The effect of dispersed SrTiO3 particles on the ionic conduction of (La,Li)Ti2O6

Ionic conductivity of La_4/3 ? y Li_3yTi₂O₆ (LLTO), where y value is 0.21, dispersed by various amount of strontium titanate (SrTiO₃) was measured by complex impedance method, and powder X-ray diffraction (XRD) measurements and scanning electron microscope (SEM) observations were carried out. With increasing SrTiO₃ concentration, the conductivity decreased. At 34 mol%, the Bragg peaks at 11, 26 and 35° in LLTO disappeared in XRD patterns and small non-angulated crystals were shown in SEM. The behavior of ionic conductivity was discussed by using the effective medium approximation (EMA) theory.     

Density-functional studies of electronic and magnetic structures for the perovskite oxides La2/3−yNdySr1/3MnO3

The effects of Nd-doping on the transport and magnetic properties of La_2/3−yNd_ySr_1/3MnO₃ (y=0, 1/3, 2/3) are studied theoretically by using the generalized-gradient-corrected full-potential method. In order to investigate the coupling between Nd and Mn, the electronic structures of La_2/3−yNd_ySr_1/3MnO₃ with ferromagnetic (FM) and antiferromagnetic (AFM) arrangements of Nd and Mn sublattices are calculated. The calculation for FM La_2/3−yNd_ySr_1/3MnO₃ yields a half-metallic band structure, while the ferrimagnetic (FiM) system is found to have a metallic character. Hybridization of Nd 4f, Mn 3d, and O 2p bands around Fermi level (E_F) is observed, suggesting the coupling between Nd and Mn is mediated by O 2p carriers. The qualitative features of transport and magnetic properties of such a two-spin system can be interpreted in terms of half-metallic FM domains being mixed up with metallic FiM domains. The proportion of FM domains varying with Nd-doping concentration has strong influences on the magnetoresistance.     

The piezoelectric effect in Pb[(Fe1/3Sb2/3) x Ti y Zr z ]O3 ceramics

The piezoelectric properties of Pb[(Fe_1/3Sb_2/3) _x Ti _y Zr _z ]O₃ with x + y + z = 1, x = 0.1, y = 0.43–0.48 ceramics have been investigated over a broad temperature range using a resonance technique. The influence of modification of PZT normal ferroelectric synthesized near the morphotropic phase boundary by a relaxor Pb(Fe_1/3Sb_2/3)O₃ compound on its physical properties was studied. The coefficients s ₁₁, k ₃₁, and d ₃₁ were calculated from the parameters characterizing the behavior of damped harmonic oscillator in the vicinity of the piezoelectric resonance. Several anomalies of the piezoelectric coefficients have been found in the temperature range 300–600 K. Two diffuse phase transitions were observed in Pb[(Fe_1/3Sb_2/3) _x Ti _y Zr _z ]O₃. The anomaly near 530 K for y = 0.43 is responsible for the transition from the rhombohedral phase to the tetragonal one. For y > 0.44 this transition is found to be very diffuse and the coexistence of rhombohedral and tetragonal phases occurs. The observation of low piezoelectric activity confirms the existence of polar regions in Pb[(Fe_1/3Sb_2/3) _x Ti _y Zr _z ]O₃ above T _m.     

Electrical conductivity and dynamics of quasi-solidified lithium-ion conducting ionic liquid at oxide particle surfaces

