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1.
Ceramic (La0.7Ca0.3)1 ? x Mn1 + x O3 samples are studied by X-ray diffraction, resistive, magnetic, 55Mn NMR, and magnetoresistance methods. The concentration changes of lattice parameter a of the cubic perovskite structure and its average ionic radius are in good agreement if the concentrations of anion and cation vacancies and nanostructured clusters with Mn2+ in the A positions increase with x. Phase transition temperatures T ms and T c weakly depend on x, and the electrical resistivity and the activation energy decrease substantially with increasing x due to a change in the imperfection of the perovskite structure. An analysis of the broad asymmetric 55Mn NMR spectra of the samples indicate a high-frequency Mn3+? Mn4+ electron superexchange and nonuniform magnetic and valence states of these ions because of a nonuniform distribution of ions and defects, which decrease the amplitude resonance frequency with increasing x. The magnetoresistive (MR) effect near phase-transition temperatures T ms and T c increases substantially with x and is caused by the effect of a magnetic field on the scattering of charge carriers by intracrystallite nanostructured heterogeneities of an imperfect perovskite structure. The second MR effect is located in the low-temperature range, is related to tunneling through mesostructural crystallite boundaries, and decreases weakly with increasing x. A correlation is found between the hyperstoichiometric manganese content, the imperfection of the perovskite structure, and the magnitude of the MR effect.  相似文献   

2.
Y2O3 transparent ceramics with different Nd concentration (0.1-7.0at%) were fabricated using ZrO2 as additive. All the samples exhibit high transparency over a broad spectral region. The elements (Y, O and Nd) are uniformly distributed in the ceramic body, and the average grain size increases with Nd content. Based on the absorption spectrum, the Judd-Ofelt intensity parameters are calculated (Ω2=4.364×10−20 cm2, Ω4=3.609×10−20 cm2 and Ω6=2.919×10−20 cm2). The absorption coefficients increase linearly with Nd3+ doping concentration. The absorption cross-section at 804 nm and stimulated emission cross-section at 1078 nm are calculated to be 1.54×10−20 and 7.24×10−20 cm2, respectively. All the emission bands exhibit the highest emission intensities with 1.0at% Nd3+ ion content, while the lifetime decreases dramatically from 321.5 μs (0.1at% Nd) to 17.9 μs (7.0at% Nd). According to the emission spectra and measured lifetime, the optimum doping concentration of Nd3+ ion in Y2O3 transparent ceramic might be around 1.0at%.  相似文献   

3.
Ba(Ti1−xFex)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(Ti1−xFex)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.  相似文献   

4.
The effect of a small amount Fe2O3 (0.1-2 mol%) doping on the electrical properties of (Na0.5K0.5)0.96Li0.04Nb0.86Ta0.1Sb0.04O3 (NKLNTS) ceramics was investigated. It was found that the B-site substitution of Fe3+ does not change the crystal structure within the studied doping level and all modified ceramics have a pure tetragonal perovskite structure at room temperature. The addition of Fe2O3 can promote the sintering of NKLNTS ceramics, and simultaneously cause the grain growth so that Fe3+-doped NKLNTS compositions show degraded densification at higher doping level. Furthermore, the dielectric properties of the NKLNTS ceramics do not show a significant change by Fe2O3 doping. However, the addition of Fe2O3 was found to have a significant influence on the electric fatigue resistance and the durability against water. The presence of oxygen vacancies caused by the replacement of Fe3+ for B-site ions makes the NKLNTS ceramics harder.  相似文献   

