A new, lead free, family of perovskites with a diffuse phase transition: NaNbO3-based solid solutions

(1−x)NaNbO₃-(x)ABO₃ perovskite solid solutions belonging to group II according to the Krainik classification [Izv. Akad. Nauk SSSR, Ser. Phys. 28 (1964) 643] exhibit a dramatic diffusion of the dielectric permittivity ε′ maximum and relaxor-type behavior when the second component concentration exceeds a threshold value x₀. The concentration phase transition to this relaxor-like phase is abrupt (of the first order kind) that is seen from the step in the dependence of the ε′(T) maximum temperature, T_m, on x. Some relaxor-like properties appear even at x<x₀ in the course of cooling while disappear during the course of heating. Due to this fact and because of coupling of the antiferroelectric (AFE) and ferroelectric (FE) order parameters a giant (up to 100 K) temperature hysteresis of ε′(T) arises at AFE-AFE first order phase transition. The T_m values of all the known NaNbO₃-ABO₃ relaxor-type compositions are well below the room temperature and the dielectric permittivity maximal values, ε′_m, are much lower than in the case of Pb-containing relaxors. However both T_m and ε′_m values can be increased substantially by Li or K-doping leading to the formation of NaNbO₃-ABO₃-LiNbO₃ (KNbO₃) solid solutions.     

Influence of mobile space charges on electrical properties of ferroelectric Bi3.5La0.5Ti3O12 thin films

Lanthanum-substituted bismuth titanate, Bi_3.5La_0.5Ti₃O₁₂ (i.e., x=0.5 in Bi_4−xLa_xTi₃O₁₂), thin films have been grown on Pt/Ti/SiO₂/Si substrates using pulsed laser deposition. The frequency dependence of the real part ε′(ω) and the imaginary part ε″(ω) of the dielectric constant has been studied. The ε′(ω) does not show any sudden change within the frequency range of 10²-10⁶ Hz. In contrast, the ε″(ω) shows a large dispersion as frequency decreases. The observed relaxation behavior in ε″(ω) can be explained in terms of a migration of oxygen vacancies in (Bi₂O₂)²⁺ layers, not in Bi₂Ti₃O₁₀ perovskite layers.     

High pressure effects on the electrical resistivity behavior of the Kondo lattice, YbPd2Si2

We report the influence of external high-pressure (P up to 8 GPa) on the temperature (T) dependence of electrical resistivity (ρ) of a Yb-based Kondo lattice, YbPd₂Si₂, which does not undergo magnetic ordering under ambient pressure condition. There are qualitative changes in the ρ(T) behavior due to the application of external pressure. While ρ is found to vary quadratically below 15 K (down to 45 mK) characteristic of Fermi-liquids, a drop is observed below 0.5 K for P=1 GPa, signaling the onset of magnetic ordering of Yb ions with the application of P. The T at which this fall occurs goes through a peak as a function of P (8 K for P=2 GPa and about 5 K at high pressures), mimicking Doniach's magnetic phase diagram. We infer that this compound is one of the very few Yb-based stoichiometric materials, in which one can traverse from valence fluctuation to magnetic ordering by the application of external pressure.     

Magnetoelectric behavior in the complex CaMn7O12 perovskite

We report a magnetoelectric effect in the double perovskite CaMn₇O₁₂, that shows a complex magnetic behavior below 90 K with two magnetic phases coexisting (one ferrimagnetic and the other modulated). A second magnetic transition, associated with changes in the magnetic modulation and magnetic ordering coherence lengths of the two magnetic phases occurs at 50 K (T_N2). A detailed structural characterization of this compound, that we have carried out by means of high-resolution X-ray powder diffraction, reveals an anisotropic thermal expansion of its lattice parameters at 50 K (T_N2). In addition, our study of the complex permittivity of this sample as a function of temperature, frequency and magnetic field shows very interesting results below 90 K and specially below 50 K: the dielectric constant ε′_r that was decreasing continuously on cooling experiences an upturn, and even more, on application of a magnetic field it shows a moderate magnetoelectric response. We attribute such dielectric behavior to the formation of electric dipoles by magnetostriction in this charge and spin ordered system, that are sensible to the presence of an external magnetic field.     