Lithium ion conducting solid-state composites consisting of lithium ion conducting ionic liquid, lithium bis(trifluoromethanesulfonyl)amide (Li-TFSA) dissolved 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)amide (EMI-TFSA), denoted by [yMLi⁺][EMI⁺][TFSA⁻] in this study, and various oxide particles such as SiO₂, Al₂O₃, TiO₂ (anatase and rutile) and 3YSZ are synthesized via a liquid route for the molar concentration of lithium, y, to be 1. The composite consists of SiO₂ and the ionic liquid with y = 0.2 was also prepared. The ionic liquid are quasi-solidified at the above oxide particle surfaces when x is below 40 for y = 1 and x is below 30 for y = 0.2, corresponding to the confinable thickness of the ionic liquid at the oxides' surfaces to be approximately 5-10 nm regardless of the oxide compositions. The electrical conductivities of x vol.%[yMLi⁺][EMI⁺][TFSA^-]-SiO₂, Al₂O₃, TiO₂s or 3YSZ composites are evaluated by ac impedance measurements. The quasi-solid-state composites exhibited liquid-like high apparent conductivity, e.g. 10^− 3.3-10^− 2.0 S cm^− 1 in the temperature range of 323-538 K for SiO₂-ionic liquid composites with y = 1. The self-diffusion coefficients of the constituent species of x vol.% [yMLi⁺][EMI⁺][TFSA⁻] (x is below 40, y = 0.2 and 1) − SiO₂ are evaluated by the Pulse Gradient Spin Echo (PGSE)-NMR technique in the temperature range of 298-348 K. By the quasi-solidification of the ionic liquid at SiO₂ particle surfaces, the absolute values of the diffusion coefficients of all constituent species decreased. The SiO₂ surfaces work to promote ionization of ion pair, [EMI⁺][TFSA⁻], while significant influence on the solvation coordination, [Li(TFSA)_n + 1]ⁿ⁻, was not observed. The apparent transport numbers of Li-containing species both in the bulk and the quasi-solidified ionic liquid showed similar values with each other, which was evaluated to be in the range of 0.010-0.017 for y = 0.2 and 0.051-0.093 for y = 1 in the abovementioned temperature range.     

Search for the stannous ion in a chloride/fluoride matrix: cases of Ba1−x Sn x Cl1+y F1−y and of Ba2SnCl6

With the exception of anhydrous SnCl₂, in divalent tin fluorides and chlorides, tin(II) is always covalent bonded, i.e. its valence orbitals are hybridized and the tin lone pair is located in one of the hybrid orbitals. This lone pair is highly stereoactive and generates a large efg, resulting in a large quadrupole splitting. A doubly disordered Ba_1?x Sn _x Cl_1+y F_1?y solid solution has been prepared and found to contain either ionic tin(II) (Sn²⁺ ions) or a mixture of ionic and covalent tin(II), depending on x, y and the method of preparation. The ionic tin(II) spectrum in Ba_1?x Sn _x Cl_1+y F_1?y gives a Mössbauer single line that is broadened by the lattice efg, like in SnCl₂. Now, Sn²⁺ has been found to be present in an undistorted octahedral coordination in a newly isolated compound, Ba₂SnCl₆. It should be the first example of Sn²⁺ that is fully ionic and has a perfectly spherical lone pair.     

Stable tetragonal HTSC Fe-doped 1-2-3 phase with oxygen excess

Mössbauer study was performed on the YBa₂Cu_2.95Fe_0.05O _y compound prepared in three different states: orthorhombic phase with y7, tetragonal non-superconducting phase with oxygen deficiency, and a new tretragonal superconducting phase with oxygen excess (y>7). The new synthesis method was used for preparation of the Fe-doped YBa₂Cu₃O _y (named 1-2-3) compound. The comparison of Mössbauer spectra of three different states allowed us to identify the oxygen environments of the Fe atoms in the Cu1 positions.     

Bonding in the Doubly Disordered Ba1−x Sn x Cl1+y F1−y Solid Solution

New materials were prepared in the SnF₂/BaCl₂ system by precipitation, and in the SnF₂/BaCl₂/BaF₂ system by direct reactions at high temperature in dry conditions. Stoichiometric BaSn₂Cl₂F₄ and BaSnClF₃?0.8H₂O, and a wide Ba_1?x Sn _x Cl_1+y F_1?y solid solution were prepared for the first time. Elemental analysis, X-ray diffraction and ¹¹⁹Sn Mössbauer spectroscopy were used for the characterization and study of bonding in the new materials. Mössbauer spectroscopy was shown to be an excellent method for probing both the type of bonding at tin(II) (ionic or covalent) and the bond strength at the tin sublattice. Tin(II) is covalently bonded in the stoichiometric phases and ionic (Sn²⁺ stannous ion) in the precipitated Ba_1?x Sn _x Cl_1+y F_1?y solid solution. The case of Ba_1?x Sn _x Cl_1+y F_1?y prepared in dry conditions is more complex. At negative y values (Cl: F <1) and more particularly at high x (solid solution rich in tin), a mixture of Sn²⁺ and covalent Sn(II) is observed, with a normal sublattice strength for Sn(II). At positive y values (Cl:F >1) and more particularly at low x (poor in tin), all the tin(II) is in the ionic form. Furthermore, at high x and high y, the tin(II) sublattice strength decreases so drastically that the tin recoil free fraction at ambient temperature is nearly zero. The bonding type and tin sublattice strength can be explained in terms of preference of covalent bonding with F and when tin clustering occurs, whereas an excess Cl around Sn(II) forms ionic bonding and tin rattling due to ionic size mismatch.     

