The p–T phase diagram of KNbO3 by a dielectric constant measurement

A dielectric constant measurement was carried out on perovskite-type ferroelectrics KNbO₃ over a wide range of temperature under high pressure. The temperature- and pressure-dependence of the dielectric constant clarified that all temperatures of the transitions from the ferroelectric rhombohedral to orthorhombic, to tetragonal and then to the paraelectric cubic phase, decrease with increasing pressure. These results indicate that the orthorhombic–tetragonal transition takes place at 8.5 GPa and the tetragonal–cubic transition at 11 GPa, at room temperature.     

K5Bi0.9Er0.1(MoO4)4的晶体生长和光学性质

在化学计量的熔料里,用提拉法生长了K₅Bi_0.9Er_0.1(MoO₄)₄单晶。该晶体属于三方晶系,空间群为R3m,z=1.5,晶胞参数为a=6.029?,c=20.823?(六方表示)。晶体具有层状结构,沿着(0001)面容易解理。晶体在室温下的吸收光谱包括有若干条吸收带,它们是稀土离子所特有的。其中三个主要的吸收峰分别相当于从Er³⁺离子的基态 ⁴I_15/2向 ⁴G_11/2, ²H_11/2和 ⁴I_13/2能级的跃迁。本文还给出晶体中相当于 ⁴I_13/2→ ⁴I_15/2跃迁的荧光发射光谱。 关键词：     

Leakage current, ferroelectric and structural properties in Pb1−xBaxTiO3 thin films prepared by chemical route

Single-phase perovskite structure Pb_1−xBa_xTiO₃ thin films (x=0.30, 0.50 and 0.70) were deposited on Pt/Ti/SiO₂/Si substrates by the spin-coating technique. The dielectric study reveals that the thin films undergo a diffuse type ferroelectric phase transition, which shows a broad peak. An increase of the diffusivity degree with the increasing Barium contents was observed, and it was associated to a grain decrease in the studied composition range. The temperature dependence of the phonon frequencies was used to characterize the phase transition temperatures. Raman modes persist above tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of breakdown of the local cubic symmetry by chemical disorder. The absence of a well-defined transition temperature and the presence of broad bands in some interval temperature above FE-PE phase transition temperature suggested a diffuse type phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in these thin films. The leakage current density of the PBT thin films was studied at different temperatures and the data follow the Schottky emission model. Through this analysis the Schottky barrier height values 0.75, 0.53 and 0.34 eV were obtained to the PBT70, PBT50 and PBT30 thin films, respectively.     

The influence of different fabrication processes on characteristics of excess Bi2O3-doped 0.95 (Na0.5Bi0.5)TiO3–0.05 BaTiO3 ceramics

In this study, we will develop the influences of the excess x wt% (x=0, 1, 2, and 3) Bi₂O₃-doped and the different fabricating process on the sintering and dielectric characteristics of 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃ ferroelectric ceramics with the aid of SEM and X-ray diffraction patterns, and dielectric–temperature curves. The 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃+x wt% Bi₂O₃ ceramics are fabricated by two different processes. The first process is that (Na_0.5Bi_0.5)TiO₃ composition is calcined at 850 °C and BaTiO₃ composition is calcined at 1100 °C, then the calcined (Na_0.5Bi_0.5)TiO₃ and BaTiO₃ powders are mixed in according to 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃+x wt% Bi₂O₃ compositions. The second process is that the raw materials are mixed in accordance to the 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃+x wt% Bi₂O₃ compositions and then calcining at 900 °C. The sintering process is carried out in air for 2 h from 1120 to 1240 °C. After sintering, the effects of process parameters on the dielectric characteristics will be developed by the dielectric–temperature curves. Dielectric–temperature properties are also investigated at the temperatures of 30–350 °C and at the frequencies of 10 kHz–1 MHz.     

Magnetic properties of Y2Fe15Cr2 single crystal

A Y₂Fe₁₅Cr₂ single crystal with the Th₂Ni₁₇-type structure has been prepared by the Czochralski method and investigated by means of Laue back-reflection, metallographic observation, X-ray diffraction, the singular point detection technique and magnetic measurements. A magnetohistory effect has been observed at a low temperature. Magnetization curves have been measured along the easy and hard directions in fields up to 6.5 T. The saturation magnetization and magnetocrystalline anisotropy field decrease with increasing temperature. The experimental magnetocrystalline anisotropy constant is in good agreement with the calculation results on first approximation.     

