High-temperature electronic transport properties of La1−xCaxMnO3+δ (0.0?x?1.0)

La_1−xCa_xMnO_3+δ (0.0?x?1.0) samples were prepared and their resistivity and Seebeck coefficients were measured in the high-temperature range. Ca doping changes the ratio of Mn³⁺/Mn⁴⁺ and influences the electronic transport behavior markedly. With the increase of Ca concentration, the samples change from a p-type semiconductor to an n-type one and Seebeck coefficient becomes increasingly negative. Low doping (x=0.2) and high doping (x=0.8) induces the drop of the resistivity compared with undoped LaMnO_3+δ and CaMnO_3+δ samples due to the rise of carrier concentration. However, the resistivity of moderate-doped samples (x=0.4, 0.6) is larger than low- and high-doped samples because dopant scattering decreases carrier mobility.     

Effect of fluorine doping on phase formation and properties of Bi(Pb)-2223 ceramics

Superconducting ceramics of Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_yF_x (x = 0–0.6) are prepared in air by conventional solid state reaction and characterized. The study shows that the melting point of the samples decreases as fluorine content increases. As a consequence, the grain size increases with the doping level and for x = 0.6, the sample is completely deformed and presents a concave shape making impossible the measurements on it. The Vickers microhardness reaches its maximum for x = 0.2. The analysis of the X-ray diffraction results reveals that all the samples are composed of only Bi(Pb)-2212 and Bi(Pb)-2223 phases. The highest proportion of the high T_c phase (Bi(Pb)-2223) is also observed for x = 0.2 and is about 67.32%. The refinement of cell parameters is done by considering the structural modulation. The results show that the doping leads to a reduction of cell volume as well as the a axis component of modulation. From resistivity versus temperature measurements, it is shown that the doped phases exhibit higher onset critical transition temperatures than the undoped one. The residual resistivity increases with fluorine content suggesting that the doping introduces structural defects and disorder into the samples. The obtained critical current density at 77 K under zero magnetic field also increases with fluorine doping.     

Effect of Y2O3 doping on the electrical transport properties of Sr2MnNiFe12O22 Y-type hexaferrite

Y₂O₃ doped Y-type composite hexa-ferrites Sr₂MnNiFe₁₂O₂₂ + xY₂O₃ (x = 0 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%) were synthesized successfully using sol-gel auto combustion technique. X-ray diffraction analysis reveals Y-type hexagonal structure with few traces of secondary phases. The decrease in grain size as a function of Yttrium content is attributed to the fact that Yttrium acts as a grain inhibitor. The DC resistivity was observed to increase with increasing Yttrium-contents due to the unavailability of Fe³⁺ ions at octahedral sites. Activation energy showed that the samples with high resistivity have high value of activation energy and vice versa. Permittivity decreases with the increase of frequency following Maxwell Wagner Model. In addition, the doped samples exhibit very low dielectric constant and low loss tangent in frequency range 20 Hz–1 MHz. The sample x = 5 wt% exhibit the lowest value of dielectric constant. The variation in imaginary part of dielectric constant and loss tangent with frequency show normal dielectric behavior for all the samples. The frequency dependent ac conductivity increases with increase in frequency and decrease with Y₂O₃ doping. These characteristics may be suitable for their potential applications in electromagnetic attenuation materials and microwave devices. The conductivity mechanism so determined was hopping mechanism. The dc resistivity of the doped ferrites measured in our case is about 10¹⁰ Ω-cm that meets the requirement for fabrication of components by electroplating.     