Dielectric and optical behaviors in relaxor ferroelectric Pb(In1/2Nb1/2)1−xTixO3 crystal

Dielectric permittivities (ε′,ε″) have been measured as functions of temperature (140-535 K) and frequency (500 Hz-2.0 MHz) in a (001)-cut Pb(In_1/2Nb_1/2)_0.7Ti_0.3O₃ (PINT30%) single crystal grown by the modified Bridgman method with Pb(Mg_1/3Nb_2/3)_0.71Ti_0.29O₃ (PMNT29%) seed crystal. A diffused phase transition was observed in the temperature region of ∼430-460 K with strong frequency dispersion. Above the Burns temperature T_B≅510 K, the dielectric permittivity was found to follow the Curie-Weiss behavior, ε′=C/(T−T_C), with parameters C=3.9×10⁵ and T_C=472 K. Below T_B≅510 K, polar nanoclusters are considered to appear and are responsible for the diffused dielectric anomaly. Optical transmission, refractive indices, and the Cauchy equations were obtained as a function of wavelength at room temperature. The unpoled crystal shows almost no birefringence, indicating that the average structural symmetry is optically isotropic. The crystal exhibits a broad transparency in the wavelength range of ∼0.4-6.0 μm.     

Synthesis and physical characterization of superconductivity-magnetism crossover compound RuSr2EuCeCu2O10−δ

We carefully studied the nonsuperconducting sample of the magneto-superconducting RuSr₂(Eu_1−xCe_x)Cu₂O_10−δ series with composition RuSr₂EuCeCu₂O_10−δ. This compound seems to exhibit a complex magnetic state as revealed by host of techniques like resistivity, thermopower, magnetic susceptibility, and MR measurements. The studied compound exhibited ferromagnetic like M(H) loops at 5, 20, and 50 K, and semiconductor like electrical conduction down to 5 K, with −MR^7 T of up to 4% at low temperatures. The −MR^7 T decreases fast above 150 K and monotonically becomes close to zero above say 230 K. Below, 150 K −MR^7 T decreases to around 3% monotonically down to 75 K, with further increase to 4% at around 30 K and lastly having a slight decrease below this temperature. The thermopower S(T) behavior closely followed the −MR^7 T steps in terms of d(S/T)/dT slopes. Further, both MR^7 T steps and d(S/T)/dT slopes are found in close vicinity to various magnetic ordering temperatures (T_mag) of this compound.     

Relaxation and conductivity behaviour in the compounds: FeRGe2O7 (R=Pr,Tb)

AC measurements were performed on the thortveitite-like layered compounds, FeRGe₂O (R=Pr,Tb) in order to study their dielectric features, e.g. as a function of temperature. The main electrical response lies on impedance plots composed of two successive arcs with depressed centers. Bulk conductivity behavior is mostly Arrhenius for the measured temperatures. The associated bulk activation energies are close to 1 eV. Raw data were used to follow the temperature dependence of the dynamic parameters, ε′(ω) and σ′(ω). From logarithmic σ′(ω) vs. ω curves the dc component was obtained. ε′(ω) vs. log ω curves exhibit a dispersive behavior at low frequencies, reflecting blocking effects. E_dc and E_ac activation energies were also calculated, the last one obtained from σ′(ω) vs. 1000/T plots. Conductivity results suggest the occurrence of an extrinsic conducting mechanism. A structural instability was detected via the temperature dependence of permittivity, which has been ascribed to the presence of Ga-O-Ga bonds having associated angles different of 180°. Analyses of the results show that the interchange of Tb and Pr in the general formula FeRGe₂O₇ (R=Pr, Tb) involves only small differences in their global ac and dc behavior.     

The optical properties of HgS under high pressures

The DOS (density of states) and the optical properties of HgS under high pressure are studied with the first-principle computations. The change of the imaginary part, ε₂(ω), of the dielectric function shows that HgS tends to metallization with increasing pressure, and this well agrees with the band gap calculations and the conductivities measurement results in the previous work. Under the pressures below 15 GPa, ε₂(ω) is relatively anisotropic and tends to be more anisotropic with increasing pressure; while under the pressures above 15 GPa, the anisotropy decreases and finally becomes almost absolutely isotropic after the phase transition. The behavior of ε₂(ω) is strongly related to the structure change in the cinnabar to rocksalt phase transition process under high pressure.     

