Synthesis and physicochemical properties of Li2 Me x Zr1 − x O3 − δ (Me = Nb,Ti; x = 0.05, 0.1) solid solutions

Complex lithium metallates Li₂ Me _x Zr_{1 ? x} O_{3 ? δ} (Me = Nb, Ti, x = 0.05, 0.1) with iso-and heterovalent substitutions for Zr⁴⁺ ions in lithium zirconate are synthesized for the first time using a citrate technique. The inclusion of Ti⁴⁺ and Nb⁵⁺ ions in the crystal structure of Li₂ZrO₃ is confirmed by means of X-ray diffraction and NMR. It is shown that in the temperature range of 750–820 K, Li₂Ti_0.1Zr_0.9O₃ solid solution has higher conductivity than phases of undoped lithium zirconate.     

Raman study of LiTaO3-related non-stoichiometric solid solutions isolated inside the ternary systems Li2O–Ta2O5–(M′O)2 with M′=Mn,Co

We have characterized by Raman spectroscopy the disorder and the local modifications of cation environment in the lithium tantalate structure resulting from the incorporation of bivalent cations Co²⁺ and Mn²⁺ as potential substitutes for Li and/or Ta ions. Frequency and damping of the E(TO1), E(TO6) and E(TO8) phonon modes of ceramic powders are studied along seven lines in the ternary phase diagrams Li₂O–Ta₂O₅–(M′O)₂ with M′=Mn and Co, and compared to those of the pure stoichiometric LiTaO₃. Raman spectroscopy is found to be very sensitive to the substitution ions and defects generated in the lattice vibration. Dopants occupy primarily the Li site in the region of lithium oxide excess. The site of Ta becomes progressively implicated in the substitution process when the concentration of dopant increases. In the Li-poor region of the ternary-phase diagram, corresponding to under-stoichiometric compositions, we retain the charge compensation mechanism involving both Li and Ta site according to: 3Li⁺+Ta⁵⁺→4M′²⁺ with M′²⁺=Mn²⁺ or Co²⁺.     

Concentration-phase transitions in solid solutions Li x Na1 − x Ta0.1Nb0.9O3, Li0.12Na0.88Ta y Nb1 − y O3, and NaTa y Nb1 − y O3 and their manifestations in Raman spectra

Using the Raman-spectroscopy method, we have studied concentration-phase transitions in the solid solutions Li _x Na_{1 ? x} Ta_0.1Nb_0.9O₃, Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, and NaTa _y Nb_{1 ? y} O₃ (x = 0?0.16, y = 0–1). It has been revealed that, for the solid solutions Li _x Na_{1 ? x} Ta_0.1Nb_0.9O₃ and Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, the concentration-phase transition is a transition between the ferroelectric and antiferroelectric states. It is accompanied by the disappearance from the spectrum of a line that corresponds to stretching bridge vibrations of oxygen atoms along the polar axis, which is forbidden by selection rules in the centrosymmetric phase, and by splitting into two components of a line that corresponds to librational vibrations of oxygen octahedra as a whole, which can be caused by doubling of the unit cell in the antiferroelectric phase. Manifestation and variation of intensities of lines with frequencies 860–873 and 900–905 cm^?1 upon variation of the concentration of tantalum for solid solutions Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, and NaTa _y Nb_{1 ? y} O₃ is caused by the formation of polar clusters in the medium, which is centrosymmetric in general due to disordering in the sublattice of niobium and tantalum.     

High temperature superconductivity in (M1−xM′x)2CuO4−δ and related compounds (M = Y,La, Eu,Sm; M′ = Ba,Sr)

