Magnetic and magnetotransport properties of Co-doped manganites with perovskite structure

A systematic study of the doping of the Mn-sites by cobalt in three series of manganites — La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals, La_2/3Ba_1/3(Mn_1−xCo_x)O₃ and La(Mn_1−xCo_x)O₃ ceramics has been performed. It was found that La(Mn_1−xCo_x)O₃ annealed at 800°C in the range 0.4x0.9 is a mixture of ferromagnetic domains with ordered Mn and Co ions and ionically disordered spin-glass domains. In the quenched samples the fraction of spin-glass-type component increases strongly. The La_2/3Ba_1/3(Mn_1−xCo_x)O₃ solid solutions exhibit also an evidence for phase separation in the range 0.5x0.8. All the La(Mn_1−xCo_x)O₃ samples show an insulating behavior, however, magnetoresistance reduces strongly when the cobalt content rises to x=0.5. The La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals show first-order phase transition below their Curie points associated with a change of ground state of the Co²⁺ ions. The magnetic phase diagrams are depicted. The results are discussed in terms of positive Mn³⁺–O–Mn⁴⁺, Mn³⁺–O–Mn³⁺, Mn⁴⁺–O–Co²⁺ and negative Mn⁴⁺–O–Mn⁴⁺, Co²⁺–O–Co²⁺, Co²⁺–O–Mn³⁺ superexchange interactions as well as Co²⁺ and Mn⁴⁺ ionic ordering.     

Structural, magnetic and magnetotransport behavior of some Nd-based perovskite manganites

A systematic investigation of Neodymium based colossal magnetoresistive manganites with general formula Nd_0.67A_0.33MnO₃, (A=Ca, Sr, Pb and Ba) has been undertaken mainly to understand their structural, magnetic as well as electrical behavior. The materials were prepared by the sol-gel route sintering at 900 °C. After usual characterization of the materials structurally by XRD, their metal-insulator transition (T_P) as well as magnetic transition (T_C) temperatures were determined and the reasons for the occurrence of ΔT_T(T_C-T_P) values have been explained. X-ray data have been analyzed by using Rietveld analysis and the variations of various parameters are explained. It has been concluded that not only A-site cation radius, 〈r_A〉 but also the size variance factor (σ²) influence both the metal-insulator as well as ferro to para magnetic transition temperatures. A systematic study of electrical conductivity of all the four materials was undertaken as a function of magnetic field upto 7 T mainly to understand the conduction mechanism in the presence of magnetic field. On analyzing the electrical resistivity data, it has been concluded that the metallic (ferromagnetic) part of the resistivity (ρ) (below T_P) can be explained by electron-electron scattering processes (∼T²) and two magnon scattering processes (∼T^4.5), while in the high temperature (T>T_P) paramagnetic insulating regime, the adiabatic small polaron and variable range hopping models are found to fit well.     

Magnetic and high-pressure magnetotransport properties of cesium-substituted lanthanum calcium manganites

The nature of the double-exchange (DE) interaction in lanthanum manganites is studied through chemical substitutions, Cs for La, and high-pressure measurements. Static and high-frequency magnetic measurements and high-pressure electrical transport studies were carried out on bulk polycrystalline and radio-frequency sputtered thin films of La_0.7-xCs_xCa_0.3MnO₃ for x=0-0.1. The samples are found to be cubic. Curie temperature T_c measurements provide evidence for bond-length-related weakening of DE as x is increased from 0 to 0.03. For higher x, the bond-angle-related changes lead to an increase in the strength of DE. High-pressure mangetoresistance data indicate both bond length and bond-angle-related increase of 10–20 K/GPa in T_c with pressure, with the largest increase measured for x=0.03. The rate of increase in the Curie temperature with pressure decreases with increasing T_c. Anomalies are observed in the magnetic parameters for x=0.03. The Cs-concentration dependence of the low-temperature saturation magnetization shows a minimum close to x=0.03. Ferromagnetic resonance studies at x-band reveal a 5% decrease in the g-value for x=0.03 relative to the end members (x=0 and 0.1). The low-field magnetostriction for x=0.03 indicates a relatively strong electron–phonon spin coupling compared to neighboring compositions. Received: 15 May 2000 / Accepted: 24 July 2000 / Published online: 9 November 2000     

Electronic structure and magnetic properties of rare-earth perovskite gallates from first principles

The density functional calculation is performed for centrosymmetric(La–Pm) GaO_3 rare earth gallates, using a full potential linear augmented plane wave method with the LSDA and LSDA+U exchange correlation to treat highly correlated electrons due to the very localized 4f orbitals of rare earth elements, and explore the influence of U = 0.478 Ry on the magnetic phase stability and the densities of states. LSDA+U calculation shows that the ferromagnetic(FM) state of RGaO_3 is energetically more favorable than the anti-ferromagnetic(AFM) one, except for LaGaO_3 where the NM state is the lowest in energy. The energy band gaps of RGaO_3 are found to be in the range of 3.8–4.0 eV, indicating the semiconductor character with a large gap.     

