Short-Range Order in Amorphous and Crystalline Ferroelectric Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript>

The microstructures of amorphous and polycrystalline ferroelectric Hf_0.5Zr_0.5O₂ films are studied by X-ray spectroscopy and ellipsometry. EXAFS spectra demonstrate that the amorphous film consists of an “incompletely mixed” solid solution of metallic oxides HfO₂ and ZrO₂. After rapid thermal annealing, the mixed Hf_0.5Zr_0.5O₂ oxide films have a more ordered polycrystalline structure, and individual Hf and Zr monoxide islands are formed in the films. These islands are several nanometers in size and have a structure that is similar to the monoclinic structure of HfO₂ and ZrO₂. The presence of the HfO₂ and ZrO₂ phases in the Hf_0.5Zr_0.5O₂ films is also detected by ellipsometry.     

DFT study on the electronic structure and chemical state of Americium in an (Am,U) mixed oxide

We investigated the electronic state of an (Am,U) mixed oxide with the fluorite structure using the all-electron full potential linear augmented plane wave method and compared it with those of Am₂O₃, AmO₂, UO₂, and La_0.5U_0.5O₂. The valence of Am in the mixed oxide was close to that of Am₂O₃ and the valence of U in the mixed oxide was pentavalent. The electronic structure of AmO₂ was different from that of Am₂O₃, particularly just above the Fermi level. In addition, the electronic states of Am and U in the mixed oxide were similar to those of trivalent Am and pentavalent U oxides. These electronic states reflected the high oxygen potential of AmO₂ and the heightened oxygen potential resulting from the addition of Am to UO₂ and also suggested the occurrence of charge transfer from Am to U in the solid solution process.     

Neutron-diffraction studies of the antiferromagnetic–ferromagnetic transition in anion-deficient cobaltites

Anion-deficient La_0.5Ba_0.5CoO_2.8 and Y_0.25Ca_0.25Sr_0.5CoO_2.62 cobaltites are studied under pressures up to 6.5 GPa in the temperature range of 5?300 K by neutron powder diffraction. Under ambient pressure both compounds are antiferromagnetic with T _N = 250 K. The applied pressure induces in the first compound a gradual transition from the antiferromagnetic to ferromagnetic state through a mixed magnetic state, whereas the second compound remains antiferromagnetic in the whole pressure range. We suggest that the magnetic ground state depends on the unit-cell volume and the magnetic transition is associated with the transition of cobalt ions from the mixed high-spin/low-spin state to the intermediate-spin/low-spin state.     

Passively Q-switched laser performance of the mixed crystals Nd:Lu0.15 Y0.85 VO4, Nd:Lu0.5 Y0.5 VO4 and Nd:Lu0.33Y0.37Gd0.3VO4 with GaAs saturable absorber

By using the mixed crystals Nd:Lu_0.15 Y_0.85 VO₄, Nd:Lu_0.5Y_0.5VO₄ and Nd:Lu_0.33Y_0.37Gd_0.3VO₄ as laser media, the LD pumped passively Q-switched mixed lasers with GaAs saturable absorber are realized. The average output power, the pulse width etc. have been measured and compared. The experimental results show that the passively Q-switched Nd:Lu_0.33Y_0.37Gd_0.3VO₄ laser can generate shorter pulse width with higher peak power due to broader fluorescence line-width. Under Gaussian spatial distribution approximation, the rate equations for LD pumped passively Q-switched lasers of the mixed crystals with GaAs saturable absorber are given. The numerical solutions of the equations are in agreement with the experimental results.     

AB INITIO CALCULATIONS OF OPTICAL PHONON DEFORMATION POTENTIALS IN DIAMOND AND ZINC-BLENDE SEMICONDUCTORS

The behavior of the internal lattice vibrational modes in (NH₄)₂Te_xSn_1-xCl₆ mixed crystals has been investigated by Raman scattering. All of the Raman-active [MX₄]^2- internal modes show two-mode property in the mixed crystals with compositions from x =0 to 1, and apart from the sample with x = 0.5, their energy positions are composition-independent, Space group calculations including site symmetry considera-tions and frequency fittings describe a good force field model. It has been demonstrated that the composition-independent two-mode behavior may come from the strong clustering effect, rather than from the character of the gap and local modes of impurities in mixed crystals. For the sample with x=0.5, the two component elements seem to form a pseudo-periodic lattice structure.     