Compounds of the form (M_1−xM′_x)₂CuO_4−δ and related compounds where M and M′ are Y, various rare earths from La to Lu, and the alkaline earths Sr and Ba, have been investigated in connection with high temperature superconductivity. High temperature superconductivity is confirmed for the system (La_1−xBa_x)₂CuO_4−δ, (La_1−xSr_x)₂CuO_4−δ and (Y_1−xBa_x)₂CuO_4−δ with superconducting transition temperature T_c onsets of 30 K, 38 K and 90 K, respectively. We have found that the related systems (Eu_1−xBa_x)₂CuO_4−δ and (Sm_1−xBa_x)₂CuO_4−δ also exhibit high temperature superconductivity with T_c onsets of 95 K and 65 K, respectively. The highest T_c onset observed in this investigation was 97 K for a sample with the nominal composition of the spinel structure Y_0.33Ba_0.67Cu₂O_4−δ. Measurements of the specific heat C as a function of temperature T on a La_0.8Sr_0.2CuO_4−δ sample reveal a break in slope in the C/T vs T curve at the T_c midpoint, but no clearly discernable jump in C at T_c. A linear term ≈ λ′T in C was observed at low temperature in the superconducting state.     

An origin of infinite range dipole-dipole correlations in soft matrices with off-center impurities: K 1−x Li x Ta 1−y Nb y O 3 and other systems

A model of cooperative behaviour for K 1 m x Li x Ta 1 m y Nb y O 3 (KLTN) and for other disordered systems like ferroelectric relaxors is considered from the point of view of contribution of infinite-range dipole-dipole interactions. It is shown that a local piezoeffect for off-center impurities in crystals with rather high electrostriction is responsible as origin of a infinite-range electric dipole-dipole interaction via elastic fields as well as for a co-existence of ferroelectric and glass-like states with reentrant glass effect.     

Structural stability,phase transition and dielectric properties of Pb(Mg1/2W1/2)1−xMxO3 (M = Zr,Sn, Ti) ceramics

ABSTRACT

Pb(Mg_1/2W_1/2)_1?xM_xO₃ (M?=?Zr,Sn,Ti) ceramics have been prepared by the conventional ceramic process. Their crystallographic, phase transition and dielectric properties have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and impedance analyzer in this paper. The solubility of the tetra-valent cation in Pb(Mg_1/2W_1/2)_1?xM_xO₃ decreases in the sequence of Ti^4+?>?Zr^4+?>?Sn⁴⁺. The doping led to the phase transition from orthorhombic antiferroelectric to cubic paraelectric phase, the microscopic nature of which could be attributed to the contraction of Pb-O₁₂ dodecahedron. A definition of the ordering parameter of the cubic phase was deduced to quantitatively evaluate the B-site ordering degree which decreased with the increase in doping concentration. Anti-site disordering of Mg²⁺ and W⁶⁺ occurred in the high-level doping compositions, which led to the relaxor behavior observed in Ti⁴⁺-doped series with x?=?0.01 composition. Both of the maximum dielectric permittivity and loss in the paraelectric phase increased with the increasing doping concentration.     

锐钛矿型氧化物XO2（X=Ti,Sn,Zr,Ir）表面氧化性对NH3气体光学气敏传感特性的影响

摘要 金属氧化物气敏传感材料一直是当今的热门研究课题,锐钛矿相金属氧化物XO2（X=Ti,Sn,Zr,Ir）是具有传感特性的常见材料。光学气敏效应是指气体分子吸附在气敏传感材料上,与表面氧空位发生氧化还原反应,由于光学性质发生改变而检测出气体的成分和浓度,因此,氧化还原反应的强弱是反应传感性能的核心原因。本文采用密度泛函理论(DFT)体系下广义梯度近似(GGA)第一性原理平面波超软赝势方法,分析和计算了含氧空位的锐钛矿相XO2（X=Ti,Sn,Zr,Ir）表面特性。通过以NH3为目标分子,研究分子表面吸附引起的氧化还原反应的机理,分析不相同的氧化物表面的几何结构、吸附能、态密度、差分电荷密度、电荷布居、电荷转移、光学性质等。研究发现：目标分子稳定吸附在氧化物表面后改变材料光学性质。SnO2表面对分子的吸附能最大,IrO2表面与分子的吸附距离最小。NH3分子与表面间存在电荷转移,其转移电子数目大小为:IrO2＞TiO2＞ZrO2＞SnO2,氧化物表面氧化性的大小为:IrO2氧空位＞TiO2氧空位＞ZrO2氧空位＞SnO2氧空位;比较吸收谱和反射谱发生变化最为明显的是TiO2表面。结论,在可见光范围内,波长在400~530nm时,SnO2表面光学气敏传感效应更好。而在530~760nm范围TiO2表面光学气敏传感效应更好。     

