High-temperature thermoelectric characteristics of B-site substituted Yb0.1Ca0.9Mn1−x Nb x O3 system (0≤x≤0.1)

The thermoelectric performance of Yb_0.1Ca_0.9MnO₃ doped with Nb⁵⁺ at B-site is investigated in this paper. It is found that there is a phase transition from O-type to O*-type orthorhombic structure with increasing of Nb doping content, which indicates that the structure distortion becomes more seriously. Since the electron–phonon interaction can be enhanced by the structure distortion, the small polaron formation is promoted in Yb_0.1Ca_0.9Mn_1?x Nb _x O₃ with increasing Nb content. In the whole measured temperature range, the electrical conductivity can be fitted very well by the adiabatic small polaron hopping model. The activated energy E _α is ascending with increasing Nb content. The temperature dependence of Seebeck coefficient S of Yb_0.1Ca_0.9Mn_1?x Nb _x O₃ shows that the S is basically inversive to the charge carrier concentration. S(T) can be fitted well by the Cutler and Mott model, which indicates that the density of state around the Fermi level is strongly affected by Nb-doping at B-site. It is contrary to those of CaMnO₃ and RE_0.1Ca_0.9MnO₃, when Nb content x>0.05, the |S| and σ show a same tendency of the temperature dependence.     

Structural, spectroscopic, magnetic and electrical characterization of Ca-doped polycrystalline bismuth ferrite, Bi(1-x)Ca(x)FeO(3-x/2) (x ≤ 0.1)

The crystal structure and physical properties of multiferroic polycrystalline Ca(2+)-doped BiFeO(3) samples have been investigated. The present experimental investigation suggests that Bi(1-x)Ca(x)FeO(3-x/2) (x ≤ 0.1) can be considered as a solid solution between BiFeO(3) and CaFeO(2.5). The oxidation state of Fe in these materials is + 3 and charge balance occurs through the creation of oxygen vacancies. For each composition, two structural phase transitions are revealed as anomalies in the variable-temperature in situ x-ray diffraction data which is consistent with the well-established high-temperature structural transformation in pure BiFeO(3). All compositions studied show antiferromagnetic behaviour along with a ferromagnetic component that increases with Ca(2+) doping. The resistivities of the Bi(1-x)Ca(x)FeO(3-x/2) samples at room temperature are of the order of 10(9) Ω cm and decrease with increasing Ca(2+) content. Arrhenius plots of the resistivity show two distinct linear regions with activation energies in the range of 0.4-0.7 and 0.03-0.16 eV. A correlation has been established between the critical temperatures associated with the structural phase transitions and the multiferroic properties. A composition of x = 0.085 is predicted to show maximum magneto-electric coupling.     

Structural and electronic properties of InNxP1-x alloy in full range (0 ≤ x ≤1)

We have performed first-principles method to investigate structural and electronic properties of InN_xP_1?x ternary semiconductor alloy in full range (0 ≤ x ≤ 1) using density functional theory. We have used modified Becke–Johnson potential to obtain accurate band gap results. From the electronic band structure calculation we have found that InN_xP_1?x become metal between 47 and 80% of nitrogen concentration. Additional to our band gap calculations, we have also used the band anticrossing model. The band anticrossing model supplies a simple, analytical expression to calculate the physical properties, such as the electronic and optical properties, of III-N_xV_1?x alloys. The knowledge of the electron density of states is required to understand and clarify some properties of materials such as the band structures, bonding character and dielectric function. In order to have a deeper understanding of these properties of the studied materials, the total and partial density of states has been calculated. Finally, we have calculated the total bowing parameter b of studied alloys, together with three contributions b_VD, b_CE, and b_SR due to volume deformation, different atomic electron negativities and structural relaxation, respectively.     

Effects of Ni doping on the structural properties and collapse of magnetic ordering in NdFe_(1-x)Ni_xO_3(0.1 ≤x≤ 0.7) orthoferrites

Nd Fe_(1-x)Ni_xO_3(0.1 ≤ x ≤ 0.7) orthoferrites are synthesized by solid state reaction method, and the structural properties of these materials are investigated by employing x-ray diffraction(XRD), scanning electron microscopy(SEM) and M o¨ssbauer spectroscopy. The orthorhombic structure is observed in all systems; however, with the increase in Ni doping,the increase in tolerance factor and the decrease in the cell volume are observed. Orthorhombic distortion decreases with Ni content increasing up to 50%, while above 50% Ni doping it increases. SEM examination indicates the increases in grain size and intermixing of grains with increase in Ni concentration. Comparison between bulk and theoretical densities shows that in each of all samples porosity is less than 2%. M?ssbauer spectroscopic investigations are performed to explain local structure, Fe oxidation states and collapse of the magnetic ordering. In these samples the Fe oxidation state remains+3 and there is no considerable increase in hole states observed; however due to mismatch of the ionic radii between Fe~(3+) and Ni~(3+), octahedral distortions, sagging and distribution of hyperfine parameters increase with increase in Ni concentration. The major factors behind the collapse of magnetic ordering in the Ni-doped systems are the weakening of the super-exchange interactions, decrease in the Neel temperature, increase in spin–spin relaxation frequency and high spin to low spin transition.     