钙钛矿锰氧化物中的极化子研究

钙钛矿锰氧化物(以下简称锰氧化物,如La_1-xSr_xMnO₃等,x为掺杂浓度)因其优异的电、磁性质受到人们广泛的关注,但是对于其材料内部载流子性质的认识至今仍没有统一定论.本文基于锰氧化物内Mn—O链的特点,建立一维紧束缚模型,对锰氧化物载流子的性质展开研究.发现在掺杂浓度x=0.5时,系统处于铁磁态,自旋能级完全劈裂,价带和导带之间存在带隙,所有电子态呈现扩展行为.进一步掺杂,将出现局域电子态,同时伴随着晶格的局域畸变,形成所谓的极化子.伴随着极化子的出现,带隙中出现极化子深能级.极化子携带的电荷量越多,形成的晶格缺陷越深,局域能级也越深.当极化子的电荷量继续增加时,极化子解离,载流子倾向于形成能量更低的正反"孤子"对.     

Magnesium,a promising dopant for the improvement of the CMR properties of perovskite manganites

The study of the substitution of magnesium for manganese in the type I Pr_0.7(Ca,Sr) _0.3MnO₃ and type II Pr_0.5Sr_0.5MnO₃ manganites has been performed. Remarkable colossal magneto resistance (CMR) properties have been evidenced for the manganites Pr_0.7Ca_0.2Sr_0.1 Mn_{1 x}Mg_xO₃, with x ≤ 0.02, for which R_OT/R_7T resistance ratio values ranging from 10⁴ to 4.10⁵ at 105 K and 70 K respectively were obtained in a magnetic field of 7 T. The study of the type II phases Pr_0.5Sr_0.5M_{1 x}Mg_xO₃, shows their similarity with the trivalent metal doped manganites Pr_0.5Mn_1?x M_xO₃ with M = Al, Ga, In, in contrast to the tetravalent metal doped manganites with M = Ti, Sn. The latter properties are interpreted in terms of two factors, the molar ratio Mn(III): Mn(IV), and the size of the doping cation.     

Homogeneity regions in manganites of rare-earth elements

Based on X-ray powder diffraction analysis of homogeneous phases and heterogeneous compositions with the general formula Ln_2?x Mn _x O_3±δ (Ln = Sc, Pr, Nd, Sm, Eu; 0.90 ≤ x ≤ 1.20; Δx = 0.02), which were obtained by a ceramic synthesis from oxides in air in the temperature range 900–1400°C, the solubility boundaries of oxides Ln₂O₃ and manganese in LnMnO_3±δ are determined. The results are represented in the form of fragments of phase diagrams of the systems Sc-Mn-O, Pr-Mn-O, Nd-Mn-O, Sm-Mn-O, and Eu-Mn-O in air. It is assumed that the solubility of Ln₂O₃ oxides in LnMnO_3±δ is determined by defects of the crystalline structure, and that of manganese oxides is determined by the disproportionation reaction 2Mn³⁺ = Mn²⁺ + Mn⁴⁺ with subsequent partial substitution of Ln³⁺ ions by divalent manganese in cuboctahedral sites of a perovskite-like crystal lattice.     

Random potential effect near the bicritical region in perovskite manganites as revealed by comparison with the ordered perovskite analogs

The orbital-charge-spin ordering phase diagram for half-doped perovskites Ln(1/2)Ba(1/2)MnO3 (Ln = rare earth) with ordered Ln/Ba cations has been investigated comparatively with that of the Ln/Ba solid-solution analogs. A large modification of the phase diagram is observed upon the A-site disordering near the original bicritical point between the charge-orbital ordering and ferromagnetic metallic phases. The random potential by quenched disorder inherent in the A-site solid solution is found to suppress the respective long-range orders and gives rise to the colossal magnetoresistive state.     