5.
Ceramic samples of manganite perovskites La0.6 ? x Pr x Sr0.3Mn1.1O3 (x = 0?0.6) have been studied using the X-ray diffraction, resistive, magnetic (χac, 55Mn NMR), microscopic, and magnetoresistive methods. It has been found that an increase in the praseodymium concentration x leads to a transition from the rhombohedral R $\bar 3$ c (x = 0–0.3) to orthorhombic Pbnm (x = 0.4–0.6) perovskite structure. It has been shown that the real perovskite structure contains anion and cation vacancies, whose concentrations increase with an increase in the praseodymium concentration x. A decrease in the metal-insulator phase transition temperature T mi and the ferromagnetic-paramagnetic phase transition temperature T c with increasing x correlates with an increase in the concentration of vacancies weakening the high-frequency electronic exchange Mn3+ ? Mn4+. For compositions with x = 0 and 0.1, when the lattice contains not only vacancies but also nanostructured clusters with Mn2+ in the A-positions, there is an anomalous hysteresis. An analysis of the asymmetrically broadened 55Mn NMR spectra of the compounds has revealed a high-frequency electronic exchange of the ions Mn3+ Mn4+ in the B-positions and a local heterogeneity of their surrounding by other ions (La2+, Pr3+, Sr2+) and vacancies. The phase diagram has demonstrated that there is a strong correlation between the composition, imperfection of the perovskite structure, phase transition temperatures T mi and T c , and magnetoresistive properties.  相似文献   

6.
Single-phase hexagonal-type solid solutions based on the multiferroic YMnO3 material were synthesized by a modified Pechini process. Copper doping at the B-site (YMn1−xCuxO3; x<0.15) and self-doping at the A-site (Y1+yMnO3; y<0.10) successfully maintained the hexagonal structure. Self-doping was limited to y(Y)=2 at% and confirmed that excess yttrium avoids formation of ferromagnetic manganese oxide impurities but creates vacancies at the Mn site. Chemical substitution at the B-site inhibits the geometrical frustration of the Mn3+ two-dimensional lattice. The magnetic transition at TN decreases from 70 K down to 49 K, when x(Cu) goes from 0 to 15 at%. Weak ferromagnetic Mn3+-Mn4+ interactions created by the substitution of Mn3+ by Cu2+, are visible through the coercive field and spontaneous magnetization but do not modify the overall magnetic frustration. Presence of Mn3+-Mn4+ pairs leads to an increase of the electrical conductivity due to thermally-activated small-polaron hopping mechanisms. Results show that local ferromagnetic interactions can coexist within the frustrated state in the hexagonal polar structure.  相似文献   

7.
The formation and specific features of the superstructure in La0.33Ca0.67Mn1?y Fe y O3 (y = 0, 0.05) manganites doped with iron are investigated using transmission electron microscopy. The electron diffraction patterns of the manganites are studied in the temperature range 90–300 K, and the high-resolution electron microscope images recorded at temperatures of 91–92 K are analyzed. In both manganites, the structural transition that is accompanied by the formation of the superstructure and which is directly observed from the appearance of additional peaks in the electron diffraction patterns occurs at a temperature that is in close agreement with the charge ordering temperature T CO determined from the temperature dependences of the magnetization M(T). In the temperature range 90 < T < 200 K, the undoped compound has a commensurate superstructure characterized by the vector q = 1/3a* and triple the unit cell «3a × b × c» (where ab ≈ √2a c , c ≈ 2a c , and a c ~ 3.9 Å is the lattice parameter of a simple perovskite). The doping with iron (5 at. %) brings about a decrease in the charge ordering temperature T CO by 50 K and the formation of an incommensurate structure for which the magnitude of the vector q is smaller by approximately 15%. The unit cell of the superstructure in the iron-doped compound is not triple the unit cell but involves defects of ordering, such as quadrupling of the unit cell, numerous translations by a c √2 along the a direction, and dislocation-type defects in the stripe structure of the charge ordering. These pseudoperiodic defects lead to a decrease in the magnitude of the vector q and are responsible for the incommensurability of the structure. A decrease in the charge ordering temperature T CO due to the doping with iron and the incommensurability of the superstructure correlate with the change in the concentration of Mn3+ Jahn-Teller ions as a result of their replacement by Fe3+ non-Jahn-Teller ions.  相似文献   