Magnetic study of Mg0.95Mn0.05Fe2O4 ferrite nanoparticles

The magnetic properties of Mg_0.95Mn_0.05Fe₂O₄ ferrite samples with an average particle size of ∼6.0±0.6 nm have been studied using X-ray diffraction, Mössbauer spectroscopy, dc magnetization and frequency dependent real χ^′(T) and imaginary χ^″(T) parts of ac susceptibility measurements. A magnetic transition to an ordered state is observed at about 195 K from Mössbauer measurements. The zero-field-cooled (ZFC) and field-cooled (FC) magnetization have been recorded at low field and show the typical behavior of a small particle system. The ZFC curve displays a broad maximum at , a temperature which depends upon the distribution of particle volumes in the sample. The FC curve was nearly flat below , as compared with monotonically increasing characteristics of non-interacting superparamagnetic systems indicating the existence of strong interactions among the nanoparticles. A frequency-dependent peak observed in χ^′(T) is well described by Vogel-Fulcher law, yielding a relaxation time and an interaction parameter . Such values show the strong interactions and rule out the possibility of spin-glass (SG) features among the nanoparticle system. On the other hand fitting with the Néel-Brown model and the power law yields an unphysical large value of τ₀ (∼6×10⁻⁶⁹ and 1.2×10⁻²² s respectively).     

Low-temperature phase transformations in weakly doped quantum paraelectrics: novel features and quantum reentrant dipolar glass state in KTa0.982Nb0.018O3

An unusual sequence of phase transitions (PT) and reentrant dipole glass-like phase formation at low temperatures was found recently in KTaO₃ weakly doped with Li and Nb (K_0.9986Li_0.0014Ta_0.976Nb_0.024O₃) [Phys. Rev. B 63 (2001) 172]. We report on detailed low frequency (100 Hz-1 MHz) permittivity and Raman light scattering studies of similar composition, but without Li admixture, KTa_1−xNb_xO₃ with x=0.018 (KTN1.8). The aim of the study is to answer the question if the reentrant dipole glass-like phase exists in KTN1.8 and what is the microscopic origin of this phase. A detailed study of the sharp low-temperature PT observed at T_C∼27 K revealed properties inherent to the reentrant glass-type state at lower temperatures. The substitution of Nb for Ta influences the TO₁ soft lattice mode and leads to PT with the long-range ferroelectric ordering. A crossover to an order-disorder polar microregion dynamics with a non-standard ε′(T) behaviour and dipole glass-like formation were found below T_C (at ∼15 K), which is attributed to the randomness of the Nb distribution. A crossover to the long-range order was found under a dc bias field.     

Effects of low frequency near metal-insulator transition temperatures on polycrystalline La0.65Ca0.35Mn1−yFeyO3 (where y=0.05-0.10) ceramic oxides

The ac electrical properties of 5-10% Fe doped polycrystalline sample have been investigated by complex impedance analysis over the frequency and temperature ranges of 1-100 kHz and 77-300 K, respectively. The average normalized change (ΔZ′/Δf)/Z₀ has been deduced for these Fe doped CMR samples which shows an increasing trend with iron doping. The most pronounced effect of frequencies is at T_c, with the increase of Fe doping it is observed that not only T_c is lowered substantially but also the height of the peaks of real part of impedance (Z′) is increased which in turn decreases considerably with the increase of the ac field. An equivalent circuit model, R_g(R_gbC_gb), i.e. a resistor-capacitor network, has been proposed to explain the impedance results at different temperatures. The plot between τ and 1/T gives a straight line from where relaxation time (τ₀) has been deduced. The correlated barrier hopping (CBH) model has been employed and the binding energy of the defect states is estimated to be between 0.39 and 0.25 eV while the minimum hoping distance varies within the range of 2.93-5.21 Å for these 5-10% Fe doped LCM samples.     

Spin-state transition, magnetic, electrical and thermal transport properties of the perovskite cobalt oxide Gd0.7Sr0.3CoO3

The magnetization, resistivity ρ, thermoelectric power (TEP) S, and thermal conductivity κ in perovskite cobalt oxide Gd_0.7Sr_0.3CoO₃ have been investigated systematically. Based on the temperature dependence of susceptibility χ_g(T) and Seebeck coefficient S(T), a combination of the intermediate-spin (IS) state for Co³⁺ and the low-spin (LS) state for Co⁴⁺ can be suggested. A metal-insulator transition (MIT) caused by the hopping of σ* electrons (localized or delocalized e_g electrons) from the IS Co³⁺ to the LS Co⁴⁺ is observed. Meanwhile, S(T) curve also displays an obvious phonon drag effect. In addition, based on the analysis of the temperature dependence of S(T) and ρ(T), the high-temperature small polaron conduction and the low-temperature variable-range-hopping conduction are suggested, respectively. As to thermal conduction κ(T), rather low κ values in the whole measured temperature range is attributed to unusually large local Jahn-Teller (JT) distortion of Co³⁺O₆ octahedra with IS state.     

