Stabilization of charge ordering in La1/3Sr2/3FeO3-delta by magnetic exchange

The magnetic exchange energies in charge ordered La1/3Sr2/3FeO3-delta (LSFO) and its parent compound LaFeO3 (LFO) have been determined by inelastic neutron scattering. In LSFO, the measured ratio of ferromagnetic exchange between Fe3+-Fe5+ pairs (JF) and antiferromagnetic exchange between Fe3+-Fe3+ pairs (JAF) fulfills the criterion for charge ordering driven by magnetic interactions (|JF/JAF|>1). The 30% reduction of JAF as compared to LFO indicates that doped holes are delocalized, and charge ordering occurs without a dominant influence from Coulomb interactions.     

TiO2 coating of LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion batteries

TiO₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ materials were prepared by the hydrolyzation of Ti(OBu)₄. The impact of TiO₂ coating on the structure and electrochemical properties of LiNi_1/3Co_1/3Mn_1/3O₂ was investigated using X-ray diffraction, scanning electron microscope, and charge–discharge tests. The results indicated that TiO₂ coating did not affect the lattice of LiNi_1/3Co_1/3Mn_1/3O₂, but exhibited obvious effects on its discharge capacity and cycling stability. As coated TiO₂ increased from 0.0 to 2.0 mol%, the initial capacity of samples decreased slightly, but the cycling stability over 2.5∼4.3 V increased remarkably. The capacity retention reached 99.5% at the 50th cycle at a coating amount of 2.0 mol%.     

(Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics with simultaneous addition of CeO2 and La2O3

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (BNBT-6) with simultaneous addition of 0.5 mol% CeO₂ and 0.25, 0.5 and 0.75 mol% La₂O₃, respectively, was prepared by a conventional ceramic fabrication technique. An addition of 0.5 mol% CeO₂ together with 0.5 mol% La₂O₃ enhanced the piezoelectric and dielectric constant of BNBT-6 ceramics significantly. At room temperature, this composition exhibits a high piezoelectric constant (d₃₃=162×10^-12 C/N) and relatively low dielectric loss (cos=2.0%) at 1 kHz. X-ray diffraction pattern shows that the coexistence of tetragonal and rhombohedral phases in the BNBT-6 composition was not changed by adding CeO₂+La₂O₃, and they diffused into the BNBT lattice during sintering. SEM observation indicates that a small amount of CeO₂+La₂O₃ almost does not affect the microstructure. PACS 77.65.Bn; 77.84.Dy; 77.22.-d     

Facile preparation and performance of novel high-TC xBi(Ni1/2Ti1/2)O3-(1-x)Pb(Zr1/2Ti1/2)O3 piezoceramics

High Curie temperature (T_C) xBi(Ni_1/2Ti_1/2)O₃-(1-x)Pb(Zr_1/2Ti_1/2)O₃ (xBNT-(1-x)PZT, BNT-PZT) piezoelectric ceramics were prepared by the conventional ceramic processing. The composition-induced morphotropic phase boundary (MPB) and its influences on structure and electrical performance were investigated. The synthesized BNT-PZT ceramics exhibit rather pure perovskite structure, and densified microstructure morphology with uniform elementals distribution in both grains and grain boundaries. With increasing the content of Bi(Ni_1/2Ti_1/2)O₃ (BNT), crystal structure of the BNT-PZT ceramics transform from tetragonal phase to rhombohedral phase, and dielectric response peaks change from narrow shape to very broad shape but all presenting dielectric frequency dispersion. The diffused and relaxation dielectric behavior can be fitted well by the quadratic law, and the Vogel-Fulcher law fitting provides additional information on the relaxation characteristic. The MPB effects are confirmed further by ferroelectric and piezoelectric properties measurements. High-T_C combined with excellent piezoelectric performance can be realized in the BNT-PZT system, which presents promising applications in geothermal exploration, aerospace and related elevated temperatures fields.     