8.
The microstructure and magnetic properties have been investigated systematically for Sn1−xMnxO2 polycrystalline powder samples with x=0.02-0.08 synthesized by a solid-state reaction method. X-ray diffraction revealed that all samples are pure rutile-type tetragonal phase and the cell parameters a and c decrease monotonously with the increase in Mn content, which indicated that Mn ions substitute into the lattice of SnO2. Magnetic measurements revealed that all samples exhibit room temperature ferromagnetism. Furthermore, magnetic investigations demonstrate that magnetic properties strongly depend on doping content, x. The average magnetic moment per Mn atom decreases with increase in the Mn content, because antiferromagnetic super-exchange interaction takes place within the neighbor Mn3+ ions through O2− ions for the samples with higher Mn doping. Our results indicate that the ferromagnetic property is intrinsic to the SnO2 system and is not a result of any secondary magnetic phase or cluster formation.  相似文献   

9.
Complex oxides demonstrate specific electric and magnetic properties which make them suitable for a wide variety of applications, including dilute magnetic semiconductors for spin electronics. A tin-iron oxide Sn1−xFexO2 nanoparticulate material has been successfully synthesized by using the laser pyrolysis of tetramethyl tin-iron pentacarbonyl-air mixtures. Fe doping of SnO2 nanoparticles has been varied systematically in the 3-10 at% range. As determined by EDAX, the Fe/Sn ratio (in at%) in powders varied between 0.14 and 0.64. XRD studies of Sn1−xFexO2 nanoscale powders, revealed only structurally modified SnO2 due to the incorporation of Fe into the lattice mainly by substitutional changes. The substitution of Fe3+ in the Sn4+ positions (Fe3+ has smaller ionic radius as compared to the ionic radius of 0.69 Å for Sn4+) with the formation of a mixed oxide Sn1−xFexO2 is suggested. A lattice contraction consistent with the determined Fe/Sn atomic ratios was observed. The nanoparticle size decreases with the Fe doping (about 7 nm for the highest Fe content). Temperature dependent 57Fe Mössbauer spectroscopy data point to the additional presence of defected Fe3+-based oxide nanoclusters with blocking temperatures below 60 K. A new Fe phase presenting magnetic order at substantially higher temperatures was evidenced and assigned to a new type of magnetism relating to the dispersed Fe ions into the SnO2 matrix.  相似文献   

10.
We investigate the chemical pressure effect due to P doping in the CeFeAs1−xPxO0.95F0.05(0≤x≤0.4) system. The compound CeFeAsO0.95F0.05 without P doping is on the boundary between antiferromagnet (AFM) and superconductor. The AFM order of Ce3+ local moments causes a significant reentrance behavior in both resistivity and magnetic susceptibility. Upon P doping, Tc increases and reaches a maximum of 21.3 K at x=0.15, and then it is suppressed to lower temperatures. Meanwhile, the AFM order of Ce3+ ions remains nearly the same in the whole doping range (0≤x≤0.4). Our experimental results suggest a competition between superconductivity and Kondo effect in the Ce 1111 system.  相似文献   

11.
Self-doped manganites with nominal composition La0.6−xSr0.4MnO3−δ (0≤x≤0.175) have been prepared by the sol–gel method. The X-ray diffraction (XRD) patterns and magnetic measurements indicate that the samples have two phases with the ABO3 perovskite structure being the dominant phase and Mn3O4 being the minor phase when the doping level x≥0.05. On the basis of the thermal equilibrium theory of crystal defects, the contents of various ions in the perovskite phases were estimated, in which there are Mn2+ ions and no vacancies at A sites. The ion contents have been corrected by Rietveld fitting of the powder samples' X-ray diffraction data. The change tendency of the Curie temperature TC vs. the Mn4+ ion content ratio at the B sites of ABO3 perovskite phase is in accord with the experimental result of the samples La1−xSrxMnO3.  相似文献   