The effect of Ru doping on the alkali-doped manganite Pr0.8Na0.2MnO3

Polycrystalline manganites Pr_0.8Na_0.2MnO₃ doped by ruthenium (0.0≤x_Ru≤0.2) were prepared by the sol-gel process. The magnetic field induced metamagnetism was observed to occur with a large resistivity drop at 3 K for x_Ru≤0.02 samples, which can be sorted into the kind of CMR phenomenon. It was found that the 0.01 Ru doping increased T_C and decreased the metamagnetic critical field than that of the undoped sample. The doped manganites show a quick increase in their magnetic moments as x_Ru increases from 0.01 to 0.04, but the larger fraction of Ru doping (0.04≤x_Ru≤0.2) reduces their M and T_C. All the five doped samples have larger magnetic moments than that of the host sample. Ru doping of x_Ru>0.01 results in a rapid disappearance for the observation of long range spin and charge ordering in the samples’ M-T curves, which is characteristic of the undoped sample. It was found that larger low-temperature MR favored decrease in the metamagnetic critical field. Finally, the phase diagram of Ru doping vs. transition temperatures is presented to summarize the experiments.     

Suppression of electron correlations in the superconducting alloys of Rh17−xIrxS15

We have studied the effect of Iridium doping (Rh_17?xIr_xS₁₅) in the rhodium sites of the strongly correlated superconductor Rh₁₇S₁₅. Even at low levels of doping (x = 1 and 2) we see a drastic change in the superconducting properties as compared to those of the undoped system. We deduce that there is a reduction in the density of states at the Fermi level from reduced Pauli susceptibility and Sommerfeld coefficient in the doped samples. Moreover, the second magnetization peak in the isothermal magnetization scan (‘fishtail’) which was very prominent in the magnetization data of the undoped crystal is suppressed in the doped samples. The temperature dependence of resistivity of the doped crystals show a remarkably different behavior from that of the undoped crystal with the appearance of a minima at lower temperatures, the position of which is fairly constant at different fields. Our data supports the notion that Iridium, which is a bigger atom than rhodium expands the lattice thereby, reduces the electron correlations that existed due to the interaction between closer lying rhodium atoms in the undoped system.     

Enhancement of optical properties and donor-related emissions in Y-doped ZnO

The Zn_1−xY_xO nanoparticles with good optical properties have been prepared by sol–gel method. The yttrium doping effect on the structures and optical properties were investigated by XRD, SEM, XPS and low temperature photoluminescence. The UV emission intensity of yttrium doped ZnO was over 300 times stronger than that of pure ZnO, which was an exciting result in enhancing the ultraviolet near band edge emission in photoluminescence from ZnO nanoparticles. The UV emission band of doped ZnO nanoparticles exhibits a red shift from 388 to 398 nm, indicating a shallow energy level near valence band has been formed due to the yttrium doping into ZnO lattices. The defect-related band is suppressed (I_D/I_UV = 1–0.83) considerably in Zn_1−xY_xO nanoparticles, revealing the quenching of the broad yellow-orange emission. The doping effect on the optical properties is investigated by temperature dependent photoluminescence. The experimental results indicated that the donor level of yttrium is deeper than that of undoped ZnO.     

Transport behavior and mechanism of conduction of simultaneously substituted Y and Fe in La0.7Ba0.3MnO3 perovskite

The electrical properties and the mechanism of conduction of the simultaneously substituted La_0.7−xY_xBa_0.3Mn_1−xFe_xO₃ perovskite (0≤x≤0.30) have been studied. The insertion of Y³⁺ and Fe³⁺ ions in the parent compound La_0.7Ba_0.3MnO₃ leads to an increase of the resistivity. The undoped sample (x=0) shows a metallic behavior, which can be fitted by the relation ρ(T)=ρ₀+ρ₂T²+ρ_4.5T^4.5, indicating the importance of electron-magnon scattering effects in this material. All the other samples (x≥0.10) are semiconductors throughout the studied temperature range (80-290 K). Several models have been used to fit their temperature-dependent resistivity: thermal activation, adiabatic nearest-neighbor hopping of small polarons (Holstein theory) and variable range hopping (VRH) models. The fits show that the electronic transport in semiconducting La_0.7−xY_xBa_0.3Mn_1−xFe_xO₃ is well described and dominated by the VRH mechanism, for which the hopping distance (a) grows with increasing Fe³⁺ doping, thus increasing the average hopping energy W.     

