Ion transport in the anion-deficient nonstoichiometric phases La0.95(Ba1−x Srx)0.05F2.95 (0⩽x⩽1)

The fluoride-ion conductivity of the nonstoichiometric tysonite phases La_0.95(Ba_1−x Sr_x)_0.05Fe_2.95 (0⩽x⩽1) is investigated by impedance spectroscopy. Electrophysical measurements are performed in the frequency range 5–5×10⁵ Hz and temperature range 300–700 K. A discontinuity is observed in the temperature dependence of the conductivity at T _c=410–430 K. The behavior of the temperature dependence of the electrical conductivity is explained within a transport model taking into account the migration of fluoride ions between different inequivalent structural sites. The maximum value of the conductivity at room temperature (293 K) is 2×10⁻⁴ Ω⁻¹ cm⁻¹ for the solid solution La_0.95Sr_0.05F_2.95. The fluorine-ion conductivity in La_0.95(Ba_1−x Sr_x)_0.05F_2.95 single crystals is almost an order of magnitude larger than the value for the commercial solid electrolyte La_0.992Eu_0.008F_2.992 (a fluorine-selective membrane) having a tysonite structure. Fiz. Tverd. Tela (St. Petersburg) 40, 658–661 (April 1998)     

Frequency response of the low-temperature ionic conductivity of single crystals R 1 − y M y F3 − y (R = La-Er; M = Ca, Sr, Ba, Cd)

The frequency response (10^?1–10^?7 Hz) of the ionic conductivity σ of R _{1 ? y} M _y F_{3 ? y} single crystals (R is a rare-earth element, and M stands for an alkaline-earth element and Cd) with a tysonite structure is studied over a wide temperature range (114–410 K), which includes (for the first time for these phases) the interval below room temperature. The dependences σ(ν) obtained are discussed within the hopping relaxation model. The characteristics of the relaxation and migration processes and the carrier concentration and mobility are determined.     

Ion-motion disorder in a tysonite superionic conductor from 19F NMR data

The disorder in ion motion in a LaF₃ superionic conductor with tysonite structure is determined from NMR spectra. The method is sensitive to dynamic effects with correlation times of 5×10⁻³<τ<10⁻⁶ s. Within the 260–400-K interval, ion movement is observed only on one of the sublattices (F₁), and it exhibits a correlation time distribution. The shape of the distribution is well fitted by a log-Gaussian. The distribution in correlation times reflects noticeable spatial fluctuations of local potentials in the LaF₃ superionic conductor. Fiz. Tverd. Tela (St. Petersburg) 41, 1616–1620 (September 1999)     

Superionic conductivity of the heterovalent solid solutions R 1−x M x F 3−x (R=REE, M=Ca, Ba) with tysonite-type structure

The fluorine-ion conductivity of anion-deficient solid solutions R _1−x Ca_xF_3−x and R _1−x Ba_xF_3−x having the tysonite (LaF₃) structure was investigated by the impedance spectroscopy method. R _1−x Ca_xF_3−x (R=La, Pr, Nd, Sm, Gd, Tb, Dy, Ho) and R _1−x Ba_xF_3−x (R=La, Pr, Nd) single crystals were grown from the melt by the Bridgman-Stockbarger method. The electrophysical measurements were performed in the frequency range 5−5×10⁵ and temperature range 300–700 K. The temperature dependences of the electrical conductivity for the crystals studied is determined by the migration of fluorine anions along various structural positions. It is shown that, from the standpoint of increasing the conductivity of tysonite matrices RF₃ (R=La, Pr, Nd), doping by CaF₂ and BaF₂ is less promising than SrF₂. Fiz. Tverd. Tela (St. Petersburg) 41, 638–640 (April 1999)     

Tysonite structure and crystal-field analysis of the Pr3+ ion in PrF3

The quadratic Zeeman effect of the Pr³⁺ ion in PrF₃ and a Raman spectroscopic investigation of the optical phonons in LaF₃ have been used to test the crystal structures proposed in the past for tysonite. We find that the twinned structure is consistent with all available experimental results. A crystal field Hamiltonian parametrized in monoclinic symmetry was used to describe the observed crystal field splittings of Pr³⁺ in PrF₃. Our best parameter set gave a r.m.s.-deviation of 12 cm^–1. As a test for the eigenfunctions the quadratic Zeeman shifts are calculated and compared with the experimental results.     