Dielectric, ferroelectric and pyroelectric properties of Pb[(Ni1/3Sb2/3)xTiyZrz]O3 ceramics

In the present study, various Pb[(Ni_1/3Sb_2/3)_xTi_yZr_z]O₃ where x+y+z=1, x=0.08 and y=0.44-0.49, ceramics in the morphotropic phase boundary (MPB) range were studied by dielectric and pyroelectric methods. The results of the investigations revealed an MPB composition range of y≅0.46. The study of the dielectric properties of these compounds as a function of temperature suggests that with increase in y the permittivity maximum increases and transition temperature shifts towards higher temperature. Well-saturated polarization versus electric field (P-E) hysteresis loops were obtained and values of P_r were calculated. The samples revealed good pyroelectric properties for y=0.44 and y=0.45 at room temperature with large figures of merit F_v=0.019 m²/C and F_D=1.34×10^-5Pa^1/2.     

A co-doping approach towards enhanced ionic conductivity in fluorite-based electrolytes

A co-dopant strategy is used to investigate the effect that the elastic strain in the lattice has on the grain ionic conductivity of doped ceria electrolytes. Based on critical dopant ionic radius (r_c), different compositions in the Lu_xNd_yCe_1−x−yO_2−δ (x + y = 0.05, 0.10, 0.15, and 0.20) system are studied. Dopants are added such that the weighted average dopant ionic radius matches r_c for all the compositions. Dense ceramic discs are prepared using conventional solid oxide route and sintering methods. Precise lattice parameter measurements are used to calculate the lattice strain. The ionic conductivity of the samples is measured in the temperature range of 250 °C to 700 °C using two-probe electrochemical impedance spectroscopy technique. The elastic strain present in Lu_xNd_yCe_1−x−yO_2−δ system is found to be negligible when compared to Lu_xCe_1−xO_2−δ (negative) and Nd_xCe_1−xO_2−δ (positive) systems. Grain ionic conductivity of Lu_xNd_yCe_1−x−yO_2−δ (where x + y = 0.05) at 500 °C is observed to be 1.9 × 10^− 3 S/cm which is twice as high as that of Lu_0.05Ce_0.95O_2−δ. These results extend the validity of the r_c concept as a strategy for co-doping ceria electrolytes and open new designing avenues for solid oxide electrolytes with enhanced ionic conductivity.     

Concentration and temperature dependences of infrared reflectivity spectra in glass ionic conductor AgI– and Ag2X–AgPO3 systems (X = S,Se, Te)

Infrared reflectivity spectra of glass ionic conductors (AgI)_y–(AgPO₃)_1−y and (Ag₂X)_y–(AgPO₃)_1−y (X = S, Se and Te) have been measured at several concentrations and temperatures. Of observed six intense bands, high or low frequency band results from PO₄ or Ag-PO₄ chain, and takes the shape similar to the reststrahlen band in crystal. Low frequency bands exhibit rapid frequency shifts at the structure transition temperatures of crystal Ag₂X (X = Se and Te). From these results, we suggest crystal like arrangements of the frame chain and doped element in addition to the intermediate range ordering, and estimate strengthened binding of PO₄ units and weakened inter-chain bindings. By proposing an empirical relationship between the ratio of short-range (f_S) to long-range (f_L) forces, f_S / f_L, and ionic activation energy, we clarify the importance of the combination of strengthened f_S and weakened f_L values for high ionic conduction and also for the expansion of inter-chain distance.     

Nonradiative energy transfer from Mn2+ to Eu3+ in K2CaP2O7:Mn2+,Eu3+ phosphor

A series of color tunable phosphors K₂Ca_1?x?yP₂O₇:xMn²⁺, yEu³⁺ are synthesized by solid state reaction method. The energy transfer phenomenon from Mn²⁺ to Eu³⁺ has been observed in the Mn²⁺/Eu³⁺ codoped non-magnetic K₂CaP₂O₇ host, which was confirmed by PL spectra and decay curves. The Mn²⁺→Eu³⁺ energy transfer is controlled by quadrupole–quadrupole interaction between sensitizer and activator. The maximum efficiency of energy transfer is estimated to be 33% with x=0.125 and y=0.03 in K₂Ca_1?x?yP₂O₇:xMn²⁺, yEu³⁺ phosphor. The phosphors can emit light from green to yellow and eventually to orange under 400 nm excitation by changing the Mn²⁺/Eu³⁺ content ratio, indicating that K₂CaP₂O₇: Mn²⁺, Eu³⁺ would be potential candidates for use in lighting and displays applications.     