Structure and superconductivity studies on (Y1-xLa x )Ba2Cu3O7 (0 ≤ x ≤ 1)

Studies on (Y_{1 - x}La _X )Ba₂Cu₃O₇, x = 0.0 - 1.0, in steps of 0.1, have been carried out. Results show that for x ≤ 0.4, orthorhombicity and high T_c of 90 K are retained. T_c decreases gradually for x ≥ 0.4. Pure LaBa₂Cu₃O₇ shows a T_C ^ZERO of 73 K. XRD data do not reveal any clearcut orthorhombic distortion for pure LaBa₂CuO₇ after annealing at 350°C for 4 days.     

Effect of Nd on the Superconductivity of Nd1+x Ba2-x Cu3O y with 0.1 ≤ x ≤ 0.35

The effect of Nd substitution at the Ba sites has been studied in Nd_1+x Ba_2-x Cu₃O _y system for 0.1 x 0.35. Orthorhombic to tetragonal structural phase transition occurs at about x = 0.17. With the increase of Nd, the T _c value decreases and T increases, where T is the difference between the onset and critical temperatures and indicates the sharpness of the transition. These changes are explained by ac-susceptibility measurements on Nd_1.1Ba_1.9Cu₃O_7.12 at 0.10 Oe. The susceptibility curves show the presence of about four phases, which are not detectable by X-ray diffraction technique.     

Magnetic ordering and magnetoresistive effect in La1−x Srx(Mn1−y Mey)O3 perovskites (Me = Nb, Mg)

Perovskites of composition La_1?x Sr_x(Mn_1?x/2Nb _x/2)O₃ and La_0.49Sr_0.51(Mn_1?y Nb_y)O₃ have been synthesized and investigated. The substitution of nonmagnetic niobium ions for manganese was shown to lead to a transition from the metallic into the insulating state due to a decrease in the number of dissimilar (different-valence) manganese atoms in the lattice. In spite of the high resistivity, the niobium-containing perovskites exhibit a large magnetoresistive effect and ferromagnetic ordering. Small additions of Nb⁵⁺ to La_0.49Sr_0.51MnO₃ stimulate the transition from the antiferromagnetic into the ferromagnetic state, whereas the substitution of Mg²⁺ for Mn stabilizes the antiferromagnetic state. It is supposed that the ferromagnetism in the insulating perovskites at hand is due to the positive superexchange of the Mn³⁺-O-Mn³⁺ type, and the magnetoresistive effect owes to the intergranular transfer of spin-polarized charge carriers and the suppression of magnetic nonuniformities by an applied magnetic field near T _C.     

Structural deformations in metastable cubic compounds Ni(1 − x)Zn x O (0.60 ≤ x ≤ 0.99)

X-ray diffraction has been used for studying the fine crystal structure of metastable cubic oxide compounds Ni_{(1 ? x)}Zn _x O (0.60 ≤ x ≤ 0.99) obtained from the initial hexagonal phase by quenching of the samples at a high temperature and under external hydrostatic pressure. It has been found that the diffraction patterns of these compounds include a system of diffuse superstructure maxima, whose number and intensity essentially depend on the composition. The origin of this superstructure has been discussed.     

Negative slope of resistivity–temperature curve and positive magnetoresistance in antiperovskite ZnCNi3−x Mn x (1.15≤x≤1.5)

In antiperovskite intermetallics ZnCNi_3?x Mn _x , the negative slope coefficient (NSC) dρ/dT of resistivity–temperature curves is observed when x=1.15,1.25,1.4,1.5. The sample with x=1.25 shows a semiconductor-like behavior in the whole temperature range of 15–290 K. By study of the magnetization, magnetoresistance, and low-temperature X-ray diffraction, it is found that Mn dopant significantly affects the physical properties of ZnCNi_3?x Mn _x by changing both the carrier density and the magnetism. The origin of the NSC dρ/dT can be ascribed to the change of hole-like carrier density, which is adjusted by Mn content. The existence of hole-like carriers can be understood rationally by the two-band model. The change of sign of magnetoresistance from positive to negative has been observed in ZnCNi_3?x Mn _x with the change of Mn content, which could be ascribed to the competition between the contribution from field-induced suppression of the thermally excited ferromagnetic spin fluctuations and the Lorentz contribution. When Mn content is low, the Lorentz contribution dominates the sign of magnetoresistance. On the other hand, when Mn content is high, the contribution from field-induced suppression of the thermally excited ferromagnetic spin fluctuations dominates the sign of magnetoresistance.     