Temperature dependence of electrical resistivity for Ca-doped perovskite-type Y1−xCaxCoO3 prepared by sol-gel process

The temperature dependences of DC electrical resistivity for perovskite-type oxides Y_1−xCa_xCoO₃ (0?x?0.1), prepared by sol-gel process, were investigated in the temperature range from 20 K up to 305 K. The results indicated that with increase of doping content of Ca the resistivity of Y_1−xCa_xCoO₃ decreased remarkably, which was found to be caused mainly by increase of carrier (hole) concentration. In the whole temperature range investigated the temperature dependence of resistivity ρ(T) for the un-doped (x=0) sample decreased exponentially with decreasing temperature (i.e. ln ρ∝1/T), with a conduction activation energy ; the resisitivity of lightly doped oxide (x=0.01) possessed a similar temperature behavior but has a reduced E_a (0.155 eV). Moreover, experiments showed that the relationship ln ρ∝1/T existed only in high-temperature regime for the heavily doped samples (T?82 and ∼89 K for x=0.05 and 0.1, respectively); at low temperatures Mott's ln ρ∝T^−1/4 law was observed, indicating that heavy doping produced strong random potential, which led to formation of considerable localized states. By fitting of the experimental data to Mott's T^−1/4 law, we estimated the density of localized states N(E_F) at the Fermi level, which was found to increase with increasing doping content.     

Non-adiabatic polaron hopping conduction in CaMn1−xCrxO3 (0?x?0.3)

DC electrical conductivity (σ_dc) of electron-doped antiferromagnetic CaMn_1−xCr_xO₃ (0?x?0.3) has been discussed elaborately in the light of polaron hopping conduction. The increase in Cr doping concentration increases the conductivity and decreases the activation energy. Non-adiabatic polaron hopping conduction is observed in all the manganites at high temperatures. The analysis of σ_dc data shows that small polarons are formed at lower concentrations (?5%) of Cr doping and undoped samples. However, large polarons are materialized at higher doping (?10%) concentrations. This is consistent with the fact that doped Cr³⁺ has larger ionic size compared to that of Mn⁴⁺. Again, strong electron-phonon (e-ph) interaction is perceived in undoped and 5% Cr-doped samples but not in manganites with larger doping concentration. This also confirms the formation of larger polarons with the increase of x. Mott's variable range hopping (VRH) model can elucidate the dc conductivity at very low temperatures. It has been detected that single phonon-assisted hopping is responsible for the dc conduction in the Cr-doped CaMnO₃ manganites.     

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.     

Dynamical transport behavior in electron-doped manganites La0.4Ca0.6(Mn1−x Ru x )O3

Measurements of the dynamical electrical transport behavior are performed on electron-doped manganites La_0.4Ca_0.6(Mn_1−x Ru _x )O₃ (x=0 and 0.02). An undoped sample possesses a robust charge-ordered antiferromagnetic ground state, and only a positive resistivity relaxation can be observed. However, a low-temperature negative relaxation behavior arises after inducing a few ferromagnetic orders to the charge-ordered matrix by tiny Ru doping. We assigned this difference to the dynamical competition between ferromagnetic metallic and charge-ordered insulating phases. Consistently, for a doped sample, the crossover from positive to negative resistivity relaxation behavior ensues around T=115 K, which is just below the ferromagnetic Curie temperature.     

