the first-principles pseudopotential plane-wave method within the local density approximation. The independent elastic constants C_ij and other elastic parameters of these compounds have been calculated for the first time. The mechanical stability of the compounds with different doping concentrations has also been studied. The electronic band structure and density of states are calculated and the effect of doping on these properties is also analyzed. It is seen that the band gap of the undoped compound narrowed with dopant concentration, which disappeared for x=0.26 for Bi doping and 0.36 for Ta doping. The materials thus become conductive oxides through the change in the electronic properties of the compound for x≤0.75, which may be useful for potential application. The calculated optical properties, e.g. dielectric function, refractive index, absorption spectrum, loss-function, reflectivity and conductivity of the undoped SnO₂ in two polarization directions are compared with both previous calculations and measurements.     

Mn:BiFeO3/Zn:BiFeO3 bilayered thin films of (1 1 1) orientation

Ferroelectric and fatigue behavior of bilayered thin films consisting of Mn⁴⁺-modified BiFeO₃ and Zn²⁺-modified BiFeO₃, which were deposited on SrRuO₃-buffered Pt coated silicon substrates, were systematically investigated. The (1 1 1) orientation is induced for the BiFe_0.95Mn_0.05O₃/BiFe_0.95Zn_0.05O₃ bilayer, due to the introduction of the bottom BiFe_0.95Zn_0.05O₃ layer. With increasing the thickness ratio of the BiFe_0.95Mn_0.05O₃ layer, their leakage current decreases, and the fatigue endurance is greatly improved owing to the introduction of the BiFe_0.95Mn_0.05O₃ layer with a lower fatigue rate. The BiFe_0.95Mn_0.05O₃/BiFe_0.95Zn_0.05O₃ bilayer with the thickness ratio of 3:1 exhibits a larger remanent polarization of 2P_r ∼ 161.0 μC/cm² than those of bilayers with different thickness ratios, while their coercive field slightly increases with increasing the thickness ratio of the BiFe_0.95Mn_0.05O₃ layer.     

Effect of Fe substitution on multiferroic hexagonal YMnO3

Polycrystalline YMn_1−xFe_xO₃ (x=0.02-0.20) powders were synthesized by means of modified citrate method. Powder X-ray diffraction gives evidence that all the samples are single phase and exhibit hexagonal structure with P6₃cm space group as observed for YMnO₃. The solubility limit of Fe was determined as about 6 wt.%. Cell parameter values were found to increase with Fe content, since Fe³⁺ and Mn³⁺ have the same ionic radii. This can be attributed to the increase of the tilting of MnO₅ bipyramid and the buckling of Y atoms. In addition, ⁵⁷Fe Mössbauer spectrometry provides evidence of two Fe³⁺ sites attributed to two different nearest atomic neighbours. Magnetic properties reveal a paramagnetic-to-antiferromagnetic transition, a possible increase of the magnetic anisotropy, and a competition between ferromagnetic and antiferromagnetic interactions.     

Synthesis and ferroelectric properties of bismuth layer-structured (Bi7−xSrx)(Fe3−xTi3+x)O21 solid solutions

Bismuth layer-structured (Bi_7−xSr_x)(Fe_3−xTi_3+x)O₂₁ (BSFT) ceramics were synthesized and the ferroelectric properties and crystal structure were investigated. X-ray powder diffraction profiles and refinement of the lattice parameters indicated single phase BSFT was obtained in the composition range 0-1.5. The lattice parameter b of BSFT remained almost constant, while a slight decrease in the lattice parameter a was observed by the Sr and Ti substitution for Bi and Fe, respectively, which indicated an increase in the orthorhombicity. The dependence of the BSFT lattice parameter on temperature implied a phase transition from the orthorhombic to the tetragonal phase, which was in good agreement with the Curie temperature. The remnant polarization P_r, of BSFT was significantly improved by the Sr and Ti substitution for Bi and Fe, and ranged from 9 to 16 μC/cm², although no remarkable variation in the coercive field E_c was observed. As a result, a well-saturated P-E hysteresis loop of BSFT ceramic was obtained at x=0.5 with a P_r of 30 μC/cm at an applied voltage of 280 kV/cm.     