Study on the structural properties and relaxation mechanisms in LiRb(1-x)(NH₄)(x)SO₄ (x=0, 0.5, and 1) mixed crystals by ¹H, ⁷Li, and ⁸⁷Rb nuclear magnetic resonance

LiRb_1?x(NH₄)_xSO₄ (x=0, 0.5, and 1) mixed crystals were grown using the slow evaporation method, and their lattice constants were determined by X-ray diffraction. The effects of replacing ammonium ions with rubidium on the phase transitions of and dynamics of LiRb_1?x(NH₄)_xSO₄ mixed crystals were studied. We investigated the structural properties and phase transition temperatures of the LiRb_1?x(NH₄)_xSO₄ mixed crystals by performing ¹H, ⁷Li, and ⁸⁷Rb NMR relaxation and DSC. When a fraction of rubidium ions in the pure LiRbSO₄ crystal is partially replaced by ammonium ions, we compare the structural properties for LiRbSO₄, LiRb_0.5(NH₄)_0.5SO₄, and LiNH₄SO₄ single crystals. The ¹H, ⁷Li, and ⁸⁷Rb NMR relaxation mechanisms of LiRb_0.5(NH₄)_0.5SO₄ are different from those of pure LiRbSO₄ and LiNH₄SO₄; the sequence of the structural phase transitions of LiRb_0.5(NH₄)_0.5SO₄ is different, which might be related to the dynamics and orientation of the sulfate tetrahedral groups in the crystal structure.     

Structural characteristics of olivine Li(Mg0.5Ni0.5)PO4 via TEM analysis

The structural characteristics of olivine-type lithium orthophosphate Li(Mg_0.5Ni_0.5)PO₄ synthesized via solid-state reaction have been studied using X-ray diffraction, ion beam technique, scanning electron microscopy, infrared spectroscopy, transmission electron microscopy and energy dispersive X-ray analysis. The parent LiNiPO₄ compound can be synthesized in olivine structure without any evidence of secondary phases as impurities. The structural quality of the parent LiNiPO₄ in the absence of secondary component phases resulted in the formation of hexagonal closed packed structure. The olivine analogue compound containing mixed M (M?=?Mg, Ni) cations, Li(Mg_0.5Ni_0.5)PO₄ contained Li₃PO₄ as a second phase upon synthesis, however a carbothermal reduction method produced a single-phase compound. The redox behaviour of carbon-coated Li(Mg_0.5Ni_0.5)PO₄ cathode in aqueous lithium hydroxide as the electrolyte showed reversible lithium intercalation.     

XPS study of U,UNi5, UCu5 and UNi0.5Cu4.5

Core and valence band spectra of U metal and the intermetallic compounds UNi₅, UCu₅ and UNi_0.5Cu_4.5 have been measured by X-ray excited photoelectron spectroscopy (XPS). The data indicate that in UNi₅ the configuration is 5f³, and in UCu₅ and Uni_0.5Cu_4.5 a mixed valence configuration with fewer 5f electrons than in UNi₅ is present.     

Structure and magnetization studies of Nd0.5−xPrxSr0.5MnO3 system

The structural and magnetic properties of Nd_0.5−xPr_xSr_0.5MnO₃ (x=0, 0.1, 0.2, 0.3, 0.4 and 0.5) system have been investigated. With the substitution of Pr in Nd_0.5Sr_0.5MnO₃, it shows a gradual structure transformation from the Imma orthorhombic symmetry to the tetragonal I4/mcm phase, and the crystallographic transition remains incomplete, even in Pr_0.5Sr_0.5MnO₃. A large bifurcation between zero-field-cooled (ZFC) and field-cooled (FC) susceptibility has been observed below Curie temperature (T_C), which is characteristic of coexistence of ferromagnetism (FM) and antiferromagnetism (AFM) at low temperature region. The magnetization of Pr_0.5Sr_0.5MnO₃ is larger than that of Nd_0.5Sr_0.5MnO₃, while Nd_0.5Sr_0.5MnO₃ with more CE-type AFM shows larger magnetization than Nd_0.3Pr_0.2Sr_0.5MnO_3, which mixed with CE-type (majority) and A-type (minority) AFM at low temperature, indicating that the magnetization of Nd_0.5−xPr_xSr_0.5MnO₃ system is affected by A-site disorder combined with orbital ordering of A-type AFM and CE-type AFM.     