在BaF2-BiF3系统中的相组成和离子电导

用固相反应法、X射线粉末衍射技术和复平面阻抗谱测量研究了BaF₂-BiF₃系统的相组成和离子电导。在此系统中发现了两种类型的Ba_1-xBi_xF_2+x固溶体:萤石型(0s≈0.5(14^1/2)a_F,c_{s< 关键词：}     

Structure and lithium ionic conduction mechanism in La4/3−yLi3yTi2O6

The solid solutions La_4/3−yLi_3yTi₂O₆ (y=0.09∼0.33) have been studied by complex impedance spectroscopy, X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) methods. The ionic conductivity shows a maximum value at around y=0.21, and keeps high values at high y concentrations. The XRD patterns show a single phase for all concentration. The crystal structure is orthorhombic with space groupPmmm for y=0.09∼0.15 and tetragonal with space groupP4/mmm for y=0.17∼0.33. The⁷Li static NMR spectra show a main central peak with a Lorenzian shape for y=0.09∼0.21. The central peak is divided into two parts for y=0.23∼0.33. The narrow intense peak is a mobile component due to mobile ions, and a small broad central peak is due to less mobile lithium ions which contribute to immobile component. The⁷Li MAS NMR spectra show negative chemical shifts which decrease with increasing y concentration. In this paper, we discuss the conduction mechanism and the structure from the analysis of conductivity, lattice parameters, occupation, atomic positions and the⁷Li static/MAS NMR spectra.     

Piezoelectric properties of PbHfO3–PbTiO3–Pb(Mg1/3Nb2/3)O3 ternary ceramics

(1 – x)Pb(Hf_1–yTi_y)O₃–x Pb(Mg_1/3Nb_2/3)O₃ (x = 0.1 ～ 0.25, y = 0.555) ternary piezoelectric ceramics were prepared using the two‐step precursor method. Morphotropic phase boundary (MPB) compositions, located at x = 0.18 ～ 0.22, were confirmed using X‐ray diffraction and by their dielectric, piezoelectric and ferroelectric properties. The optimum dielectric and piezoelectric properties were achieved for the MPB composition 0.8Pb(Hf_0.445Ti_0.555)O₃–0.2Pb(Mg_1/3Nb_2/3)O₃, with dielectric permittivity ε_r, piezoelectric coefficient d₃₃, planar electromechanical coupling k_p and Curie temperature T_C being on the order of 2800, 680 pC/N, 70% and 276 °C, respectively. Of particular significance is that the new ternary ceramics exhibit comparable piezoelectric and electromechanical properties to commercial PZT5H ceramics, but with much improved T_C, showing a potential for applications at elevated temperature. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ionic conduction and chemical bonds of Li ion in La4/3−yLi3yTi2O6

The electronic state of La_4/3−yLi_3yTi₂O₆ (y=0.21) was studied by the DV-Xα cluster method. Four model clusters were used to calculate the density of state (DOS), the bond overlap population (BOP) and the net charge (NC). A Li ion in the model cluster was moved from 1b site to another 1b site along the x axis, and the BOP and the NC calculated were discussed. Furthermore, we calculated the potential energy with the movement of the Li ion along the x axis. Paper presented at the Patras Conference on Solid State Ionics - Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Lithium ion conductivity of the B-site substitution in Li3xLa0.67−xRE y III Ti1−2yPyO3 system (REIII=Sc3+, Y3+, Nd3+, Sm3+, Eu3+, Yb3+)

The B-site substituted perovskite solid solution systems Li_3xLa_0.67−xRE_yTi_1−2yP_yO₃ (RE=Sc, Y, Nd, Sm, Eu, Yb) have been investigated. Perovskite solid solutions formed in the range of x=0.10, y<0.10 for RE=Sc³⁺, Y³⁺, Yb³⁺, x=0.10, y≤0.05 for RE=Nd³⁺, Sm³⁺, Eu³⁺. Li_0.3La_0.57Nd_0.05Ti_0.9P_0.05O₃ has the highest bulk conductivity of 4.31×10⁻⁴ S·cm⁻¹ and the highest total conductivity of 2.52×10⁻⁴ S·cm⁻¹ at room temperature in all prepared compositions. The compositions have low activation energies of about 24–30 kJ/mol in the temperature ranges of 298–523 K. SEM studies showed that the sample made by solid-state reaction has a sphere-like morphology and a rough particle with particle size of about 50 μm. The research results also indicated that the reaction temperature decreases and the electrochemical stabilities of the titanate-based perovskite-type solid solutions are improved by using RE³⁺ and P⁵⁺ replaced Ti⁴⁺ on B-site in the Li_3xLa_0.67−xTiO₃ parent.     