Ionic conductivity in tysonite-type solid solutions La1−xBaxF3−x

The ionic conductivity of single crystals of tysonite-type solid solutions La_1?xBa_xF_3?x(0?x?0.095) has been studied parallel and perpendicular to the crystallographic c axis in the temperature range 293–1300 K. Three regions can be discerned in the compositional dependence of the ionic conductivity: (i) the “pure” crystal, in which at room temperature no exchange occurs between different types of anion sites in the tysonite structure; (ii) an intermediate region(0 < x < 7 × 10^-2) which reveals changes in both the conductivity activation enthalpy and the magnitude of the conductivity; (iii) a concentrated solid-solution region (x > 7 × 10^-2), where fluoride ions interchange easily among the different anion sublattices. Diffusion coefficients calculated from ionic conductivity results, are in good agreement with those calculated from ¹⁹F NMR measurements. Using the present data, along with ¹⁹F NMR data, dielectric relaxation data and structural considerations, mechanisms governing the ionic conductivity are proposed.     

Bulk conductivity and polarization of ionic crystals exhibiting defect exchange between inequivalent sites

The bulk conductivity of ionically conducting crystals in which Schottky or Frenkel defects jump between inequivalent sites can be appreciably more complex than that of simpler materials. An equivalent electrical circuit is derived to describe the bulk ac response of crystals of the tysonite type. The circuit has the form of a two-component Maxwell-Wagner capacitor and includes a capacitative element which represents a frequency-dependent bulk polarization not associated with dipolar complexes. The application of the model to LaF₃ is discussed.     

Dielectric relaxation properties of tysonite-type solid solutions La1−xBaxF3−x

Dielectric relaxation properties of solid solutions La_1?xBa_xF_3?x (x ? 0105) have been studied by thermally stimulated depolanzation current (TSDC)- and a c. dielectric loss (DL) techniques.For x < 30 × 10^?3 the dielectric spectra show a relaxation peak which is ascribed to a simple associate of a substitutional dopant ion and a fluoride ion vacancy (Ba_LaV_F)^x in nearest-neighbour position, the vacancy being confined to the B sublattice For x values of about 1.3 × 10^?2 a relaxation peak appears which is tentatively attributed to a similar type of defect associate with the vacancy now confined to the A sublattice of the tysonite anion array One broad relaxation peak dominates the TSDC and DL spectra over the whole concentration range This peak is due to the relaxation of macroscopic space charge, i e ionic conductivity The low-temperature ion conductivity has been determined for several solid solutions, and extrapolates to the high-temperature conductivity determined previously with impedance spectroscopy Below liquid-nitrogen temperature three relaxations are observed, and ascribed to electronic transitions in cenum impurities. A computer programme has been developed to analyse TSDC relaxation peaks, taking dipole-dipole interactions into account Relaxation parameters and dipole concentrations are presented.     

Anisotropy of Anionic Conductivity in Single Crystals of CeF3 Superionic Conductor

Physics of the Solid State - In this paper, the anisotropy of anionic conductivity in CeF3 superionic conductor crystals with tysonite structure (sp.gr. $$P\bar {3}c1$$ ) is studied for the first...     

A novel double-recessed 4H-SiC MESFET with partly undoped space region

In this paper, a novel double-recessed 4H-SiC metal semiconductor field effect transistor (MESFET) with partly undoped space region (DRUS-MESFET) is introduced. The key idea in this work is to improve the DC and RF characteristics of the device by introducing an undoped space region. Using two-dimensional and two-carrier device simulation, we demonstrate that breakdown voltage (V_BR) increases from 109 V in conventional double recessed MESFET (DR-MESFET) structure to 144.5 V in the DRUS-MESFET structure due to the modified channel electric field distribution of the proposed structure. The maximum output power density of the DRUS-MESFET structure is about 25.4% larger than that of the DR-MESFET structure. Furthermore, lower gate-drain capacitance (C_GD), higher cut-off frequency (f_T), larger maximum available gain (MAG), and higher maximum oscillation frequency (f_max) are achieved for the DRUS-MESFET structure. The results show that the f_max and f_T of the proposed structure improve 95.6% and 13.07% respectively, compared with that of the DR-MESFET structure. Also, the MAG of the DRUS-MESET is 4.5 dB higher than that of the DR-MESFET structure at 40 GHz. The results show that the DRUS-MESFET structure has superior electrical characteristics and performances in comparison with the DR-MESFET structure.     