Heat capacity and the magnetocaloric effect in Pr0.6Sr0.4Mn1–x Fe x O3 manganite

The heat capacity and the magnetocaloric effect of Pr_0.6Sr_0.4Mn_1–xFe_xO₃(x = 0 and 0.1) manganite have been studied in the temperature range 80–350 K and magnetic fields to 18 kOe. The magnetocaloric effect is estimated using two independent methods: the method of magnetic field modulation (direct method) and from the data on the heat capacity in magnetic field and without magnetic field (indirect method). The substitution of Fe atoms for Mn atoms (x = 0.1) shifts T _C by 167 K to lower temperatures; in this case, the magnetocaloric effect (MCE) is changed insignificantly in magnetic field 18 kOe with ΔS _M = 2.05 and 2.31 J/kg K for x = 0 and 0.10, respectively.

     

La0.67-xSmxSr0.33MnO3(0.40≤x≤0.60)体系的TCR研究

通过测量La0.67-xSmxSr0.33MnO3(x=0.40,0.50,0.60)体系的M～T曲线和ρ～T曲线,研究了La位Sm掺杂对体系电阻温度系数 (TCR)的影响.实验结果表明:Sm掺杂引起的电阻率曲线急剧变化,导致大的TCR出现;TCR在x=0.40时出现峰值,随Sm掺杂的增加,TCR值逐渐减小.体系出现大的TCR,来源于Sm掺杂引起的晶格畸变和额外磁性.     

Synthesis and native defectivity of Zn1−x V x O (0 ≤ x ≤ 0.03) photocatalysts

Nanodisperse solid solutions Zn_1?x V _x O (0 ≤ x ≤ 0.03) with high numbers of defects in an oxygen sublattice are synthesized via the precursor technique. ESR analysis reveals that V _O ⁺ oxygen vacancies are the main defects of the oxygen sublattice in the Zn_1?x V _x O structure. The Zn_1?x V _x O (0 < x ≤ 0.15) solid solutions exhibit high photocatalytic activity during hydroquinone oxidation in water upon irradiation with UV and visible light.     

Electro-optic effect in SrTiO3 and Sr1–x Ca x TiO3 (x = 0.014)

The results of the investigation of the quadratic electro-optic effect in Sr_1–x Ca _x TiO₃ with x = 0.014 (SCT) and in nominally pure SrTiO₃ (STO) at room temperature in applied direct-current (dc) and alternating-current (ac) electric fields have been presented. It has been shown that the quadratic (in polarization) electro-optic coefficients of STO and SCT crystals coincide within the accuracy of the determination (±5%). It has been found that, in nominally pure STO measured in a dc electric field, there is a relaxation of the electro-optic effect with a relaxation time τ ≈ 30 s due to the formation of a space charge in the sample. No similar effect in SCT has been observed. A possible mechanism for the formation of a space charge in STO and SCT has been discussed.     

Evolution of structural,magnetic and magnetocaloric properties in Sn-doped manganites La0.57Nd0.1Sr0.33Mn1−x Sn x O3 (x = 0.05–0.3)

Structural and magnetic properties of manganites series La_0.57Nd_0.1Sr_0.33Mn_1?x Sn _x O₃ with (0.05 ≤ x ≤ 0.30) have been investigated, and the critical exponents and magnetocaloric effect are studied around the room temperature, to shed light on Sn substitution influence. A solid-state reaction method was used in the preparation. A structural study using Rietveld refinement of XRD patterns indicates rhombohedral structure with R \( \overline{3} \) c space group for (0.05 ≤ x ≤ 0.20) and shows the existence of a secondary phase attributed to the neodymium tin oxide (Nd₂Sn₂O₇) pyrochlore for x = 0.3. The variation of the magnetization (M) vs. temperature (T), under an applied magnetic field of 0.05 T, reveals a ferromagnetic–paramagnetic transition at the Curie temperature T _C. In addition, it was discovered that increasing the tin content leads to a reduction in magnetization and a lowering of T _C from 282 K (x = 0.05) to 158 K (x = 0.20) with increasing Sn substitution. The samples exhibit the characteristics of spin/cluster-glass state which is evident from (zero-field-cooled and field-cooled) magnetization vs. temperature curves. Indeed, the thermal evolution of magnetization in the ferromagnetic phase at low temperature varies as T ^3/2, in accordance with Bloch’s law. The spin-stiffness constant D obtained from the Bloch constant was determined. A large magnetocaloric effect has been observed in both samples (x = 0.05 and x = 0.10): the maximum entropy change, \( \left| {\varDelta S_{\text{M} }^{\text{peak}} } \right| \) , reaches the highest value of 3.22 J/kg K under a magnetic field change of 5 T with a RCP value of 56 J/kg for x = 0.10 composition. This opens an interesting opportunity to this compound to compete with materials which work as magnetic refrigerants near room temperature. Besides, we show that the samples follow the conventional behavior of a second-order ferromagnetic transition. This was possible by investigating the critical behavior at the transition region by adopting the modified Arrott plot method. The values of the critical exponents (β, γ, δ and n) are determined and they are between those predicted by the three-dimensional Heisenberg model.     