Site preference and magnetism of Fe3−xCrxAl0.5Si0.5

In order to gain better insight into the origin of the observed differences between Fe_3−xCr_xAl and Fe_3−xCr_xSi, alloys of Fe_3−xCr_xAl_0.5Si_0.5 (x=0, 0.125, 0.250, 0.375 and 0.5) were prepared and studied by means of X-ray and neutron diffraction as well as by magnetization measurements. Electronic structure calculations of these alloys have been performed by means of TB-LMTO-ASA method. It was expected, and experimentally verified, that the presence of silicon and aluminum atoms in 1:1 proportion will result in the independence of the lattice parameter on the iron/chromium concentration. All samples have been proved to be a single phase of the DO₃-type of structure. Theoretical and experimental results indicate that chromium atoms locate preferentially in B sublattice. Cr magnetic moments are oriented antiparallel to Fe magnetic moments. Neutron measurements show a linear dependence of the magnetic moments of Fe(A,C), Fe(B) and Cr(B) as a function of Cr concentration. However the calculated total magnetic moment decreases faster with chromium content than indicated by the experiment.     

High temperature ferromagnetism of the vacuum-annealed (In1−xFex)2O3 powders

(In_1−xFe_x)₂O₃ (x = 0.02, 0.05, 0.2) powders were prepared by a solid state reaction method and a vacuum annealing process. A systematic study was done on the structural and magnetic properties of (In_1−xFe_x)₂O₃ powders as a function of Fe concentration and annealing temperature. The X-ray diffraction and high-resolution transmission electron microscopy results confirmed that there were not any Fe or Fe oxide secondary phases in vacuum-annealed (In_1−xFe_x)₂O₃ samples and the Fe element was incorporated into the indium oxide lattice by substituting the position of indium atoms. The X-ray photoelectron spectroscopy revealed that both Fe²⁺ and Fe³⁺ ions existed in the samples. Magnetic measurements indicated that all samples were ferromagnetic with the magnetic moment of 0.49-1.73 μ_B/Fe and the Curie temperature around 783 K. The appearance of ferromagnetism was attributed to the ferromagnetic coupling of Fe²⁺ and Fe³⁺ ions via an electron trapped in a bridging oxygen vacancy.     

CO2 adsorption on Cr(1 1 0) and Cr2O3(0 0 0 1)/Cr(1 1 0)

We attempt to correlate qualitatively the surface structure with the chemical activity for a metal surface, Cr(1 1 0), and one of its surface oxides, Cr₂O₃(0 0 0 1)/Cr(1 1 0). The kinetics and dynamics of CO₂ adsorption have been studied by low energy electron diffraction (LEED), Aug er electron spectroscopy (AES), and thermal desorption spectroscopy (TDS), as well as adsorption probability measurements conducted for impact energies of E_i = 0.1-1.1 eV and adsorption temperatures of T_s = 92-135 K. The Cr(1 1 0) surface is characterized by a square shaped LEED pattern, contamination free Cr AES, and a single dominant TDS peak (binding energy E_d = 33.3 kJ/mol, first order pre-exponential 1 × 10¹³ s⁻¹). The oxide exhibits a hexagonal shaped LEED pattern, Cr AES with an additional O-line, and two TDS peaks (E_d = 39.5 and 30.5 kJ/mol). The initial adsorption probability, S₀, is independent of T_s for both systems and decreases exponentially from 0.69 to 0.22 for Cr(1 1 0) with increasing E_i, with S₀ smaller by ∼0.15 for the surface oxide. The coverage dependence of the adsorption probability, S(Θ), at low E_i is approx. independent of coverage (Kisliuk-shape) and increases initially at large E_i with coverage (adsorbate-assisted adsorption). CO₂ physisorbs on both systems and the adsorption is non-activated and precursor mediated. Monte Carlo simulations (MCS) have been used to parameterize the beam scattering data. The coverage dependence of E_d has been obtained by means of a Redhead analysis of the TDS curves.