Study of the magnetization and transport properties of the La(2+x)/3Sr(1−x)/3Mn1−xCrxO3 (0≤x≤0.2) system

The samples with the Mn³⁺/Mn⁴⁺ ratio fixed at 2:1 La_(2+x)/3Sr_(1−x)/3Mn_1−xCr_xO₃ (0≤x≤0.20) have been prepared. The magnetic, electrical transport, and magnetoresistance properties have been investigated. Remarkable transport and colossal magnetoresistance (CMR) effect, as well as cluster glass (CG) behaviors have been clearly observed in the samples studied. It was found that the Curie temperature T_c and insulator−metal transition temperature T_p1 are strongly affected by Cr substitution. The experiment observations are discussed by taking into account the variety of tolerance factors t; the effects of A-site radius 〈r_A〉 and the A-site mismatch effect (σ²).     

Influence of Pr-doping on structural, electronic transport, magnetic properties of perovskite molybdates Sr1−xPrxMoO3 (0≤x≤0.15)

The effect of Pr-doping on structural, electronic transport, magnetic properties in perovskite molybdates Sr_1−xPr_xMoO₃ (0≤x≤0.15) has been investigated. The Pr-doping at Sr-site does not change the space group of the samples, but decreases the lattice parameter a. The magnitude of resistivity ρ increases initially (x≤0.08) and then decreases with further increasing Pr-doping level x and ρ(T) behaves as T² and T dependence in the low-temperature range blow T* and high-temperature range of 150 K<T<350 K, related to the electron-electron (e-e) and electron-phonon (e-ph) scattering, respectively. The magnetic susceptibility χ value of the sample increases with increasing x and the χ(T) curve for all samples can be well described by the model of exchange-enhanced paramagnetism. The specific heat magnitude in the low-temperature region increases with increasing Pr-doping level. The specific heat value agrees with the classical Dulong-Petit phonon specific heat, C_cl=3k_BrN_A=124.7 J/mol K in the high-temperature region and the temperature dependence of the specific heat can be well described by the formula C_p(T)/T=γ_e+β_pT² in the low-temperature range. These behaviors can be explained by the competition between the increase in the density of state (DOS) at Fermi energy level and the disorder effect due to Pr-doping.     

Analysis of low temperature specific heat in Nd0.5Sr0.5MnO3 and R0.5Ca0.5MnO3 (R=Nd,Sm, Dy and Ho) compounds

We report on the specific heat C(T) of doped manganites Nd_0.5Sr_0.5MnO₃, Nd_0.5Ca_0.5MnO₃, Sm_0.5Ca_0.5MnO₃, Dy_0.5Ca_0.5MnO₃ and Ho_0.5Ca_0.5MnO₃ in the temperature range 2?T?300 K using modified rigid ion model (MRIM). The present specific heat results are in general satisfactory agreement with experimental data except at very low temperatures (i.e. T?12 K). Also a sharp peak observed in the experimental results for these compounds around 5 K could not be revealed by our computed results as they arise due to Schottky-like anomaly. Besides, we have reported the cohesive and the thermal properties of these compounds. The results obtained by us are discussed in detail.     

Cr-doping effect on the structural, magnetic, transport properties and Raman spectroscopy of La(2+x)/3Sr(1−x)/3Mn1−xCrxO3 perovskites

A series of the double-doping samples La_(2+x)/3Sr_(1−4x)/3Mn_1−xCr_xO₃ (0?x?0.25) with the Mn³⁺/Mn⁴⁺ ratio fixed at 2:1 have been fabricated. The structural, magnetic, transport properties and Raman spectroscopy have been investigated, and no apparent crystal structure change is introduced by Cr doping up to x=0.25. But the Curie temperature T_C and metal-insulator transition temperature T_MI are strongly affected by Cr substitution. The room temperature Raman spectra start exhibiting some new features following the increasing concentration of Cr substitutions. Moreover, it is worth noting that the frequency of the A_1g phonon mode can also be well correlated with the A-site mismatch effect (σ²), which is influenced mainly by the variety of the Sr content.     