Solid-state electrochemical CO2 sensor by coupling lithium ion conductor (Li2CO3-Li3PO4-Asl2O3) with oxide ion-electron mixed conductor (La0.9Sr0.1MnO3)

A solid-state electrochemical cell of the type O₂(air), PtLa_0.9Sr_0.1MnO₃/Li₂CO₃(+5 mol% Li₃PO₄ + 6 mol% Al₂O₃)/Au, CO₂, O₂ was composed to determine CO₂ concentration, where Li₂CO₃, a lithium ion conductor, was used as an electrolyte, and the perovskite-type oxide (La_0.9Sr_0.1MnO₃)/O₂-electrode as a reference electrode. The electromotive force (EMF) of the cell was found to be proportional to the logarithm of CO/₂ partial pressure in CO₂/O₂/N₂ gas mixtures at temperatures between 300 and 400 °C. The EMF responded to changes of CO₂ partial pressure within 1 min at 400 °C. The sensitivity to CO₂ of this cell was not affected by coexistence of O₂, and the EMF remained constant after the first 15 days. The mechanism for sensing CO₂ is discussed.     

Properties of (Bi1/9Na2/3)(Mn1/3Nb2/3)O3 analysed within dielectric permittivity,conductivity, electric modulus and derivative techniques approach

The (Bi_1/9Na_2/3)(Mn_1/3Nb_2/3)O₃ ceramics with perovskite structure were sintered. The XRD test proved that the samples are cubic (a?=?3.920?±?0.001?Å). Microstructure and atomic composition were determined with a SEM (JSM-5410) equipped with energy dispersion X-ray analyser (ISIS-300). The fluctuation in the chemical composition was found indicating on local disorder. Broadband dielectric spectroscopy in the range 10^?1–3?·?10⁷?Hz was applied within the range of 100–650?K. The real, ?′(f,?T), and imaginary, ?″(f,?T), parts of complex dielectric permitivity characteristics, both in the temperature and frequency domain, show relaxation processes partially covered by electric conductivity. At high temperatures the electric conductivity exhibits a thermally activated behaviour σ(f,?T)?∝?exp(?E _a/kT) but the variable range hopping (VRH) dependence σ?∝?exp[?(T ₀/T)^1/4] is manifested at low temperatures. The derivatives technique in the frequency (??log??/??log?ω) and temperature (??log??/?T) domain enabled various relaxation processes to be distinguished. The data converted to electric modulus representation, M*(f,?T)?=?1/?*, exhibited clearly resolved relaxation peaks. The relaxation times obtained from the peaks position show a slightly non-Arrhenius temperature behaviour with the activation energy varying in 0.4–0.6?eV range and characteristic time of the electric conductivity relaxation of the order of 10^?12?s. The relaxation times can be fitted at better accuracy with the VRH dependence where T ₀ are of the order of 10⁸?K. It is shown that the low frequency ac-conductivity converges to dc-conductivity and the relation σ(0)?～?ω_m?～?τ_m ^?1 typical for the disordered solids applies. The conduction current relaxation relationship behaves in accord with the VRH system: σ_dc?∝?(T/T ₀)^q (e ²/kT) ω_c, where ω_c?=?ν_ph exp[?(T ₀/T)^1/4] is valid for the locally disordered (Bi_1/9Na_2/3)(Mn_1/3Nb_2/3)O₃ compound.     

Dielectric and impedance measurements on (1−x)Ba(Fe1/2Ta1/2)O3-xBa(Zn1/3Ta2/3)O3 ceramics

In this work, ((1−x)Ba(Fe_1/2Ta_1/2)O₃-xBa(Zn_1/3Ta_2/3)O₃), ((1−x)BFT-xBZT) ceramics with x = 0.00–0.12 were synthesized by the solid–state reaction method. X-ray diffraction data revealed that both the powders and ceramics were of a pure-phase cubic perovskite structure. All ceramics showed large dielectric constants. For the x = 0.12 sample, a very high dielectric constant (>20,600) was observed. A lowering in the dielectric loss compared to pure BFT ceramics was observed with the BZT addition. The impedance measurements indicated that BZT has a strong effect on the bulk grain and grain boundary resistance of BFT ceramics. These results are in agreement with the measured dielectric properties. Based on dielectric and impedance results, (1−x)BFT-xBZT ceramics could be of great interest for high performance dielectric materials applications due their giant dielectric constant behavior.     