An ab initio study of 5d noble metal nitrides: OsN2, IrN2, PtN2 and AuN2

The crystal structure, phonon stability, elasticity and electronic properties of four noble metal nitrides (PtN₂, IrN₂, OsN₂ and AuN₂) with three structural types (pyrite, marcasite and CoSb₂ structure) were studied by first principles calculations. In agreement with experiments and previous theoretical predictions, it is found that the most stable structure for OsN₂ is marcasite, for PtN₂ is pyrite, and for IrN₂ is the CoSb₂ structure. It is found that these three compounds are thermodynamically metastable with respect to solid N₂ and the metal at zero pressure. The structures are mechanically and dynamically stable. The lowest energy structure of AuN₂ is the CoSb₂ structure. The formation energy of AuN₂ is found to be very high compared to the other three nitrides studied here. This underlies the experimental difficulty in the synthesis of this compound. OsN₂ is found to be metallic, while IrN₂ and PtN₂ are both semiconductors.     

Electronic structure of novel multiple-band superconductor SrPt<Subscript>2</Subscript>As<Subscript>2</Subscript>

The electronic structure of the recently discovered superconductor SrPt₂As₂ with T _c = 5.2 K has been calculated in the local-density approximation. Despite its chemical composition and crystal structure are somehow similar to FeAs-based high-temperature superconductors, the electronic structure of SrPt₂As₂ is very much different. The crystal structure is orthorhombic (or tetragonal if idealized) and has layered nature with alternating PtAs₄ and AsPt₄ tetrahedra slabs sandwiched with Sr ions. The Fermi level is crossed by Pt-5d states with rather strong admixture of As-4p states. Fermi surface of SrPt₂As₂ is essentially three-dimensional, with complicated sheets corresponding to multiple bands. We compare SrPt₂As₂ with 1111 and 122 representatives of FeAs-class of superconductors, as well as with isovalent (Ba,Sr)Ni₂As₂ superconductors. Brief discussion of superconductivity in SrPt₂As₂ is also presented.     

The Intrinsic Fluorine-Ion Conductivity of Crystalline Matrices of Fluoride Superionics: BaF2 (Fluorite Type) and LaF3 (Tysonite Type)

Physics of the Solid State - The intrinsic fluorine-ion conductivity σlat of BaF2 (CaF2 fluorite type) and LaF3 (tysonite type) crystals is studied by the impedance spectroscopy method. These...     

5d过渡金属二硼化物的结构和热、力学性质的第一性原理计算

利用基于密度泛函理论的第一性原理系统地研究了5d过渡金属二硼化物TMB₂ (TM=Hf–Au) 的结构、热学、力学和电学性质. 我们考虑了三种结构, 分别为AlB₂, ReB₂和WB₂结构. 计算得到的晶格常数与先前的理论和实验研究符合得很好. 通过计算生成焓预测了化合物的热力学稳定性; 从HfB₂到AuB₂, 生成焓的整体趋势是逐渐增加的. 在所考虑的结构中, 对HfB₂和TaB₂, AlB₂结构是最稳定的; 对WB₂, ReB₂, OsB₂, IrB₂和AuB₂, ReB₂结构是最稳定的; 对PtB₂, WB₂结构是最稳定的. 在所考虑的化合物中, ReB₂结构的ReB₂具有最大的剪切模量(295 GPa), 是最硬的化合物, 与先前的理论和实验结果相符. 计算得到的总态密度显示所有结构都具有金属特性. 讨论了系列化合物的变化趋势. 关键词： 弹性性质 热力学性质 第一性原理 5d过渡金属二硼化物     

A mixed domain structure in ferrite-garnet films

A stable static mixed domain structure consisting of strip domains and a cylindrical magnetic domain (CMD) is obtained in (Bi_0.7Lu_0.3)₃ (Fe_0.8Ga_0.2)₅ O₁₂ ferrite-garnet films. An analytic theory of the mixed domain structure is constructed. An analytic solution is obtained for the shape of a distorted strip domain, which is in good agreement with experimental results.     