Improved microstructure, dielectric and ferroelectric properties of microwave-sintered Sr0.5Ba0.5Nb2O6

Ferroelectric strontium barium niobate (SBN) powder was synthesized by solid-state route. The green compacts were sintered in the temperature range 1250–1350 °C in a microwave furnace. The microstructural study, using SEM, revealed the grain size in the range 2–20 μm without microcracks, depending on the sintering temperature. This is in contrast to that obtained conventionally for sintered SBN powder synthesized by solid-state route, which resulted in duplex microstructure with microcracks [N.S. VanDamme, A.E. Sutherland, L. Jones, K. Bridger, S.R. Winzer, J. Am. Ceram. Soc. 74 (1991) 1785; P.K. Patro, A.R. Kulkarni, C.S. Harendranath, Ceram. Int. 30 (2004) 1405; P.K. Patro, Trans. Ind. Inst. Metals 59 (2006) 229]. Impedance analyzer and ferroelectric hysteresis loop tracer were used for the dielectric, ferroelectric, I–V and electric fatigue measurements. Microwave sintering also resulted in a dielectric maxima ε_max 2590 at 1 kHz (compared to 1103 for conventional sintering [P.K. Patro, A.R. Kulkarni, C.S. Harendranath, Ceram. Int. 30 (2004) 1405]) for the sintering temperature of 1350 °C. Similar improvement in microwave-sintered SBN was observed depending on their sintering condition. The origin of this difference is attributed to microstructural differences arising from difference in heating method. In this paper the observed dielectric and ferroelectric behavior have been correlated with different sintering conditions and consequent microstructure due to microwave sintering.     

Structural and electrical behavior of Pb(Mg1/4Cd1/4Mo1/2)O3 ceramics

Preliminary X-ray structural analysis of polycrystalline Pb(Mg_1/4Cd_1/4Mo_1/2)O₃ ceramics, prepared by a solid-state reaction technique, provides single-phase orthorhombic structure at room temperature. Detailed dielectric studies of the material as a function of temperature reveal a sharp phase transition at temperature T_c=49°C obeying Curie-Weiss behavior. Scanning electron microscope (SEM) studies of the sample show the uniform distribution of grains in the samples. A dielectric anomaly and ferroelectric phase transition observed at 49°C was supported by polarization studies. The activation energy of the sample was calculated from the dielectric data. The variation of dc resistivity with temperature suggests that the compound behaves as a negative temperature coefficient resistor (NTCR).     

Na1−xLixNbO3 ceramics studied by X-ray diffraction, dielectric, pyroelectric, piezoelectric and Raman spectroscopy

Na_1−xLi_xNbO₃ ceramics with composition 0.05≤x≤0.30 were prepared by solid-state reaction method and sintered in the temperature range 1100-1150 °C. These ceramics were characterised by X-ray diffraction as well as dielectric permittivity measurements and Raman spectroscopy. Dielectric properties of ceramics belonging to the whole composition domain were investigated in a broad range of temperatures from 300 to 750 K and frequencies from 0.1 to 200 kHz. The Rietveld refinement powder X-ray diffraction analysis showed that these ceramics have a single phase of perovskite structure with orthorhombic symmetry for x≤0.15 and two phases coexistence of rhombohedral and orthorhombic above x=0.20. The evolution of the permittivity as a function of temperature and frequency showed that these ceramics Na_1−xLi_xNbO₃ with composition 0.05≤x≤0.15 present the classical ferroelectric character and the phase transition temperature T_C increases as x content increases. The polarisation state was checked by pyroelectric and piezoelectric measurements. For x=0.05, the piezoelectric coefficient d₃₁ is of 2pC/N. The evolution of the Raman spectra was studied as a function of temperatures and compositions. The results of the Raman spectroscopy study confirm our dielectric measurements, and they indicate clearly the transition from the polar ferroelectric phase to the non-polar paraelectric one.     

Structural changes in RNiO3 perovskites (R=rare earth) across the metal–insulator transition

Rare earth nickel oxide perovskites (RNiO₃, R=rare earth) have, except for LaNiO₃, a metal–insulator (MI) phase transition as temperature decreases. The transition temperature (T_MI) increases as the R-ion becomes smaller. They also present, at low temperatures, a complex antiferromagnetic order. For lighter R-ions (e.g. Pr and Nd), the antiferromagnetic transition temperature (T_N) is close to T_MI, while for heavier R-ions (e.g. Eu, Sm), T_MI and T_N are very far apart, suggesting that the magnetic and electronic behaviors are not directly coupled. Even though Ni³⁺ is a Jahn–Teller ion, no distortion in the NiO₆ octahedra was found for RNiO₃ perovskites with R=Pr, Nd, Sm and Eu. In this work we have measured EXAFS at Ni K edge for samples of PrNiO₃, NdNiO₃ and EuNiO₃. The Fourier transform spectra for the three samples show a clear splitting in the first peak at the insulating phase. This splitting corresponds to two or more different Ni–O distances. This indicates that there is either a distortion in the NiO₆ octahedra or there are two different Ni sites at the insulating phase.     