Sr掺杂钙钛矿型氧化物Y1-xSrxCoO3的溶胶-凝胶制备及电阻率温度关系研究

采用溶胶-凝胶方法成功制备了Sr的替代化合物Y_1-xSr_xCoO₃ (x=0, 0.01, 0.05, 0.10, 0.15, 0.20), 系统地研究了20–720 K温度范围内Y_1-xSr_xCoO₃的电阻率温度关系. 研究表明, 随着Sr的替代含量的增加, Y_1-xSr_xCoO₃的电阻率迅速地降低, 这主要是由于载流子浓度的增加引起. 样品x=0和0.01在低于330和260 K的温度范围内, 电阻率与温度之间满足指数关系lnρ∝1/T, 获得导电激活能分别为0.2950和0.1461 eV. 然而, 实验显示lnρ∝1/T关系仅成立于重掺杂样品的高温区; 在低温区莫特定律lnρ∝T^-1/4成立, 且表明重掺杂引入势垒, 导致大量局域态的形成. 根据莫特T^-1/4定律拟合实验数据, 评估了局域态密度N(E_F), 它随着掺杂量的增加而增加. 关键词： 热电材料 溶胶-凝胶 3')" href="#">YCoO₃     

Lu-induced spin entropy enhancement in Ca3Co4O9+δ system

The magnetothermopower have been studied in Lu-doped Ca_3?xLu_xCo₄O_9+δ. A strong magnetic field suppression of thermopower indicates large spin entropy contribution. The magnetothermopower for doped samples are overall enhanced compared with that for undoped Ca₃Co₄O_9+δ, providing an experimental evidence for the enhancement of spin entropy. Magnetic results confirm that Co⁴⁺ concentration is reduced by Lu doping. We suggest that the reduction in Co⁴⁺ concentration results in the enhanced spin entropy.     

Influence of Y3+ doping on the high-temperature transport mechanism and thermoelectric response of misfit-layered Ca3Co4O9

The high-temperature transport and thermoelectric characteristics of Ca_3−x Y _x Co₄O₉ (x=0–0.75) series were studied up to 1000 K. The results reveal that the substitution of Y³⁺ for Ca²⁺ not only increases resistivity but also gradually alters the transport mechanism. The localization of carriers narrows bandwidth, which induces the evolution of the system from metal to variable-range hopping semiconductor and then to thermally activated semiconductor. The increasing thermopower with doping originates from the reduction of carrier concentration along with enhanced electronic correlations. Thermoelectric figure of merit ZT of Ca₃Co₄O₉ system is improved by Y doping. However, the optimal thermoelectric performance is found to only exist at the critical doping level where doping-induced metal–semiconductor transition occurs. This result suggests an intrinsic correlation between transport mechanism and thermoelectric response in this system.     

Impact of Bi2O3 addition on the normal state properties of Bi3.4Pb0.3Sr2Ca1.3−x RExCu2Oy ceramics

The impact of Bi₂O₃ addition on the structural, microhardness (Vickers microhardness (VHN)), resistivity and Hall coefficient measurements of Bi_3.4Pb_0.3Sr₂Ca_1.3−x RE_xCu₂O_y ceramic samples with various x and RE is investigated. X-ray diffraction results indicate that all the peaks belong to Bi: 2212 and 2201 phases. The moderate amount of 2212 phase exists as a major phase, while the 2201 phase as a minor. The net intensity of all peaks I_max for 2212 phase increases with Y as compared to undoped sample, followed by a gradual decrease with further increase in rare earth (RE) up to La. While the vice versa is recorded for both 2201 phase and VHN. Except Y sample, a good link between flake-type grains is observed in the SEM photographs of the considered samples. The electrical resistivity turns from quiet metallic for undoped sample to semiconducting behavior for all substituted samples without any transition to the superconducting state. The Hall coefficient sign is found to be positive for undoped and Y samples and it changed from positive to negative for the other RE-substituted samples. The possible reasons for superconductivity quenching by RE substitution in this type of ceramic materials are reported.     