Comparative analysis of the twin and heterophase structures in (1−x)Pb(Mg1/3Nb2/3)O3−xPbTiO3 crystals

The specific features of the coexistence of phases in heavily twinned crystals of the (1?x)Pb(Mg_1/3Nb_2/3)O₃?xPbTiO₃ system in the vicinity of the morphotropic phase boundary (0.30≤x≤0.40) are investigated. The phase transformations in crystals at x = const during cooling are considered at electric field strengths E=0 and 0.1 MV/m. The conditions of the formation of interphase boundaries (zero net strain planes) are determined for different first-order phase transitions. The results of calculating the tetragonal-monoclinic M _C and monoclinic-monoclinic (M _C –M _A ) phase transitions are represented in the form of “twin state-interphase boundary” diagrams. The effect of a 90° domain (twin) structure of the tetragonal phase on the heterophase state associated with the presence of monoclinic phases is analyzed.     

The structure and magnetotransport properties of La2/3Sr1/3MnO3/Ba(La)TiO3 composites

The effect of Ba(La)TiO₃ doping on the structure and magnetotransport properties of La_2/3Sr_1/3MnO₃(LSMO)/xBa(La)TiO₃ (x=0.0, 1.0, 5.0 mol%) have been investigated. The X-ray diffraction patterns and microstructural analysis show that BaTiO₃ and LSMO phases exist independently in BaTiO₃-doped composites. The metal-insulator transition temperature (T_MI) decreases whereas the maximum resistivity increases very quickly by the increase of BaTiO₃ doping level. The partial substitution of Ba by La(0.35 mol%) results in a decrease in resistivity of LSMO/xBa(La)TiO₃ composites. Magnetoresistance of BaTiO₃-doped composites decreases monotonously in the temperature range 200-400 K in a magnetic field of 5 T, which is completely different from that of LSMO compound. The value of MR decreases at low field (H<1 T) and increases at high fields (H>1 T) with increasing the BaTiO₃ doping level at low temperatures below 280 K. These investigations reveal that the magnetotransport properties of LSMO/xBa(La)TiO₃ composites are dominated by spin-dependent scattering and tunneling effect at the LSMO/BaTiO₃/LSMO magnetic tunnel junction.     

Phase transition, structural and electrical properties of Pb(Zn1/3Nb2/3)O3-doped Pb(Ni1/3Nb2/3)O3-PbTiO3 ceramics prepared by solid-state reaction method

Phase pure perovskite (1−x−y)Pb(Ni_1/3Nb_2/3)O₃-xPb(Zn_1/3Nb_2/3)O₃-yPbTiO₃ (PNN-PZN-PT) ferroelectric ceramics were prepared by conventional solid-state reaction method via a B-site oxide mixing route. The PNN-PZN-PT ceramics sintered at the optimized condition of 1185 °C for 2 h exhibit high relative density and rather homogenous microstructure. With the increase of PbTiO₃ (PT) content, crystal structure and electrical properties of the synthesized PNN-PZN-PT ceramics exhibit successive phase transformation. A morphotropic phase boundary (MPB) is supposed to form in (0.9−x)PNN-0.1PZN-xPT at a region of x=32-36 mol% confirmed by X-ray diffraction (XRD) measurement and dielectric measurement. The MPB composition can be pictured as providing a “bridge” connecting rhombohedral ferroelectric (FE) phase and tetragonal one since crystal structure of the MPB composition is similar to both the rhombohedral and tetragonal lattices. Dielectric response of the sintered PNN-PZN-PT ceramics also exhibits successive phase-transition character. 0.64PNN-0.1PZN-0.26PT exhibits broad, diffused and frequency dependent dielectric peaks indicating a character of diffused FE-paraelectric (PE) phase transition of relaxor ferroelectrics and 0.40PNN-0.1PZN-0.50PT exhibits narrow, sharp and frequency independent dielectric peaks indicating a character of first-order FE-PE phase transition of normal ferroelectrics. The FE-PE phase transition of 0.56PNN-0.1PZN-0.34PT is nearly first-order with some diffused character, which also exhibits the largest value of piezoelectric constant d₃₃ of 462pC/N.     