Mn nuclear magnetic resonance studies in RMn2Ge2 (R = rare earths)

The ⁵⁵Mn NMR in RMn₂Ge₂ (R= La,Nd and Gd) were observed as a function of temperature. In Nd and Gd compounds the ⁵⁵Mn NMR frequencies exhibit anomalous temperature dependences owing the effects of rare earth sublattices. The ordering temperatures of the Nd and Gd sublattices are found to be 30 and 95 K, respectively.     

顺磁性La2/3Sr1/3MnO3层对Bi0.8Ba0.2FeO3薄膜多铁性能的影响

界面效应在提升异质结构材料的多铁性能方面有着重要的作用. 本文采用脉冲激光沉积技术在SrTiO₃(STO)基片上制备了Bi_0.8Ba_0.2FeO₃(BBFO)/La_2/3Sr_1/3MnO₃(LSMO)异质结. X-射线衍射图谱表明异质结呈现单相外延生长, 利用高分辨透射电镜进一步证实了BBFO为四方相结构. X-射线光电子能谱证实异质结中只存在Fe³⁺ 离子, 没有产生价态的变化, 揭示了异质结铁电和铁磁性的增强与BBFO/LSMO的界面有关. 同时, 测试了磁电阻(MR)和磁介电(MD), 当磁场强度为0.8 T, 温度为70 K时, MR约为-42.2%, MD约为21.2%. 并且发现在180 K时出现磁相的转变. 实验结果揭示出异质界面效应在提升材料的多铁性和磁电耦合效应方面具有超常的优点, 是加快多铁材料实际应用的有效途径.     

Magnetic behavior of 3d dopants in superconducting REBa2Cu3−xFexO7+δ (RE=Dy, Er)

Mössbauer studies on ⁵⁷Fe-doped superconducting REBa₂Cu₃O_7+δ (RE=Er, Dy) were made as a function of temperature for x=0.15 and 0.30. The magnetic behavior of the 3d dopants, which mainly occupy Cu(1) sites, undergoes antiferromagnetic ordering which is coexistent with superconductivity at low temperature. The dimensionality of the magnetic interaction changes from 2D to 3D when the rare earth changes from Er to Dy. the line-widths of the Mössbauer subspectra are characteristic of magnetic fluctuation behavior in the vicinity of a phase transition. Combining these results with those of Fe-doped Y-123 (pseudo 1D) and Gd (3D), the magnitude of the rare earth moments appears to be strongly correlated with the dimensionality of the magnetic interaction of Fe dopants in these compounds. However, the Mössbauer spectrum for ¹⁵⁵Gd in GdBa₂Cu_2.85Fe_0.15O_7+δ (T_{N(Fe) 14 K}) shows no magnetic order at 4.9 K.     

Decoupling of the order-disorder and displacive contributions to the phase transition in NH4H(ClH2CCOO)2

The effects of hydrostatic pressure and substitution of Rb⁺for the ammonium cations on the ferroelectric phase transition temperature in NH₄H(ClH₂CCOO)₂ have been studied by electric permittivity measurements. The transition temperature (T_c) decreases with increasing pressure up to 800 MPa and the pressure coefficient dT_c/dp=−1.4×10⁻² [K/MPa] has been experimentally determined. The substitution of Rb⁺ for the ammonium cations has been shown to considerably lower the ferroelectric phase transition temperature T_c. In mixed crystals, additional electric permittivity anomaly has been clearly evidenced. The results are discussed assuming a model, which combines polarizability effects, related to the heavy ion units, with the pseudo-spin tunnelling.     

Ferromagnetic resonance in Sr doped rare earth orthocobaltites, Ln1−xSrxCoO3†

FMR measurements have been carried out on several members of the Ln_1−xSrxCoO₃ (Ln = Rare earth) system. The results show that g_eff in these systems is around 1.25 independent of x as well as the rare earth ion. It is suggested that this unusual value of g_eff is due to the localized intermediate-spin Co³⁺ ions (t⁵_2g e¹_g) located at the top of the π^* band.     

Impurity effect on the Raman spectra of Sr0.6Ba0.4Nb2O6

Impurity effect on the rare earth ion doped Sr_0.6Ba_0.4Nb₂O₆(SBN40) was studied at room temperature. Doping the rare earth ions of Pr³⁺ or Nd³⁺ changed the Raman profile: spectral broadening, central frequency shifts and relative intensity decreasing. Two reasons are considered according to the ferroelectric and optical properties of the rare earth ion doped SBN40: impurity-induced crystal disorder and the crystal structure change. SBN40 is the general disorder crystal and the disorder which is enhanced by doping the rare earth ion is especially strong along the x?y plane of the material compared with that along the polar C-axis.     