Effect of carbon coating process on the structure and electrochemical performance of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>O<Subscript>2</Subscript> used as cathode in Li-ion batteries

LiNi_0.5Mn_0.5O₂ powder was synthesized by a coprecipitation method. LiOH.H₂O and coprecipitated [(Ni_0.5Mn_0.5)C₂O₄] precursors were mixed carefully together and then calcined at 900°C. Surface modified cathode materials were obtained by coating LiNi_0.5Mn_0.5O₂ with a thin layer of amorphous carbon using table sugar and starch as carbon source. Both parent and carbon-coated samples have the characteristic layered structure of LiNi_0.5Mn_0.5O₂ as estimated from X-ray diffractometry measurements. Transmission electron microscope showed the presence of C layer around the prepared particles. TGA analysis emphasized and confirmed the presence of C coating around LiNi_0.5Mn_0.5O₂. It is obvious that the carbon coating appears to be beneficial for the electrochemical performance of the LiNi_0.5Mn_0.5O₂. A capacity of about 150 mAh/g is delivered in the voltage range 2.5–4.5 V at current density C/15 for carbon coated LiNi_0.5Mn_0.5O₂ in comparison with about 165 mAh/g obtained for carbon free LiNi_0.5Mn_0.5O₂ at the same current density and voltage window. About 92% and 82% capacity retention was obtained at 50th cycle for coated LiNi_0.5Mn_0.5O₂ using sucrose and starch, respectively; whereas, 75% was retained after only 30th cycle for carbon free LiNi_0.5Mn_0.5O₂. This improvement is mainly attributed to the presence of thin layer of carbon layer that encapsulate the nanoparticles and improve the conductivity and the electrochemical performance of LiNi_0.5Mn_0.5O₂.     

Synthesis of LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> nano/microspheres with adjustable hollow structures for lithium-ion battery

High-voltage spinel LiNi_0.5Mn_1.5O₄ nano/microspheres with adjustable hollow structures have been fabricated based on the Kirkendall effect. The main characteristic is that the wall thickness of the hollow structure as well as the cavity size of the hollow structure can be adjusted by the different ratio of mixed precipitation agents. Especially, the diagrammatic sketch for the formation process of various LiNi_0.5Mn_1.5O₄ materials with adjustable hollow structures is discussed. Besides, the results of electrochemical performance test show that LiNi_0.5Mn_1.5O₄ obtained from 10:1 Na₂CO₃/NaOH (in mole) ratio is worth looking forward to, owing to its special hierarchical nano/microsphere and moderate hollow structures.     

Mixed valency of europium in magnetically ordered EuFe4Al8

X-ray, susceptibility and Mössbauer effect (ME) studies of EuFe₄Al₈ and EuFe_3.5Cu_0.5Al₈ were performed. The susceptibility and the ⁵⁷FeME studies indicate an antiferromagnetic phase transition of the iron sublattic at 140 K. The ¹⁵¹EuME studies show a temperature dependent isomer shift typical of a mixed valent state with an interconfiguration excitation energy (ICE) of 1100 K and width 400 K. At temperatures below 140 K also the Eu ions become magnetically ordered. In EuFe_3.5Cu_0.5Al₈ the europium ICE is strongly dependent on local environment.     

Phonon-assisted luminescence anomalies in Eu2+ doped Ca1-xSrxF2 mixed crystals

Abstract

With increasing X on Ca_1-xSr_xF₂ mixed crystals doped with Eu²⁺ (4f⁶5d) ions, the absorption peak shifted linearly to that of SrF₂:Eu, while the luminescence one moved parabolically with a minimum at around x=0.5. The linewidth broadened nearly twice as large as that of CaF₂ in the vicinity of x=0.5 and subsequently renarrowed for x > 0.5. The temperature dependences of the luminescence intensity and life time revealed that the nonradiative activation energy has a minimum of 0.40 eV around x=0.5. From the calculated result of the lineshape, these non-linear behaviors against x were explained by adjusting the electron-phonon coupling strength.     

Phonon-phonon interactions in (Lu, Y)Ni2B2C

The temperature dependence of the Δ₄ acoustic and optic mode, measured at q=(0.5,0,0) in LuNi₂B₂C, YNi₂B₂C were extended to 1000 K and new measurements on the mixed compound, Y_0.5Lu_0.5Ni₂B₂C, were undertaken to explore the mode coupling in these materials. The temperature behavior of each is different and cannot be explained by a simple mode coupling scheme of the acoustic and optic modes.     

Actively Q-switched performance of a mixed crystal Nd:Lu<Subscript>0.5</Subscript>Y<Subscript>0.5</Subscript>VO<Subscript>4</Subscript> at 1.34 μm

The actively Q-switched laser performance of the mixed Nd:Lu_0.5Y_0.5VO₄ crystal was demonstrated for the first time. At the pump power of 7.26 W, the minimum pulse width of 46.6 ns was obtained at the pulse repetition rate of 5 kHz with the cavity length of 80 mm, and the single pulse energy and peak power were calculated to be 42 μJ and 901.3 W, respectively.     

