Effect of Dy substitution on structural,magnetic and optical properties of BiFeO3 ceramics

Bi_1−xDy_xFeO₃ (x=0.0, 0.03, 0.05, 0.07, 0.10 and 0.12) ceramics were synthesized by solid state reaction method. Effects of Dy substitution on structural distortion, magnetic and optical properties of BiFeO₃ were examined by X-ray diffraction, Raman and UV–Visible spectroscopy. The samples were found to crystallize in rhombohedral structure of BiFeO₃ with R3c space group. The reduction in lattice parameters and unit cell volume indicate the distortion in FeO₆ octahedra of the rhombohedral structure without any signature of phase transformation up to x=0.12. The predictable weak ferromagnetic hysteresis loops can be observed in the Dy doped samples with maximum remnant magnetization of 0.2103 emu/g for x=0.12. The weak ferromagnetism is ascribed to the suppressed spiral spin structure and magnetically active characteristic of Dy³⁺ ions together with ferromagnetic coupling between Dy³⁺ and Fe³⁺ ions. With optical band gap in visible region, Dy doped BiFeO₃ ceramics are potential material for optoelectronic device and solar cell applications.     

The substitution of Fe2+ ions by Ni2+ ions in green rust one compounds

The oxidation of Fe(OH)₂ in the presence of Cl^– or CO ₃ ^2– ions leads, in the first stage of the reaction, to chloride-containing green rust one (GR1), 3Fe(OH)₂· Fe(OH)₂Cl·nH₂O, or carbonate-containing GR1, 4Fe(OH)₂·Fe₂(OH)₄CO₃·nH₂O, respectively. These GR1 compounds give the ferric oxyhydroxides by further oxidation. If a hydroxide Ni _x Fe_1–x (OH)₂ is initially precipitated, the reaction leads to a nickelous-ferric compound isomorphous to the ferrous-ferric GR1, but stable with respect to the oxidizing action of air. Similarly, the oxidation of a nickelous-ferrous hydroxide, in the presence of excess OH^– ions, leads to a nickelous-ferric GR1, a layered hydroxide with anionic interlayers made of OH^– ions and water molecules. The Mössbauer spectra of these nickelousferric GR1 display two ferric doublets, D₀ withIS=0.34 mm/s andQS=0.45 mm/s and D₁ withIS=0.36 mm/s andQS=0.86 mm/s. The existence of a ferrous-ferric GR1 incorporating OH^– ions, a compound never observed so far, is strongly suspected.     

Influence of Fe doping on the structural,optical and magnetic properties of ZnS diluted magnetic semiconductor

Fe doped ZnS nanoparticles with different concentrations of Fe, synthesized by microwave assisted co-precipitation method have been reported. The incorporation of Fe²⁺ and Fe³⁺ ions into ZnS lattice are confirmed by X-ray diffraction (XRD) and Electron Paramagnetic resonance (EPR) study. XRD and High Resolution Transmission electron Microscope (HRTEM) results confirm the phase purity of the samples and indicate a reduction of the particle size with increase in Fe concentration. EDAX analysis confirms the presence of Zn, S and Fe in the samples. A yellow–orange emission peak is observed in Photoluminescence (PL) spectra which exhibits the Characteristic ⁴T₂ (4G)–⁶A₁ (6S) transition of Fe³⁺ ion. The room temperature magnetic studies as analyzed from M–H curves were investigated from vibrating samples magnetometer (VSM) which shows a weak ferro and superparamagnetic like behavior in 1% and 3% Fe-doped ZnS nanocrystals, whereas; at 10% Fe-doping concentrations, antiferromagnetism behavior is achieved. The ZFC-FC measurement reveals that the blocking temperature of the nanoparticle is above the room temperature.     

Spin states of Ni3+ ions in PrSrAl1−x Ni x O4 ceramics

Solid solutions PrSrAl_1−x Ni _x O₄ have been synthesized and studied by electron paramagnetic resonance (EPR). It is shown that atx≤0.2 the Ni³⁺ ions may be present both in the high- and low-spin states. Asx increases, the part of high-spin centers increases as well. Models of the paramagnetic centers accounting for micro-heterogeneous structure of these ceramics are proposed. The observed features of the temperature dependence of the EPR signals are explained by the interaction of the nickel ions with fast-relaxing Pr³⁺ ions.     

The substitution of Fe2+ ions by Ni2+ ions in the green rust 2 compound studied by Mössbauer effect

Green rust 2 is usually obtained by oxidizing an initial mixture of FeSO₄ and NaOH solutions and a complete oxidation leads mainly towards γ oxyhydroxide known as lepidorocite. By adding some NiSO₄ one can stop at the first stage and Mössbauer spectra reveral only ferric doublets. This implies that the initial formula 4Fe(OH)₂, 2FeOOH, FeSO₄ of green rust 2 must be replaced byxNi(OH)₂, (6?x)FeOOH, NiSO₄, wherex scans from 2 to 4. It also means that all initial ferrous ions become oxidized into the ferric state leaving the Ni₂₊ ions unchanged. Therefore the end product of oxidation is the nickel containing green rust 2 at the place of the usual lepidocrocite.     