Suppression of charge ordering and thermal hysteresis of electronic transport and magnetisation in La0.5Ca0.5Mn1−xNixO3

A series of polycrystalline La_0.5Ca_0.5Mn_1?xNi_xO₃ (x = 0.00, 0.025, 0.050, 0.075, 0.100 and 0.125) was synthesised using solid state reaction. Measurements in a cooling and warming cycle between 300 and 80 K were carried out to study the Ni-doping effects on the electrical resistivity, thermopower and magnetisation of single-phase La_0.5Ca_0.5Mn_1?xNi_xO₃. Partial substitution of Ni for Mn leads to the suppression of charge ordering state, the evidence of which is shown by the dramatic decrease in electrical resistivity and thermal hysteresis width in electrical resistivity, thermopower and magnetisation. However, the magnitude of both electrical resistivity and thermopower increases with increasing Ni content. This can be attributed to an increase in the Mn⁴⁺ concentration, which favours the antiferromagnetic state and leads to a gradual disappearance of ferromagnetic double exchange interaction. Besides, the metal–nonmetal transition temperature decreases with increasing Ni content until x = 0.075, which might arise from increased electron–phonon coupling due to less ordered spins at temperatures above ferromagnetic transition. For samples with x greater than 0.075, no metal–nonmetal transition is observed due to the suppression of double exchange mechanism.     

Ca3－x AgxCo4O9(x=0—0.05)氧化物的电输运性能

Ca位掺杂可以优化Ca₃Co₄O₉复合氧化物的电输运性能. 采用柠檬酸溶胶凝胶结合放电等离子烧结制备了Ca位微量掺杂Ag的Ca_3-xAg_xCo₄O₉(x=0—005)氧化物块体试样,通过X射线衍射、扫描电子显微镜、电参数测试仪分析了所得试样. 试验结果表明: 产物呈单一物相,Ca位微量掺杂Ag降低了Ca_{关键词： 3}Co₄O₉')" href="#">Ca₃Co₄O₉ 掺杂 电输运     

Influence of magnetic (Fe) and non-magnetic (Ga) ion doping at Mn-site on the transport and magnetic properties of La0.7Ca0.3MnO3

The modifications in electrical and magnetic properties of polycrystalline bulk La_0.7Ca_0.3Mn_1−xT_xO₃ (T=Fe, Ga) samples at relatively higher doping concentration (x=0.08-0.12) are investigated. All the synthesized, single phase samples were subjected to resistivity measurements in the temperature range 50-300 K. No insulator-metal transition (T_P) was observed for Fe doped samples with x=0.12. For all the other samples the transition temperature decreased with increase in doping concentration. The small polaron hoping energy was found to increase, rather slowly, with increase in doping concentration. The effect on magnetic properties is also prominently observed with respect to doping element and doping concentration. Interestingly, with the increase in doping concentration, the Curie temperature (T_C) and T_P separate out significantly indicating decoupling of electric and magnetic properties. Changes in these properties have been analyzed on the basis of magnetic disorder introduced in the system due to the magnetic and nonmagnetic nature of these ions rather than strong lattice effects which is insignificant due to similar ionic radii of Fe⁺³ and Ga⁺³ when compared to that of Mn⁺³.     

Influences of Doping and Annealing on the Structural and Photoluminescence Properties of Y2O3 Nanophosphors

This paper reports the structural and optical properties of rare earth doped and codoped yttrium oxide nanophosphors. Dysprosium (Dy³⁺) and Terbium (Tb³⁺) doped and codoped yttrium oxide (Y₂O₃) phosphors were prepared by combustion synthesis method and subsequently annealed to high temperature to eliminate the hydroxyl group (?OH) and to get more crystallinity. The formation of compounds was confirmed by the X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR). The diffuse reflectance spectra (DRS) of doped and codoped Y₂O₃ powder phosphors were measured and it is observed that the absorption edge of the doped samples is shifted towards blue region with respect to undoped sample. The bandgap of the prepared samples were evaluated with the help of Kubelka-Munk function using Diffuse Reflectance Spectra (DRS) and an increase in bandgap was observed with the decrease in crystallite size. A strong characteristics emission from Tb³⁺ and Dy³⁺ ions was identified and the influence of doping concentration and annealing temperature on photoluminescence properties was systematically studied. Transfer of energy was observed in dysprosium–terbium codoped Y₂O₃ nanophosphor at room temperature from Dy³⁺ ions toTb³⁺ ions.     

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.