静水压下锆锡钛酸铅铁电陶瓷相变和介电性能研究

研究了铌掺杂锆锡钛酸铅铁电陶瓷Pb_0.99Nb_0.02[(Zr_0.90Sn_0.10)_0.96Ti_0.04]_0.98O₃(PZST 90/10-4-2Nb)在静水压(0-300 MPa)下的电荷释放量和介电性能. 对压力诱导的低温铁电三方(F_R(LT))→反铁电正交(A_O)相变进行了研究. PZST 90/10-4-2Nb铁电陶瓷分为未极化、极化和压力去极化三种. 极化PZST 90/10-4-2Nb陶瓷F_R(LT)→A_O相变过程中,电荷释放量为29.3 μC/cm²,相变压力为140 MPa. 介电性能表明:极化PZST 90/10-4-2Nb陶瓷相变压力为136 MPa,而未极化陶瓷相变压力为104 MPa,压力去极化陶瓷未表现出明显的相变特征. 关键词： 静水压 铁电陶瓷 相变 介电     

Li2O-Nb2O-SiO2系统非晶态离子导体的结构与电学性能

本文采用红外吸收光谱法、X射线散射法和EXAFS方法研究了LiO-Nb₂O-SiO₂系统非晶态离子导体的结构,认为Nb⁵⁺在非晶结构网络中主要是以[NbO₆]形式存在。非晶结构随Nb₂O₅含量的多少而变化。低Nb₂O₅含量时,[NbO₆]相互间以边相连,并与[SiO₄]组成多元环后,形成非晶网络结构。高Nb₂O₅含量时,非晶网络结构主要是以角顶相连的[NbO₆]所组成。根据电导测试结果,讨论了结构与电学性能的关系,认为Li₂O含量在0.45左右,Nb₂O₅,含量在0.3左右组成的非晶材料有最高的电导率。 关键词：     

High pressure synthesis of the mixed valent and nonsuperconducting ternary YbRhxSny compound

The ternary compound YbRh_1.4Sn_4.6 with the phase I structure (simple cubic) when subjected to a pressure of 40 kbar at 800°C is found to transform to phase III structure (f.c.c.) with the composition YbRh_1.1Sn₃. The latter compound has a lattice parameter of $\text{a = 13.735}\text{A}\text{?}$ which suggests that the Yb is in an intermediate valence state. The temperature dependence of magnetic susceptibility suggests that the Yb is in a homogeneously mixed valence state in the pressure synthesized product. In the phase I structure YbRh_1.1Sn_4.6 is superconducting at 8.6°K, but in the phase III structure the compound YbRh_1.1Sn₃ is not superconducting down to 0.9°K. It is suggested that superconductivity and mixed valence are incompatible.     

A comparative study of electronic structure and magnetic properties of SrCrO3 and SrMoO3

A comparative study of electronic structure and magnetic properties of SrCrO₃ and SrMoO₃ has been carried out using FPLAPW method with density-functional theory. The calculated results suggest that both compounds are nonmagnetic (NM) metal in cubic structures at room temperature, and they exhibit very similar band structure and electronic properties except more extend Mo 4d orbitals than Cr 3d electronic states. However, the electronic structure and magnetic properties exhibit remarkable differences between them in the low temperature phases. SrCrO₃ is with a C-AFM ground state with magnetic moment of 1.18μ_B/Cr in the tetragonal structure, while SrMoO₃ is with a NM ground state in the orthorhombic structure. It is assumed that the extend 4d orbitals may be the reason which results in NM solution at low temperature phase of SrMoO₃.     

The Equilibrium Structure of Silyl Fluoride

The experimental equilibrium structure of silyl fluoride has been determined using new sets of accurate rotational constants that have recently been obtained by taking into account the most important interactions between the excited vibrational states. The equilibrium structure has also been calculated at the CCSD(T) level of theory with the cc-pVQZ+1 basis set (including corrections for the core correlation). The anharmonic force field up to semidiagonal quartic terms has been calculated at the MP2 level of theory and the equilibrium structure has been derived from the experimental rotational constants and the ab initio rovibrational interaction parameters. Finally, the average structure of both ²⁸SiH₃F and ²⁸SiD₃F has been reevaluated and used to derive the equilibrium structure. These structures are compared and the experimental structure is found to be in slight disagreement with the other ones. The preferred structure is obtained by calculating the median value of the different structures. The results are r_e(SiF)=1.5907 (9) Å, r_e(SiH)=1.4696 (13) Å, ∠_e(HSiF)=108.32(15)°, and ∠_e(HSiH)=110.60(14)°.