12.
The structure, lattice imperfection, and properties of ceramic samples La0.6 ? x Nd x Sr0.3Mn1.1O3-δ (x = 0–0.4) have been investigated using the X-ray diffraction, resistive, magnetic (χac, 55Mn NMR), magnetoresistive and microscopic methods. It has been shown that there is a satisfactory agreement between the concentration decrease in the lattice parameters a of the rhombohedral (x = 0, 0.1, 0.2) and cubic (x = 0.3, 0.4) perovskite structures and the average ionic radii $\bar R$ for the lattice containing anion vacancies, cation vacancies, and nanostructured clusters with Mn2+ ions in A-positions. With an increase in the neodymium concentration x, the vacancy-type imperfection increases, the cluster-type imperfection decreases, the temperatures of metal-semiconductor phase transition T ms and ferromagnetic-paramagnetic phase transition T C decrease, and the content of the ferromagnetic phase decreases. The anomalous hysteresis is associated with the appearance of unidirectional exchange anisotropy induced in a clustered perovskite structure consisting of a ferromagnetic matrix and a planar antiferromagnetic cluster coherently coupled with it. An analysis of the asymmetrically broadened 55Mn NMR spectra has revealed a high-frequency electronic double exchange (Mn3+-O2?-Mn4+) ? (Mn4+-O2?-Mn3+) and an inhomogeneity of the magnetic and charge states of manganese due to the heterogeneous environment of the manganese ions by other ions and defects. The observed changes in the resonant frequency and width of the resonance curve are caused by changes in the ratio Mn3+/Mn4+ and magnetic inhomogeneity. An increase in the neodymium concentration x leads to a decrease in the ferromagnetic phase content determined from the dependences 4πNχac(T) and the 55Mn NMR curves. The phase diagram characterizes an interrelation between the composition, the imperfection of the structure, and the transport, magnetic, and magnetoresistive properties of lanthanum neodymium manganite perovskites. It has been found that there is a correlation between the imperfection, magnetic inhomogeneity, coercive force, and magnetoresistance effect exhibited by the perovskite structure.  相似文献   

13.
Fe-doped (Ba1−xSrx)TiO3 ceramics were prepared by solid-state reaction, and ferromagnetism was realized at room temperature. The microstructure and magnetism were modified by the Sr concentration control (0≤x≤75 at%) at a fixed Fe concentration, and the relevant magnetic exchange mechanism was discussed. All the samples are shown to have a single perovskite structure. When increasing the Sr concentration, the phase structure is transformed from a hexagonal perovskite into a cubic perovskite, with a monotonic decrease in lattice parameters induced by ionic size effect. The room-temperature ferromagnetism is expected to originate from the super-exchange interactions between Fe3+ on pentahedral and octahedral Ti sites mediated by the O2− ions. The increase in Sr addition modifies two main influencing factors in magnetic properties: the ratio of pentahedral to octahedral Fe3+ and the concentration of oxygen vacancies, leading to a gradually enhanced saturation magnetization. The highest value, obtained for Fe-doped (Ba0.25Sr0.75)TiO3, is an order of magnitude higher than that of the Fe-doped BaTiO3 system with similar Fe concentration and preparation conditions, which may indicate (Ba1−xSrx)TiO3 as a more suitable matrix material for multiferroic research.  相似文献   