Coexistence of magnetic and ferroelectric properties in Y0.1Co1.9MnO4

The magnetic,conductivity,and dielectric properties have been investigated in single-phase polycrystalline Y0.1 Co1.9 MnO4.The temperature-dependent magnetisation reveals the ferromagnetic transition in sample at a low temperature (～186 K).Magnetisation as a function of field H (M-H loop) indicated the weak ferromagnetism of the sample at room temperature.The constant ε and dielectric loss tgδ measurements represent a ferroelectric phase transition at a higher temperature (～650 K),while the conductivity shows an insulator-metallic transition.The ferroelectric hysterisis loops and capacitance-voltage measurements confirm the ferroelectric nature of the sample at room temperature.The observed ferromagnetism and ferroelectric nature in this material suggests a potential multiferroic application.     

Handling the particle size and distribution of Fe3O4 nanoparticles through ball milling

A series of samples consisting of spinel Fe₃O₄ nanoparticles with controlled particle sizes and increasing concentration has been obtained through ‘mild’ ball milling (BM) experiments by using an organic carrier liquid. We have succeeded in producing quite narrow particle size distributions with mean values d7–10 nm by an appropriate choice of the milling time for each concentration. The method proved to be practical to tailor the final particle size without formation of undesirable phases. All samples showed superparamagnetic behavior at room temperature, with transition to a blocked state at T_B10–20 K. The mean value and distribution width of the size distributions for the three samples studied were obtained from M(H) cycles recorded at T>T_B showing good agreement with X-ray diffraction and electron microscopy results. The effect of increasing interparticle interactions was to shift T_B upwards, as inferred from magnetization measurements. Mössbauer spectra at low temperatures showed no evidence of enhanced spin disorder.     

Magnetic structures of R3Cu4Si4 (R=Dy, Ho and Er)

Polycrystalline samples of R₃Cu₄Si₄ (R=Dy, Ho, Er) intermetallics were studied with neutron diffraction methods. All of them crystallize in the orthorhombic structure of Gd₃Cu₄Ge₄-type and order antiferromagnetically at low temperatures. Magnetic moments localized at the rare earth atoms, that occupy two non-equivalent 2d and 4e sublattices, order simultaneously in Dy₃Cu₄Si₄. The order is described by the propagation vector accompanied by , δ=0.025(2). In Ho₃Cu₄Si₄ two propagation vectors are needed to model the magnetic order. These are: for the 4e sublattice, which disorders as the first when the temperature increases, and for the 2d sublattice. A similar situation is observed for Er₃Cu₄Si₄ where the propagation vectors are: k=(0,1−δ,0), δ=0.097(2) for the 4e sublattice, which disorders as the first with increasing temperature, and , δ=0.0015(6) for the 2d sublattice.     

Observation of complex magnetic behavior in the perovskite rare earth copper oxide systems, R2CuO4

EPR, microwave absorption, and dc magnetization measurements were made on single crystals of the form R₂CuO₄, which are the host compounds for the newly discovered series of electron cuprate superconductors. These measurements reveal two characteristic transition temperatures associated with a novel complex magnetic behavior, including weak ferromagnetism, two sharp peaks in the low field DC magnetization, an unusual anisotropy in the EPR resonance field for R = Gd, and two additional anisotropic microwave absorption modes. The higher characteristic transition temperature, at ≈270K, is attributed to AF ordering of the Cu moments, and the lower, at ≤20K, to a spontaneous canted spin reorientation. An understanding of this magnetic behavior is important in order to ascertain its relationship to possible mechanisms of high temperature superconductivity.     

Phase transition in Pb4.9A0.1Ge2.7Si0.3O11 (A=Ca,Sr,Ba) ferroelectrics

Polycrystalline samples of modified lead germanate Pb_4.9A_0.1Ge_2.7Si_0.3O₁₁ (A=Ca,Sr,Ba) have been prepared by solid-state reaction technique. X-ray studies have been carried out to check the formation of single-phase composition and to obtain preliminary structural data. Measurements of dielectric permittivity () and loss (tan δ) have been studied both as a function of frequency (10²–10⁴ Hz) and temperature (room temperature to 180°C). Phase transition was observed in all three cases but with different T_c value. From the plots of conductivity vs. temperature using dielectric data, collected at 10 kHz activation energy was calculated to investigate the conduction mechanism in them.