Influence of Fe ions in characteristics and optical properties of mesoporous titanium oxide thin films

Fe-doped mesoporous titanium dioxide (M-TiO₂-Fe) thin films have been prepared on indium tin oxide (ITO) glass substrates by sol–gel and spin coating methods. All films exhibited mesoporous structure with the pore size around 5–9 nm characterized by small angle X-ray diffraction (SAXRD) and further confirmed by high resolution transmission electron microscopy (HRTEM). Raman spectra illustrated that lower Fe-doping contributed to the formation of nanocrystalline of M-TiO₂-Fe thin films. X-ray photoelectron spectroscopy (XPS) data indicated that the doped Fe ions exist in forms of Fe³⁺, which can play a role as e⁻ or h⁺ traps and reduce e⁻/h⁺ pair recombination rate. Optical properties including refractive indices/n, energy gaps/E_g and Urbach energy width/E₀ of the thin films were estimated and investigated by UV/vis transmittance spectra. The presence of Fe content extended the light absorption band and decreased the values of n, implying enhanced light response and performance on dye-sensitized solar cells (DSSC). The optimum Fe content in M-TiO₂-Fe thin films is determined as 10 mol%, for its compatibility of well crystalline and well potential electron transfer performance.     

Effect of lanthanum ions on magnetic properties of Y3Fe5O12 nanoparticles

Lanthanum ion (La³⁺)-substituted garnet nanoparticles Y_3?x La _x Fe₅O₁₂ (x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0) were fabricated by a sol–gel method. Their crystalline structures and magnetic properties were investigated by using X-ray diffraction (XRD), vibrating sample magnetometer (VSM), and Mössbauer spectrum. The XRD results show that samples of Y_3?x La _x Fe₅O₁₂ (0.0 ≤ x ≤ 0.8) are all single phase and the sizes of particles range from 32 to 65 nm. Those of Y₂LaFe₅O₁₂ consisted of peaks from garnet and LaFeO₃ structures. Compared to pure YIG, the saturation magnetization is larger when the La concentration x = 0.2. However, with increasing La concentration (x), it decreases obviously. Meanwhile, may be due to the enhancement of the surface spin effects, the saturation magnetization rises as the particle size is increased. Different from the pure YIG, the Mössbauer spectra of Y_2.8La_0.2Fe₅O₁₂ and Y_2.2La_0.8Fe₅O₁₂ are composed of four sets of six-line hyperfine patterns. The results tell us that the substitution of La³⁺ ions with large ionic radius (1.061 Å) will give rise to a microscopic structure distortion of the a- and d-sites to different degrees, and the Zeeman sextets from a- and d-sites begin to split into two sub-sextets, which is helpful to explain the phenomenon observed in the study of the magnetic property.     

Effect of Fe substitution on the magnetic properties of half-Heusler alloy CoCrAl

The effect of Fe substitution for the vacant site in half-Heusler alloy CoCrAl is studied. A series of single phase CoFe_xCrAl (x=0.0, 0.25, 0.5, 0.75 and 1.0) alloys has been successfully synthesized. The lattice constant is found to increase almost linearly with increasing Fe content, indicating Fe atoms enter the lattice of CoCrAl instead of existing as a secondary phase. When Fe entering the vacant site, spin polarization occurs and the alloy turns from a semimetal in CoCrAl to a half-metallic ferromagnet (HMF) in CoFeCrAl. This is due to the reconstruction of the energy band with Fe substitution. The Curie temperature and saturation magnetic moments are enhanced and increase monotonically with increasing Fe content. The variation of the spin moment follows the Slater-Pauling curve and agrees with the theoretical calculation as well.     

The optical properties of Yb3+ ions in LiTaO3:Nd,Yb crystals

3+ ions excited by energy transfer from Nd³⁺ ions in LiTaO₃:Nd, Yb crystals are presented. The emission band of Yb³⁺ ions is broad, due to the strong phonon-coupling and to the relative large Stark-splitting of the ground ²F_7/2 multiplet. The emission cross-section was evaluated by the reciprocity method, and a value of 0.53×10^-20 cm² was obtained. The gain coefficients derived for the inversion parameters in the range 0.05 to 0.5 indicate positive gain in the 985–1070 nm range. Received: 17 March 1997/Revised version: 10 June 1997     

Influence of the small substitution of Z=Ni, Cu, Cr, V for Fe on the magnetic, magnetocaloric, and magnetoelastic properties of LaFe11.4Si1.6