Effect of cobalt on the magnetoresistance characteristics of rare-earth doped manganites

The effect of cobalt-doping on the magnetic, transport and magnetoresistance characteristics of La_1-xSr_xMnO₃ was investigated. The results show that the magnetoelectric property of rare-earth doped manganites is greatly affected by substitution of Co for Mn sites. The Curie temperature as well as the magnetic moment decreases with the increase of doping concentration, and the samples exhibit obvious characteristics of the spin glass state. Moreover, the magnetoresistance is evidently modulated by doping concentration, and the relevant temperature dependence is also suppressed. In addition, low-temperature magnetoresistance is significantly promoted as doping concentration increases, which renders a value of approximately 50% in the temperature range of 5--200~K and varies within 12.5%. It can be attributed to the effect of spin scattering, induced by cobalt doping, on the itinerant electrons of Mn ions, thus introducing a spin-disorder region into the ferromagnetic region of double-exchange interaction between neighbouring Mn³⁺ and Mn ³⁺ ions.     

Electronic structure of hexagonal rare-earth manganites RMnO<Subscript>3</Subscript>

The optical spectra of single crystals of hexagonal rare-earth manganites RMnO₃ (R=Sc, Y, Er) are studied in the range from 0.7 to 5.4 eV. It is found that the spectra substantially differ from the spectra of orthorhombic manganites in both the positions of spectral features and their polarization anisotropy. It is shown that the optical absorption edge is determined by an abnormally strong (k?1) and narrow electric dipole transition with the center at approximately 1.6 eV with light polarization in the basal plane of the crystal. This transition can be treated with confidence as charge transfer from oxygen to manganese. The experimental results are in many instances substantially different from the first-principles calculations of the electronic structure of YMnO₃ published recently and, hence, may serve as a reliable basis for the further improvement of computational methods.     

Low temperature magnetism in the rare-earth perovskite GdScO_3

The magnetic phase diagram of rare-earth perovskite compound, GdScO_3, has been investigated by magnetization and heat capacity. The system undergoes an antiferromagnetic phase transition at T_N= 2.6K, with an easy axis of magnetization along the a axis. The magnetization measurements show that it exists a spin-flop transition around 0.3 T for the applied field along the a axis. The critical magnetic field for the antiferromagnetic-to-paramagnetic transition is near 3.2 T when temperature approaches zero. By scaling susceptibilities, we presume this point(B = 3.2 T, T = 0 K) might be a fieldinduced quantum critical point and the magnetic critical fluctuations can even be felt above TN.     

Geometric simulation of perovskite frameworks with Jahn-Teller distortions: applications to the cubic manganites

A new approach is presented for modeling perovskite frameworks with disordered Jahn-Teller (JT) distortions and has been applied to study the elastic response of the LaMnO3 structure to defects in the JT ordering. Surprisingly, antiphase domain boundary defects in the pattern of ordered JT octahedra, along the [110] and [110] bonding directions, are found to produce 1D stripe patterns rotated 45 degrees along a* directions, similar to stripe structures observed in these systems. Geometric simulation is shown to be an efficient and powerful approach for finding relaxed atomic structures in the presence of disorder in networks of corner-shared JT-distorted octahedra such as the perovskites. Geometric modeling rapidly relaxes large supercells (thousands of octahedra) while preserving the local coordination chemistry, and shows great promise for studying these complex systems.     

Identifying a perovskite phase in rare-earth nickelates using X-ray photoelectron spectroscopy

We demonstrate a practical way to identify the presence of a perovskite phase in rare-earth nickelates (RNiO₃) using X-ray photoelectron spectroscopy (XPS). By varying the calcination temperature, we prepared RNiO₃ powders with different degrees of chemical reaction. We found that perovskite RNiO₃ becomes predominant after high-temperature calcination (≥1,000 °C) in X-ray diffraction and XPS (at Ni 3p and O 1s edges) measurements. While the observed spectra at the Ni 3p edge are similar for all powders, a sizable difference was observed in the O 1s-edge spectra depending on the calcination temperature. With the formation of a perovskite phase with a trivalent Ni³⁺ state, an XPS peak corresponding to oxygen ions in the perovskite lattice distinctly emerges. Our work shows that the Ni³⁺ state cannot be determined by analyzing the Ni 3p edge solely and rather, the O 1s edge should be simultaneously monitored for explicit identification.     