14.
《Current Applied Physics》2010,10(2):526-530
Pb0.99Nb0.02(Zr0.95Ti0.05)0.98O3 (PNZT95/5) ceramics with 1 mol% and without Mn doping were prepared via conventional solid state reaction process. X-ray diffraction patterns show that the PNZT95/5 and Mn-doped PNZT95/5 (PNZTM95/5) ceramics, with composition near the boundary of the ferroelectric phase (FE)/antiferroelectric phase (AFE), have a rhombohedral perovskite structure. The ferroelectric behavior of PNZT95/5 ceramics is strongly affected by Mn doping. Without any aging process the PNZTM95/5 ceramics possess double hysteresis loops (P–E loops), whereas the PNZT95/5 ceramics possess normal single hysteresis loops. Due to the defect dipoles formed by effectively negatively charged Mn3+ dopants and positively charged O2− vacancies, the PNZTM95/5 ceramics exhibit the double P–E loops. The defect dipole effect has been proved by investigating the P–E loops under different external fields. As a result, the PNZTM95/5 ceramics become “hardened”, exhibiting a high mechanical quality factor (1300).  相似文献   

15.
Ceramic samples of lanthanum strontium manganite perovskites La0.6Sr0.2Mn1.2 ? x Ni x O3 ± ?? (0 ?? x ?? 0.3) have been investigated using the X-ray diffraction, magnetic (??ac), 55Mn NMR, resistive, and magnetoresistive methods. The specific features of the influence of the composition on the structure and properties of nonstoichiometric manganite perovskites have been established. It has been found that the rhombohedrally (R $\bar 3$ c) distorted perovskite structure contains cation and anion vacancies, as well as nanostructured clusters with Mn2+ ions in the A-positions. The substitution of Ni3+ ions (r = 0.74 ?) for Mn3+ ions (r = 0.785 ?) leads to a decrease in the lattice parameter a, the ferromagnetic-paramagnetic phase transition temperature T C, and the metal-semiconductor phase transition temperature T ms due to the disturbance of the superexchange interactions between heterovalent manganese ions Mn3+ and Mn4+. The observed anomalous magnetic hysteresis at 77 K has been explained by the antiferromagnetic effect of the unidirectional exchange anisotropy of the ferromagnetic matrix structure on the magnetic moments of the superstoichiometric manganese Mn2+ ions located in nanostructured planar clusters. An analysis of the asymmetrically broadened 55Mn NMR spectra of the compounds has revealed a high-frequency electronic superexchange of the ions Mn3+ ? O2? ? Mn4+; a local heterogeneity of their surrounding by other ions, vacancies, and clusters; and a partial localization of Mn4+ ions. The local hyperfine interaction fields on 55Mn nuclei have been determined. The concentration dependences of the activation energy and charge hopping frequency have confirmed that the Ni ions decrease the electrical conductivity due to the weakening of the electronic superexchange Mn3+ ? O2? ? Mn4+. Two types of magnetoresistive effects have been found: one effect, which is observed near the phase transition temperatures T C and T ms, is caused by scattering at intracrystalline nanostructured heterogeneities, and the other effect, which is observed in the low-temperature range, is induced by tunneling through intercrystalline mesostructured boundaries. The phase diagram has demonstrated that there is a strong correlation between magnetic and electrical properties in rare-earth manganites.  相似文献   

16.
The structural, resistive, magnetic, and magnetoresistive properties of the La0.6Sr0.3 ? x Bi x Mn1.1O3 ceramics have been studied. The substitution of Bi ions for Sr ions increases the lattice parameter of the rhombohedral perovskite structure, decreases the metal-semiconductor and ferromagnet-paramagnet phase transition temperatures and the peak of the magnetoresistive effect, and increases the resistivity, approaching the system to the ferroelectric state. The 55Mn NVR study indicates on the high-frequency Mn3+ ? Mn4+ superexchange and heterogeneity of the valence and magnetic states of manganese due to the nonuniformity of distribution of all ions and defects. The phase diagram has been constructed, which shows a strong correlation between the structural, magnetic, and magnetoresistive properties.  相似文献   