Preparation and ferroelectric properties of pyrochlore-free Pb(Ni1/3Nb2/3)O3-based solid solutions

Polycrystalline ceramics of the perovskite solid solution 0.5Pb(Ni_1/3Nb_2/3)O₃-(0.5-x)-Pb(Zn_1/3Nb_2/3)O₃–xPb(Zr_1/2Ti_1/2)O₃; x=0.0–0.5 (PNN–PZN–PZT) were synthesized by a modified columbite method. Highly dense ceramics lacking parasitic pyrochlore phases were prepared at a calcination temperature of 950 °C by using a double-crucible configuration, excess PbO (2 mol %), and a fast heating/cooling rate (20 °C/min). The ceramics were characterized by a variety of techniques including X-ray diffraction, ferroelectric hysteresis loop measurements, field-induced longitudinal strain measurements, and electron microscopy. It was observed that the remanent polarization exhibited a significant increase with increasing x. In addition, the squareness of the hysteresis loop increased quasi-linearly as the molar fraction of PZT increased. The maximum spontaneous polarization and remanent polarization for the x=0.5 composition were 31.9 μC/cm² and 25.2 μC/cm², respectively. Moreover, the data were analyzed to show the evolution of the micro-domain state as a function of the molar fraction of PZT. PACS 77.22.-d; 77.80.Bh; 77.84.Dy; 61.10.Nz; 77.80.Dj     

Ferroelectric (Na1/2Bi1/2)TiO3 thin films showing photoluminescence properties

Polycrystalline lead-free (Na_1/2Bi_1/2)TiO₃ (NBT) ferroelectric thin films doped with 1 mol% of rare earth (RE) elements are processed on Pt-terminated silicon substrates using a solution deposition method. The thin films that exhibit single-phase perovskite structure show photoluminescence properties with highest intensities in the wavelength range between 700 and 850 nm, depending on RE element. The ferroelectric properties of the pure NBT film (P _r: 20.5 µC cm^?2, E _c: 150 kV cm^?1) are somewhat decreased for the doped films, which is ascribed to decreasing of the number of Bi lone pairs through the substitution of Bi with RE elements in the perovskite lattice.     

Phase Transition and Band Structure Tuned by Strains in Al_(1/2)Ga_(1/2)N Alloy of Complex Structure

Phase transition and band structure tuned by uniaxial and biaxial strains are systematically investigated based on the density-functional theory for ordered Al_(1/2)Ga_(1/2)N alloys of complex structures.Although the structural transformations to graphite-like from wurtzite are energetically favorable for both types of strain,the phase transitions are different in nature:the second-order transition induced by uniaxial strain is jointly driven by the mechanical and dynamical instabilities and the first-order transition by biaxial strain only by the mechanical instability.The wurtzite phase always shows the direct band gap,while the band gap of the graphite-like phase is always indirect.Furthermore,the band gaps of the wurtzite phase can be reduced by both types of strain,while that of the graphite-like phase is enhanced by uniaxial strain and is suppressed by biaxial strain.     

Field-induced piezoelectric response in Pb(Mg1/3Nb2/3)O3–PbTiO3 single crystals

The electric field induced strain, piezoelectric and electromechanical response in relaxor based single crystal piezoelectrics (1−x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃(PMNT100x) were investigated as a function of dc bias and temperature along the crystallographic [001] orientation. With increasing temperature and dc bias, monoclinic and rhombohedral phases were found to coexist in the crystals, exhibiting large strain hysteresis, while above a threshold temperature and dc bias, the induced monoclinic and tetragonal phases were found to show very low strain hysteresis. The electric field level for the monoclinic to tetragonal phase transformation was found to exponentially decay with temperature. The mechanical quality factor Q for the tetragonal phase exhibits higher values when compared to rhombohedral and monoclinic phases, displaying improved domain stability. The domain stability of tetragonal crystals as a function of sample thickness was also studied, it was found that a higher dc bias was needed for thinner tetragonal crystals in order to stabilize the single domain configuration and reduce the strain hysteresis.     

The transition from ferromagnet to cluster-glass in La(1-x)Tb(x)Mn1/2Sc1/2O3

We report the structural and magnetic properties of the La(1-x)Tb(x)Mn(1/2)Sc(1/2)O(3) series. LaMn(1/2)Sc(1/2)O(3) shows a long range ferromagnetic ordering in agreement with a fully polarized Mn-sublattice. The substitution of La with Tb produces structural changes which affect the magnetic properties. This substitution leads to a contraction in the unit cell volume that mainly reduces the M-O-M bond angle (M = Mn, Sc). The bending of this angle decreases the Mn-O-Mn superexchange interaction and enhances the competition between nearest-neighbour and next-nearest-neighbour interactions. Accordingly, the magnetic ground state changes from ferromagnetic to a glassy magnetic state. Large thermal irreversibility between zero-field-cooled and field-cooled conditions is observed for all samples. The study of the dynamic magnetic properties has been performed using the frequency dependent real part of the ac magnetic susceptibility. The use of both the Vogel-Fulcher law and the conventional critical slowing down law yields similarly good accuracies in the fits. The relaxation times obtained from both laws concur with the existence of a cluster-glass for x ≥ 0.5 samples.     