Properties of the solid solution (1−x)Na0.5Bi0.5TiO3-(x)BiFeO3

This study shows that remarkable electric and magnetic properties are encountered within the (1−x)Na_0.5Bi_0.5TiO₃ (NBT)-(x)BiFeO₃ (BF) solid solution. Dual ferroelectric and magnetic properties are observed in the BF-rich part of the solid solution implying intrinsic multiferroic character of the compounds. In addition, a relaxation phenomenon is evidenced within the overall compositional domain of the solid solution. This study emphasizes that in the NBT-rich part, the relaxor behaviour is very similar to that of NBT, while beyond x=0.5, it turns to a different mechanism of relaxation probably induced by the presence of oxygen vacancies resulting from the mixed valence of the iron cations.     

Preparation and electrical conductivity of LISICON thin films

LISICON thin films have been prepared with RF sputtering and subsequent heat-treatment. The crystal phases of sputtered films depend on the sputtering conditions, especially the target composition and ambient gas atmosphere. Though the as-sputtered films in Ar-O₂ mixed gas (target composition: Li₃Zn_0.5GeO₄+0.5 ZnO, gas pressure: 9×10^-2 Torr, oxygen gas content: 74.6%) were amorphous; LISICON single phase thin films were obtained after annealing at 600°C for 6 h. The conductivity of the film at 500°C is 5×10^-3ω^-1cm^-1 which is slightly lower than that for ceramic Li₃Zn_0.5GeO₄.     

Lead-free BFN ceramics doped by chromium,lithium or manganese

The material of the study was lead-free BaFe_0.5Nb_0.5O₃ ceramics subject to modification. The base composition BaFe_0.5Nb_0.5O₃ as well as the chromium, lithium and manganese modified ones were obtained using conventional mixed oxides and carbonates method. Synthesis was performed by the powder calcination method at high temperature 1250 °C for 4 h, while the densification was carried out by free sintering method under conditions 1350 °C/4 h. The paper presents a complex study of admixtures influence on the crystal structure, microstructure and dielectric properties of the BFN type samples. The mentioned dopants chromium, lithium or manganese in the BFN-type ceramics among other caused the reduction of the electric permittivity maximum as well as significant decrease in value of dielectric loss.     

The nature of antimony-enriched surface layer of Fe-Sb mixed oxides

Antimony segregation is a common feature in Fe-Sb mixed oxides, which have been widely applied as catalysts in selective oxidation and ammoxidation reactions. This paper attempts to shed a light on the cause of such a common feature and on the nature of the antimony-enriched surface layer over FeSbO₄ by means of XPS surface analysis. Single-phase FeSbO₄ samples prepared by different methods were studied, and the antimony in their surface layer is a mixture of both Sb⁵⁺ and Sb³⁺ rather than single Sb⁵⁺. Their surface composition is close to FeSb₂O₆, which could be described as (FeSbO₄)(Sb₂O₄)_δ, δ = 0.5, and it is not “Fe(II)Sb(V)₂O₆” as suggested in literature. Fe-Sb mixed oxides with Sb/Fe > 1 (mol/mol) are mixtures of FeSbO₄ and Sb₂O₄, and the surface of FeSbO₄ grains would be a layer of (FeSbO₄)(Sb₂O₄)_δ, δ ≥ 0.5. Fe-Sb mixed oxides with Sb/Fe < 1 are mixtures of FeSbO₄ and Fe₂O₃, and the surface of FeSbO₄ grains would be a layer of (FeSbO₄)(Sb₂O₄)_δ, δ ≤ 0.5, but the remaining Fe₂O₃ would be encapsulated by a layer of FeSbO₄.     

Identification of a spin-glass and a cluster-glass by Mössbauer measurements: Fe0.5Mn0.5TiO3 and Fe0.2Mg0.8TiO3

Summary M?ssbauer measurements have been made on two kinds of spin-glass (SG) systems: one is the magnetically non-diluted mixed compound Fe_0.5Mn_0.5TiO₃ with the SG-freezing temperatureT _SG=21.5K, and the other is the diluted one Fe_0.2Mg_0.8TiO₃ withT _SG=6K. We have shown that the temperature variation of the M?ssbauer spectrum of Fe_0.2Mg_0.8TiO₃ above and around itsT _SG is essentially different from that of Fe_0.5Mn_0.5TiO₃: the former is typical of a cluster-glass and the latter of an ordinary spin-glass. The present work has clearly demonstrated that the M?ssbauer spectroscopy is the most useful and unique technique to distinguish a cluster-glass from an ordinary spin-glass. Paper presented at the ICAME-95, Rimini, 10–16 September 1995