Near-threshold photoionization from the excited mp<Superscript>5</Superscript>(m + 1)p J = 0−3 levels of Ar,Kr and Xe (m = 3−5)

Using the configuration interaction Pauli-Fock including core polarization (CIPFCP) approach we have calculated absolute total and partial cross sections for photoionization of excited mp ⁵(m + 1)p J = 0−3 levels in Ar, Kr and Xe (m = 3−5) near threshold. Particular emphasis is paid to the lineshapes of the odd mp _1/2⁵ n(s/d)′ autoionizing resonances and their variation with the character of the intermediate excited J = 0−3 state. For selected intermediate levels of Ar and Kr the computed cross sections are compared with laser spectroscopic measurements; good agreement between the theoretical and experimental lineshapes and branching ratios for different resonances is observed.     

Photoluminescence Enhancement Effect of CeO2 in Rare Earth Composites MM′O3/CeO2 and MM′O3/CeO2: Pr3+ (M = Ca, Sr; M′ = Ti, Zr)

In the context, a modified sol-gel technology was afford to the synthesis of rare earth composite ceramic phosphors MM′O₃/CeO₂ and MM′O₃/CeO₂: Pr³⁺ (M = Ca, Sr; M′ = Ti, Zr) with multicomponent hybrid precursors were composed. The micromorphology, particle size and photoluminescence properties were studied with XRD, SEM and luminescent spectroscopy in detail. Both XRD and SEM indicated the particle sizes were in the submicrometer range of 100 ∼ 300 nm. The photoluminescence for these ceramic phosphors were studied in details with the different component of host (molecular ratio of Sr, Ca and Ti, Zr), presenting a broad spectral band in the visible blue-violet region with the maximum excitation peak at 449 nm and a wide emission range with a maximum peak at 619 nm, which was ascribed to be the characteristic transition of Pr³⁺ (¹D₂ → ³H₄). These phosphors can be expected for visible light conversion (blue → red) materials. Especially it can be found that the introduction of CeO₂ can enhance the luminescence intensity of MM′O₃ and MM′O₃: Pr³⁺.     

A study of the system Ag3−xTlxFe(CN)6, (x =0, 1, 2, 3) by Mössbauer spectroscopy

The ferricyanides Ag_3−xTl_xFe(CN)₆, (x = 0, 1, 2, 3) have been measured by Mössbauer spectroscopy. The results indicate a negative EFG for all samples except for x = 1, that is positive. The isomer shift for Tl₃Fe(CN)₆ is the more negative, indicating a strong contribution from the empty p-orbitals of Tl⁺ ions.     

Spectral properties of the Nd<Superscript>3+</Superscript> ion in inorganic solvents POCl<Subscript>3</Subscript>—MeCl<Subscript>n</Subscript> (Me = Sn,Zr, Ti,or Al)

The absorption and luminescence spectra of Nd³⁺ ions in inorganic solvents POCl₃—MeCl_n (Me = Sn, Zr, Ti, or Al) are measured. The spectra are analyzed in terms of the Judd—Ofelt theory. The Judd—Ofelt parameters, oscillator strengths, spontaneous emission probabilities, luminescence quantum yields, and stimulated emission cross sections for the laser transition ⁴F_3/2 → ⁴I_11/2 of the Nd³⁺ ion in POCl₃—MeCl_n—Nd³⁺ solutions are calculated.     

Quantum-chemical modeling of the electronic structure and magnetic properties of Sn1 − x − y M x Sb y O2, M = Cr, Mn, Co, or Ni (x = 0.25; y = 0, 0.25)

The electronic and magnetic structures of the Sn_0.75 M _0.25O₂ and Sn_0.5 M _0.25Sb_0.25O₂ (M = Cr, Mn, Co, Ni) compounds with a structure that is derivative of the rutile structure are modeled using the ab initio spin-polarized tight-binding linear muffin-tin orbital (TB-LMTO) method. The magnetic moments of the transition metal atoms are calculated. The data obtained are used to analyze the influence of the composition of Sn_{1 ? x ? y} M _x Sb _y O₂ phases on their electronic spectra and the magnetic and transport characteristics.     