Effects of strontium on the characteristics of Pb(Zr1/2Ti1/2)O3--Pb(Zn1/3Nb2/3)O3 ceramics

The dielectric and piezoelectric properties of pyrochlore-free lead zirconate titanate-lead zinc niobate ceramics were investigated systematically as a function of Sr doping. The powders of Pb_{(1? x )}Sr _x [0.7(Zr_{1 / 2}Ti_{1 / 2})–0.3(Zn_{1 / 3}Nb_{2 / 3})]O₃, where x?=?0–0.06 were prepared using the columbite-(wolframite) precursor method. The ceramic materials were characterized using X-ray diffraction, dielectric spectra, hysteresis and electromechanical measurements. The phase-pure perovskite phase of Sr-doped PZN--PZT ceramics was obtained over a wide compositional range. The results showed that the optimized electrical properties were also achieved at composition x?=?0.0, which were K _P?=?0.69, d ₃₃?=?670?pC?N^?1, P _r?=?31.9?µC?cm^?2 and ε_rmax?=?18600. Maximum dielectric constant values of the systems decreased rapidly with increasing Sr concentration. Moreover, with increasing Sr concentration dielectric constant versus temperature curves become gradually broader. The diffuseness parameter increased significantly with Sr doping. Furthermore, Sr doping has been shown to produce a linear reduction in the transition temperature (T _m)?=?294.1–12.7x°C with concentration (x). Sr shifts the transition temperature of this system at a rate of 12.7°C?mol^?1%.     

La2/3Ca1/3Mn1-xCuxO3(x=4%)中的热弛豫现象

采用溶胶-凝胶法并经不同温度烧结而制备了名义组分为La2/3Ca1/3MnO3和La2/3Ca1/3Mn1-xCuxO3(x=4%)的系列样品,对它们进行了阻温关系测量.从试验结果观察到:在La2/3Ca1/3MnO3样品中,降温和升温测量的阻温曲线几乎完全重合,没有观察到明显的热弛豫现象.而在不同温度烧结的La2/3Ca1/3Mn1-xCuxO3(x=4%)样品中,阻温关系有明显的热弛豫现象.同时试验还观察到该热弛豫现象随样品烧结温度(颗粒尺寸)的增加逐渐消失.     

Sol-gel法制备Er3+-Yb3+共掺杂Al2O3粉末光致发光特性

采用异丙醇铝[Al(OC₃H₇)₃]为前驱体,溶胶-凝胶(Sol-gel)法制备Er³⁺-Yb³⁺共掺杂Al₂O₃粉末.实验结果表明:900 ℃烧结的粉末为固溶Er³⁺、Yb³⁺的γ-(Al,Er,Yb)₂O₃相和少量θ-(Al,Er,Yb)₂O₃相的混合物.Er³⁺-Yb³⁺共掺杂Al₂O₃粉末具有中心波长为1.533 μm的光致发光(PL)特性.1 mol % Er³⁺和1 mol% Yb³⁺共掺杂的Al₂O₃粉末的PL强度较1 mol % Er³⁺掺杂提高2倍,半峰宽从53 nm增加到63 nm.随泵浦功率的提高,PL强度呈线性增加后渐呈饱和趋势.     

0.90(Bi1/2Na1/2)TiO3–0.05(Bi1/2K1/2)TiO3– 0.05BaTiO3 transducer for ultrasonic wirebonding applications

Lead-free piezoelectric ceramic 0.90(Bi_1/2Na_1/2)TiO₃–0.05(Bi_1/2K_1/2)TiO₃–0.05BaTiO₃ (BNKBT-5) rings (OD=12.7 mm, ID=5.1 mm and 2.3-mm thick) were fabricated and characterized. Four ceramic rings were used as the driving element in an ultrasonic wirebonding transducer and the performance of the transducer was characterized. The lead-free transducer was found to have comparable voltage rise and fall times as a lead-based PZT transducer and has a relatively large vibration amplitude, thus showing that BNKBT-5 has the potential to be used in fabricating lead-free ultrasonic wirebonding transducers. PACS 77.22.Ej; 77.84.-s; 85.50.-n