Optical properties and electronic structure of rare-earth ferroborates

The optical absorption spectra of single-crystal ferroborate GdFe₃(BO₃)₄ and GdFe_2.1Ga_0.9(BO₃)₄ are measured and interpreted. It is found that the absorption edge and the absorption bands A, B, and C observed below the edge are close to those for FeBO₃. A many-electron model of the band structure of GdFe₃(BO₃)₄ is suggested including strong electron correlations between the iron d states. It is shown that GdFe₃(BO₃)₄ has a charge-transfer dielectric gap. A rise in pressure is predicted to result in a crossover between the high-spin and low-spin states of the Fe³⁺ ion, collapse of the magnetic moment, a weakening of Coulomb correlations, an abrupt reduction in the energy gap, and an insulator-semiconductor transition.     

On the structure and magnetic properties of rare-earth small particles

It is pointed out that the changes in structural and magnetic properties of small gadolinium, terbium and holmium particles reported by P.E. Chizhov, A.N. Kostigov & V. Petinov, Solid State Commun.42, 323 (1982) may be due to contaminants (hydrogen and oxygen) in their samples and not to size-dependent new phases of the rare-earth metals.     

Magnetic properties and electronic structure of the LaGaO3 perovskite doped with nickel

Solid solutions of the composition LaGa_{1 ? x} Ni _x O₃ (0.01 ≤ x ≤ 0.10) are synthesized, and their magnetic and electrical properties are investigated. It is established that the ground state of the Ni(III) atoms is the low-spin state ² E _g ; however, in the temperature range under investigation, there occurs the ² E _g ? ⁴ T _1g spin equilibrium. An increase in the nickel concentration leads to an increase in the electron conduction of the solid solutions. The band structure of the LaGa_0.5Ni_0.5O₃ model compound is calculated using the ab initio full-potential linearized augmented-plane-wave method within the generalized gradient approximation (FLAPWGGA). It is shown that the dominant role in the variations observed in the magnetic and electrical properties of the nonmagnetic semiconductor LaGaO₃ upon doping with nickel is played by the Ni 3d(e _g ↑, ↓) states.     

The effect of average A-site cation radius on TC in perovskite manganites

Three series of samples Ln_0.7T_0.3MnO₃ (I), Ln_0.7T_0.3Mn_0.9Cr_0.1O₃ (II), and Ln_0.7T_0.3Mn_0.9Fe_0.1O₃ (III) (Ln=La, (La, Nd), (La, Y), T=Ca, CaSr, Sr) were prepared by sol–gel technique. The effect of the average A-site cation radius 〈r_A〉 on the ferromagnetic transition temperature T_C has been investigated. T_C was obtained from M–T curves measured by vibrating sample magnetometer. For a little Nd³⁺ doped at the A-site, the T_C of Ln_0.7T_0.3MnO₃ (I) drops linearly with decreasing 〈r_A〉 (1.18 Å<〈r_A〉<1.25 Å). Similar behavior has been observed in series II and III, which have lower T_C values than series I due to the weakening of the influence of double-exchange interactions upon substituting Fe and Cr for Mn.     

Applications and functions of rare-earth ions in perovskite solar cells

The emerging perovskite solar cells have been recognized as one of the most promising new-generation photovoltaic technologies owing to their potential of high efficiency and low production cost. However, the current perovskite solar cells suffer from some obstacles such as non-radiative charge recombination, mismatched absorption, light induced degradation for the further improvement of the power conversion efficiency and operational stability towards practical application. The rare-earth elements have been recently employed to effectively overcome these drawbacks according to their unique photophysical properties. Herein, the recent progress of the application of rare-earth ions and their functions in perovskite solar cells were systematically reviewed. As it was revealed that the rare-earth ions can be coupled with both charge transport metal oxides and photosensitive perovskites to regulate the thin film formation, and the rare-earth ions are embedded either substitutionally into the crystal lattices to adjust the optoelectronic properties and phase structure, or interstitially at grain boundaries and surface for effective defect passivation. In addition, the reversible oxidation and reduction potential of rare-earth ions can prevent the reduction and oxidation of the targeted materials. Moreover, owing to the presence of numerous energetic transition orbits, the rare-earth elements can convert low-energy infrared photons or high-energy ultraviolet photons into perovskite responsive visible light, to extend spectral response range and avoid high-energy light damage. Therefore, the incorporation of rare-earth elements into the perovskite solar cells have demonstrated promising potentials to simultaneously boost the device efficiency and stability.