We have studied the magnetic, magnetocaloric, and magnetostriction properties of LaFe_11.4Si_1.6 and La(Fe_0.99Z_0.01)_11.4Si_1.6 (Z=Ni, Cu, Cr, V) compounds using magnetization and strain gauge techniques. It was found that substitution of 1% of the Fe by Z-elements results in an increase in the Curie temperature (T_C), and affects the magnetostriction and magnetocaloric properties of the parent compound, LaFe_11.4Si_1.6. A maximum shift in T_C of about 11 K, and significantly smaller hysteresis losses in the vicinity of T_C compared with those of the base compound, were found for Z=V. The maximum magnetovolume coupling constant was estimated to be n_dd≈2.7×10⁻³ (μ_B/Fe atom)⁻² for the parent compound. The changes in the volume magnetostriction, the magnetovolume coupling constant, and the magnetocaloric properties are strongly correlated with composition. The relative effects of the variation in cell parameters and electron concentration on the magnetostriction, T_C, and the magnetocaloric properties are discussed.     

Structural,thermal, and optical properties of Er3+/Yb3+ co-doped oxyhalide tellurite glasses,glass-ceramics and ceramics

Glass-ceramics and ceramics containing nano-crystals of different phases doped with Er³⁺/Yb³⁺ ions have been successfully prepared by heat treatment of the precursor oxyhalide glasses synthesized by the melt-quench method. X-ray diffraction patterns and transmission electron microscopy (TEM) images verify the precipitation of nano-crystals. Emission of Er³⁺ enhances several times when Yb³⁺ ion is added with the matrix. The Stark splitting and the intensity of different emission bands increase to a great extent when we approach to ceramics from glasses via glass-ceramics. The intensity of the blue and green emission bands increases much faster than the red and NIR emission bands. Intense upconversion emission observed by the naked eye has been quantified in terms of standard chromaticity diagram (CIE). Power dependence study shows that the upconversion of NIR radiation to visible radiation takes place mainly via photon avalanche (PA) process.     

Influence of V substitution for Fe on the transport and magnetic properties of Sr2FeMoO6

We have investigated the crystal structure, magnetization and magnetoresistance of the double perovskite compounds Sr₂(Fe_1−xV_x)MoO₆ (0≤x≤0.1). The lattice constants and the cation ordering decrease monotonously with the V content. The Curie temperature, saturation magnetization and low field magnetoresistance of the compounds decrease with increasing x due to the reduced degree of ordering. The resistivity of Sr₂FeMoO₆ and lightly doped samples shows semiconductive behavior, while the samples with higher doping levels exhibit a semiconductor-metal transition around 80 K.     

Influence of partial rare-earth substitution for Sm in the giant intrinsic magnetic hardness compound SmCo2Ni3

The phenomenon of giant intrinsic magnetic hardness is investigated in compounds R_1?x Sm _x Co₂Ni₃ with R=Y, Pr, Gd, Tb, Er. Partial Er substitution for Sm actually increases magnetic hardness while all other substitutions decrease magnetic hardness. The strength of coercivity is thus dependent on both the sign and magnitude of the crystal field interaction. The temperature dependence of coercivity is complex in the case of Pr substitution as a result of competing effects from thermal activation and a decrease in anisotropy at low temperatures.     

Evolution of the optical properties and the electrical resistivity of CaMnO3 during the substitution of Mo for Mn ions

The reflectance, the optical density, and the optical conductivity spectra of CaMn_{1 ? x} Mo _x O₃ (x ≤ 0.07) polycrystals are studied over a wide spectral region. The substitution of Mo⁶⁺ ions for Mn⁴⁺ ions leads to a strong decrease in the first high-energy phonon band, which is related to vibrations in the MnO₆ octahedron. The appearance of band-type charge carriers is detected in CaMn_{1 ? x} Mo _x O₃ with x ≤ 0.04, and carrier localization is observed in CaMn_0.93Mo_0.07O₃. This localization increases at T < 160 K, i.e., during the transition from the paramagnetic to the antiferromagnetic state with orbital ordering and a monoclinic structure. The optical conductivity spectrum of CaMn_0.93Mo_0.07O₃ exhibits a strong shift of fundamental absorption bands, which is associated with a change in the band structure because of a decrease in the splitting of the 3d levels of Mn in the crystal field.     

Effect of Ca substitution on structural,magnetic and dielectric properties of BiFeO3

Bi_1-xCa_xFeO₃ (x = 0.40, 0.50) compounds are synthesized by conventional solid-state reaction method. The effect of Ca²⁺ substitution is investigated on structural, dielectric and magnetic properties. Rietveld refinement confirms that crystal structures of both the samples are tetragonal with P4mm symmetry. The highest values of remnant magnetization (M_r ) and coercive field (H_c ) are 0.002 emu/g and 0.23 kOe, respectively, for x = 0.50. The electric modulus formalism is used to distinguish and separate out the relaxation process which is dominated by the transport phenomenon. The relaxation process has activation energy ～0.32 eV which is found to be related to both the hopping mechanisms, i.e. electronic and oxide ions.