Effect of Al-Mo codoping on the structure and ionic conductivity of sol-gel derived Li<Subscript>7</Subscript>La<Subscript>3</Subscript>Zr<Subscript>2</Subscript>O<Subscript>12</Subscript> ceramics

Al-Mo codoped Li₇La₃Zr₂O₁₂ ceramics with fine grain were prepared by sol-gel method. The influences of Al-Mo codoping on the structure, microstructure, and conductivity of Li₇La₃Zr₂O₁₂ were investigated by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and impedance spectroscopy. The cubic phase Li₇La₃Zr₂O₁₂ has been stabilized by partial substitution of Al for Li and Mo for Zr. Li_6.6-3yAl_yLa₃Zr_1.8Mo_0.2O₁₂ (0?≤?y?≤?0.1) has been sintered at 1040–1060 °C for 3 h. The liquid sintering facilitated its densification. The relative density of the composition with x?=?0.075 was approximately 96.4%. Results indicated that the Al-Mo codoped LLZO synthesized by sol-gel method effectively lowered its sintering temperature, accelerated densification, and improved the ionic conductivity.     

Enhanced luminescence of Ca3B2O6:Dy phosphors by Na-codoping for LED applications

The Ca_2.95−yDy_0.05B₂O₆:yNa⁺ (0≤y≤0.20) phosphors were synthesized at 1100 °C in air by the solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), photoluminescence excitation (PLE), photoluminescence (PL) spectra and thermoluminescence (TL) spectra. The PLE spectra show the excitation peaks from 300 to 400 nm due to the 4f-4f transitions of Dy³⁺. This mercury-free excitation is useful for solid-state lighting and light-emitting diodes (LEDs). The emission of Dy³⁺ ions on 350 nm excitation was observed at 480 nm (blue) due to the ⁴F_9/2→⁶H_15/2 transitions, 575 nm (yellow) due to ⁴F_9/2→⁶H_13/2 transitions and 660 nm (red) due to weak ⁴F_9/2→⁶H_11/2 emissions. The PL results from the investigated Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors show that Dy³⁺ emissions increase with the increase of the Na⁺ codoping ions. The integral intensity of yellow to blue (Y/B) can be tuned by controlling Na⁺ content. By the simulation of white light, the optimal CIE value (0.328, 0.334) can be achieved when the content of Na⁺-codoping ions is y=0.2. The results imply that the Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors could be potentially used as white LEDs.     

Energy bands and electron densities of Li3N

Self-consistent band-structure calculations on the fast ionic conductor lithium nitride are performed by means of the linearized augmented plane wave (LAPW) method within the local density formalism. The corresponding density of states is decomposed into local (inside spheres), partial (l-like) and symmetry (p _x p _y ;p _z ) components from which an only very small covalent contribution to the bonding in Li₃N can be deduced. Electron density maps reveal Li₃N to be highly ionic (near Li⁺ and N^3–). A simple Watson model, although a good first approximation, cannot account for all details. For instance a remarkable non-spherical electrons density is found around N which may explain the high electric field gradient experimentally observed on this site; furthermore a reduced electron density around the Li-sites appears in contrast to a simple supper-possition of N^3– ionic densities. However, calculated x-ray structure factors and difference electron densities are in good qualitative agreement with recent x-ray diffraction experiments.This work has been supported by the Hochschuljubiläumsstiftung der Stadt Wien. All calculations were carried out at the Rechenzentrum der Technischen Universität Wien     

插层化合物钨青铜单晶的物理研究

本工作利用X射线衍射分析、电导测量、红外、喇曼散射等手段,对用熔盐电解法生长的K_xWO₃,Na_yWO₃和K_xNa_yWO₃单晶进行了深入的研究,得出K_xNa_yWO₃是钠离子插入到K_xWO₃的结论,提出了K_xNa_{y关键词：}