17.
Aurivillius type (NaBi)0.5?x(LiCe)xBi2Nb2O9 ceramics were prepared by the standard ceramics route. The single crystal structural ceramics were achieved for all compositions and lattice distortion was decreased by (LiCe) dopants. The temperature dependent dielectric properties revealed that all compositions possess a high Curie-temperature (>780 °C). A modified Curie–Weiss relationship is used to study the diffuseness behavior of a ferroelectric phase transition indicating the degree of diffuseness of NBN-based ceramics increased with (LiCe) modifications. The degradation of resistance implied a plausible model that Ce4+ ions entered into the B-site of the pseudo-perovskite structure and acted as acceptor doping. Further investigation demonstrated that both electrical conduction and dielectric relaxation processes were associated with the oxygen vacancies produced by the substitution of Nb5+ ions by the Ce4+ ions.  相似文献   

18.
研究了La2O3对Yb:Y2O3透明陶瓷光谱性能的影响,添加适量La2O3以后,Yb:Y2O3透明陶瓷的吸收峰和发射峰的位置不变,但由于La3+的离子半径大于Y3+的离子半径,在Y2O3中引入La3+离子后,导致Y2O3晶格常数变大,晶场强度变弱,同时降低了Y2O3晶体的有序度,致使发射峰强度有所下降,发射截面变小.过量的La2O3x=0.16)造成Yb3+激活离子发射强度明显下降;其荧光寿命在添加La2O3后总体增大45%—60%. 关键词: 氧化镧 氧化钇 透明陶瓷 光谱性能  相似文献   

19.
The structural and superconducting properties of Bi1.7Pb0.3Sr2Ca2−xYxCu3Oy superconducting samples are investigated by X-ray diffraction (XRD), resistivity and thermoelectric power (TEP) measurements. XRD results reveal that the volume percentage of the 2223 high Tc phase decreases with an increase in Y content. The replacement of the Ca2+ ion by the Y3+ ion does not influence the tetragonal structure of the pure Bi (Pb): 2223 system and the lattice parameters vary with Y content. The results of resistivity indicate that the critical temperatures Tc of the samples decrease monotonically with an increase in Y content. Further, the critical concentration of Y to completely suppress superconductivity in the Y-doped Bi (Pb):2223 system is higher (0.60) than that reported (0.20) for the other rare-earth elements. On the other hand, the values of TEP at room temperature are found to be negative for Y=0.00 and 0.10 samples, and it changed to positive with further increase in Y content. The hole-carrier concentration per Cu ion (P) is deduced by using two different ways: the first in terms of Tc values in the superconducting state and the other in terms of TEP values in the normal state. Interestingly, it is found that the values of P deduced from the formal way are not consistent with the reported parabolic behavior for superconducting systems in the under-doped region, and consequently disagree with the general roles of substitution. However, the vice versa is recorded for the values of P deduced from the latter way. The results are discussed in terms of the possible reasons for the suppression of superconductivity in the considered system.  相似文献   

20.
The effects of Cr doping on Mn sites in the electron-doped manganites La0.9Te0.1MnO3 have been studied by preparing the series La0.9Te0.1Mn1−xCrxO3 (0.05≤x≤0.20). Upon Cr doping, both the Curie temperature TC and magnetization M are suppressed. The resistivity measurements indicate that there exists a weak metal-insulator (M-I) transition for the sample with x=0.05, with an increase in the doping level, the M-I transition disappears and the resistivity increases. Thermopower S(T) exhibits a maximum near TC for all samples. By fitting the S(T) and ρ(T) curves, it is found that the temperature dependences of both S(T) and ρ(T) in the high temperature paramagnetic (PM) region follow the small polaron conduction (SPC) mechanism for all samples. The fitting parameters obtained imply changes of both the average-hopping distance of the polarons and the polaron concentration with Cr doping in our studied samples. In the case of the thermal conductivity κ(T), the variation of κ(T) is analyzed based on the combined effects due to the suppression of the local Mn3+O6 Jahn-Teller (JT) lattice distortion because of the substitution of Cr3+ for Mn3+ ions, which results in the increase in κ, and the introduction of the disorder due to Cr-doping, which contributes to the decrease in κ.  相似文献   

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