Intrinsic inhomogeneity and non-linear conduction in charge-ordered Bi0.5Ca0.4Sr0.1MnO3

Systematic studies of X-ray, magnetic, electronic transport, and elastic properties have been performed on polycrystalline Bi_0.5Ca_0.4Sr_0.1MnO₃ sample. The sample exhibits charge ordering (CO) state below T_CO (=304 K), accompanied by a distinct maximum in magnetization. The softening of Young's modulus in the vicinity of T_CO indicates that there is a strong coupling of electron-phonon due to Jahn-Teller (JT) effect. The dynamic ferromagnetic spin correlations are observed at high temperatures above T_CO, which are replaced by antiferromagnetic (AFM) spin fluctuations at a concomitant CO transition. Below 32 K, a spin-glass (SG) state dominates at low temperatures. The voltage-current (V-I) characteristics measurement results indicate that the non-linear conduction starts above a threshold current, giving rise to a region of negative differential resistance (NDR). The origin of the non-linear conduction is discussed in view of current induced collapse of CO state associated with phase-separation mechanism.     

Maxwell-Wagner characterization of dielectric relaxation in Ni0.8Zn0.2Fe2O4/Sr0.5Ba0.5Nb2O6 composite

Dense composites were prepared through incorporating the dispersed Ni_0.8Zn_0.2Fe₂O₄ ferromagnetic particles into Sr_0.5Ba_0.5Nb₂O₆ ferroelectric matrix. Extrinsic dielectric relaxation and associated high permittivities of the materials are reported in the composites. We used an ideal equivalent circuit to explain electrical responses in impedance formalism. A Debye-like relaxation in the permittivity formalism was also found. Interestingly, real permittivity (ε′) of the sample containing 30% Ni_0.8Zn_0.2Fe₂O₄ shows obvious independence of the temperature at 100 kHz. Dielectric relaxation and high-ε′ properties of the composites are explained in terms of the Maxwell-Wagner (MW) polarization model.     

Plasticity and ab initio characterizations on Fe4N produced on the surface of nanocrystallized 18Ni-maraging steel plasma nitrided at lower temperature

18Ni-maraging steel has been entirely nanocrystallized by a series of processes including solution treatment, hot-rolling deformation, cold-drawn deformation and direct electric heating. The plasma nitriding of nanocrystallized 18Ni-maraging steel was carried out at 410 °C for 3 h and 6 h in a mixture gas of 20% N₂ + 80% H₂ with a pressure of 400 Pa. The surface phase constructions and nitrogen concentration profile in surface layer were analyzed using an X-ray diffractometer (XRD) and the glow discharge spectrometry (GDS), respectively. The results show that an about 2 μm thick compound layer (mono-phase γ′-Fe₄N) can be produced on the top of the surface layer of nanocrystallized 18Ni-maraging steel plasma nitrided at 410 °C for 6 h. The measured hardness value of the nitrided surface is 11.6 GPa. More importantly, the γ′-Fe₄N phase has better plasticity, i.e., its plastic deformation energy calculated from the load-displacement curve obtained by nano-indentation tester is close to that of nanocrystallized 18Ni-maraging steel. Additionally, the mechanical properties of γ′-Fe₄N phase were also characterized by first-principles calculations. The calculated results indicate that the hardness value and the ratio of bulk to shear modulus (B/G) of the γ′-Fe₄N phase are 10.15 GPa and 3.12 (>1.75), respectively. This demonstrates that the γ′-Fe₄N phase has higher hardness and better ductility.     

Antiferromagnetism and spin-glass transition in the FeInxCr2−xSe4 series of selenides

The magnetic behavior of the FeIn_xCr_2−xSe₄ system (with x=0.0, 0.2 and 0.4) has been investigated by magnetic and Mössbauer spectroscopy. Hyperfine parameters indicate that iron is in the Fe²⁺ oxidation state, with a minor (∼9%) Fe³⁺ fraction, located at different layers in the structure. Low-field magnetization curves as a function of temperature showed that the antiferromagnetic (AFM) order temperature is T_N=208(2) K for FeCr₂Se₄ and decreases to 174(3) K for FeIn_0.4Cr_1.6Se₄. The effective magnetic moment μ_eff decreases with increasing In contents, and shows agreement with the expected values from the contribution of Fe²⁺ (⁵D) and Cr³⁺ (⁴F) electronic states. A second, low-temperature transition is observed at T_G∼13 K, which has been assigned to the onset of a glassy state.