A density functional theory study on size-dependent structures,stabilities,and electronic properties of bimetallic M_nAg_m(M=Na,Li;n + m≤7) clusters

The equilibrium geometries,relative stabilities,and electronic properties of Mn Agm(M=Na,Li;n + m ≤ 7) as well as pure Ag n,Na n,Li n(n ≤ 7) clusters are systematically investigated by means of the density functional theory.The optimized geometries reveal that for 2 ≤ n ≤ 7,there are significant similarities in geometry among pure Ag n,Na n,and Li n clusters,and the transitions from planar to three-dimensional configurations occur at n = 7,7,and 6,respectively.In contrast,the first three-dimensional(3D) structures are observed at n + m = 5 for both Na n Ag m and Li n Ag m clusters.When n + m ≥ 5,a striking feature is that the trigonal bipyramid becomes the main subunit of Li n Ag m.Furthermore,dramatic odd-even alternative behaviours are obtained in the fragmentation energies,secondorder difference energies,highest occupied and lowest unoccupied molecular orbital energy gaps,and chemical hardness for both pure and doped clusters.The analytic results exhibit that clusters with an even electronic configuration(2,4,6) possess the weakest chemical reactivity and more enhanced stability.     

Al,F-doped new perovskite lithium fast ion conductor Li3x La2/3−x□1/3−2x Ti1−y Al y O3−y F y (x=0.11)

Al, F-doped new perovskite lithium ion conductors (x=0.11) have been prepared by solid state reaction. It is found that a pure perovskite-structured phase with space group of P4mm(99) exits in the composition range of 0<y≤0.10. The sample with y=0.02 possesses the highest ionic conductivity of 1.06×10⁻³ S/cm at room temperature, and its decomposing voltage is 2.3 V. The factors affecting the conductivity of this system are discussed.     

Lattice dynamics, ferroelectric and antiferroeelctric instabilities, and the ferroelectric phase transition in disordered PbB′1/2B″1/2O3 (B′ = Ga, In, Lu; B″ = Nb, Ta) solid solutions

The lattice vibration spectra, rf permittivity, and dynamic Born charges of disordered PbB′_1/2B″_1/2O₃ (B′ = Ga, In, Lu; B″ = Nb, Ta) solid solutions are calculated in terms of the generalized Gordon-Kim model. All the compounds are found to have soft modes related to the center (Γ₁₅) and boundary point R (R ₁₅) of the Brillouin zone; the frequencies of these modes are close. The ferroelectric phase transition temperatures and the spontaneous polarization in the ferroelectric phase are calculated for the solid solutions using a model Hamiltonian in the local mode approximation and the Monte Carlo method. These temperatures for the tantalum compounds are found to be higher than for the niobium compounds, and temperature t _s increases with the atomic number of ion B′. A model where the antiferroelectric state is related to the condensation of modes Γ₁₅ and R ₁₅ is proposed. It is found that, for all compounds except for PbSc_1/2Nb_1/2O₃ and PbSc_1/2Ta_1/2O₃, the ferroelectric phase, which is only related to the condensation of mode R ₁₅, and the antiferroelectric phase have similar energies. In PbIn_1/2Ta_1/2O₃, the antiferroelectric phase turns out to be energetically favorable.     

Calculations of the lattice dynamics and spontaneous polarization for thin ferroelectric films of disordered solid solutions PbB′1/2 B″1/2O3 (B′ = Sc,Ga, In,Lu; B″ = Nb,Ta)

Physics of the Solid State - The lattice dynamics and spontaneous polarization in thin ferroelectric films of disordered solid solutions PbB′1/2 B″1/2 O3 (B′ = Sc, Ga, In, Lu;...     

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.