A change from second- to first-order transition in (La(1-x)Eu(x))0.67Ca0.33MnO3 (0 ≤ x ≤ 0.2)

A detailed investigation of the paramagnetic to ferromagnetic transition in (La(1-x)Eu(x))(0.67)Ca(0.33)MnO(3) having small Eu(3+)-content (0 ≤ x ≤ 0.2) has been carried out through resistivity and magnetization measurements. X-ray diffraction patterns of the compounds reveal a single phase (La(1-x)Eu(x))(0.67)Ca(0.33)MnO(3) (0 ≤ x ≤ 0.2) of an orthorhombic crystal structure after annealing the precursor at 800 °C for 2 h in air. With increasing Eu(3+)-content, the second-order transition (at x = 0 and 0.1) changes to first-order at x = 0.2. The experimental results demonstrate thermomagnetic irreversibility of the transition for x = 0.2 composition. This arises between the supercooling and superheating regimes where both the ferromagnetic and paramagnetic phases coexist.     

Eu~(3+)离子激活荧光粉Ca_(1.9)Eu_(0.1)NaMg_(2-x)Zn_x(VO_4)_3(0≤x≤1)的发光性质

采用固相反应法合成了Eu~(3+)离子激活的Ca_(1.9)Eu_(0.1)NaMg_(2-x)Zn_x(VO_4)_3(0≤x≤1),并研究了其发光和热猝灭性能。经粉末X射线衍射确认,反应产物由目标相和微量杂质相EuVO_4构成。在355 nm激发下,样品中均能同时观察到来自[VO_4]_3-基团和Eu~(3+)离子的特征发光。研究结果表明:随着x值的增加,上述两种发光的强度均先增加后降低;而它们的最强激发峰位置由347 nm逐渐地红移至356 nm,Stokes位移也逐渐地减小。这种现象应归因于Zn3d轨道和O2p轨道间很强的轨道杂化效应,这种效应随着x值的增加而逐渐增强。此外,Eu~(3+)离子荧光发射强度最大值对应的x值与自激活荧光的不同。当x=1.0时,两者的相对强度差别最大。经荧光热猝灭测试确认,上述现象是由样品中的自激活荧光表现出比Eu~(3+)离子荧光更严重的荧光热猝灭造成的。因而,在紫外光激发下,样品发出荧光的颜色具有温度敏感性。     

Structural phase transition,antiferromagnetism and two superconducting domes in LaFeAsO_(1-x)F_x(0<x≤0.75)

We report~(75) As nuclear magnetic resonance(NMR)/nuclear quadrupole resonance(NQR) and transmission electron microscopy(TEM) studies on LaFeAsO_(1-x)F_x. There are two superconducting domes in this material. The first one appears at 0.03 ≤ x ≤0.2 with T_c~(max) = 27 K, and the second one at 0.25 ≤x≤0.75 with T_c~(max) = 30 K. By NMR and TEM, we demonstrate that a C4-to-C2 structural phase transition(SPT) takes place above both domes, with the transition temperature T_s varying strongly with x. In the first dome, the SPT is followed by an antiferromagnetic(AF) transition, but neither AF order nor low-energy spin fluctuations are found in the second dome. By ~(75) As nuclear spin-lattice relaxation rate(1/T_1) measurements, we find that AF order and superconductivity coexist microscopically in LaFeAsO_(0.97) F_(0.03). In the coexisting region, 1/T_1 decreases at T_c but becomes proportional to T below 0.6 T_c, indicating gapless excitations. Therefore, in contrast to the early reports, the obtained phase diagram for x ≤ 0.2 is quite similar to the doped BaFe_2As_2 system. The electrical resistivity p in the second dome can be fitted by ρ = ρ0 + AT~n with n = 1 and a maximal coefficient A at around xopt = 0.5-0.55 at which T_s extrapolates to zero and Tc is the maximal, which suggests the importance of quantum critical fluctuations associated with the SPT. We have constructed a complete phase diagram of LaFeAsO_(1-x)F_x, which provides insight into the relationship between SPT, antiferromagnetism and superconductivity.