A tunable green alkaline-earth silicon-oxynitride solid solution (Ca1? x Sr x )Si2O2N2:Eu2+ and its application in LED

A series of (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ (x=0.0–0.97, y=0.03) phosphors were synthesized by high-temperature solid-state reaction. The XRD patterns confirm the formation of a solid solution of (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺. An intense tunable green light is observed with the increasing ratio of Sr/Ca. With an increase in x, the excitation and emission spectra show a redshift and blueshift, respectively, due to large centroid shift and small Stokes shift. The temperature dependent luminescence is also investigated in the temperature range of 77–450 K. The Huang–Rhys factor and the thermal-quenching temperature are determined. Intense green LEDs were successfully fabricated based on the (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ phosphor and near-ultraviolet (∼395 nm) GaN/blue (460 nm) InGaN chips. All the results indicate that the solid solution (Ca_1−x−y Sr _x )Si₂O₂N₂:yEu²⁺ is a promising phosphor applicable to near-UV and blue LEDs for solid-state lighting.     

Antiferroelectric–ferroelectric phase transition in lead zinc niobate modified lead zirconate ceramics: crystal studies, microstructure, thermal and electrical properties

The combination of antiferroelectric PbZrO₃ (PZ) and relaxor ferroelectric Pb(Zn_1/3Nb_2/3)O₃ was prepared via the columbite precursor method. The basic characterizations were performed using X-ray diffraction (XRD), scanning electron microscopy (SEM), linear thermal expansion, differential scanning calorimetry (DSC) techniques, dielectric spectroscopy, and hysteresis measurement. The XRD result indicated that the solid solubility limit of the (1−x)PZ–xPZN system was about x=0.40. The crystal structure of (1−x)PZ–xPZN transformed from orthorhombic to rhombohedral symmetry when the concentration of PZN was increased. A ferroelectric intermediate phase began to appear between the paraelectric and antiferroelectric phases of pure PZ, with increasing PZN content. In addition, the temperature range of the ferroelectric phase increased with increasing PZN concentration. The morphotropic phase boundary (MPB) in this system was located close to the composition, x=0.20.     

Magnetic properties of small amounts of iron dissolved in copper palladium alloys

The magnetic susceptibilities of copper-rich Cu_1−x Pd _x Fe _y alloys,x=0−0.40,y=30−300 ppm, have been measured in the temperature range 1.7 K–300 K. The results imply that an iron atom induces a magnetic moment of about 0.35μ _B on a nearest neighbour palladium atom. Conversely the effect of the nearest neighbour palladium atom on the iron atom itself leads to a stabilization of the iron moment indicated by a lowering of its Kondo temperature.     

Galvanomagnetic properties of Hg1−x MnxTe1−y Sey semimagnetic semiconductors

The galvanomagnetic properties of single crystals of the semimagnetic semiconductors Hg_1−x Mn_xTe_1−y Se_y with 0.01<y<0.1 and x=0.05 and 0.14 in the temperature range 4.2–300 K are investigated. The features of the temperature dependence of the Hall coefficient R _H and the complicated behavior of R _H in a magnetic field are attributed quantitatively to the existence of three groups of current carriers, viz., electrons and two types of holes, for which the temperature dependences of the densities and mobilities are obtained. A transition from p-type to n-type conductivity is observed as the Se content is increased, and the negative magnetoresistance simultaneously gives way to positive magnetoresistance. Zh. éksp. Teor. Fiz. 112, 1809–1815 (November 1997)     

Dielectric properties of (1−x)[0.7PbZrO3·0.3K0.5Bi0.5TiO3]·xSrTiO3 solid solutions in the vicinity of phase transitions

The dielectric properties of polycrystalline (1−x)[0.7PbZrO₃·0.3K_0.5Bi_0.5TiO₃]·xSrTiO₃ solid solutions, where x=0–0.7, are studied in the temperature range 150–600 K. Systematic spreading of the ferroelectric phase transition with increasing strontium titanate content is discovered. The dispersion of the dielectric constant at frequencies from 10⁻¹ to 10⁶ Hz is investigated for a composition with x⋍0.7. The existence of two relaxation processes characterized by diffuse relaxation time spectra, which broaden with decreasing temperature, is established. It is postulated that a transition to a glasslike state takes place in the material with x⋍0.7. Zh. Tekh. Fiz. 69, 35–38 (March 1999)     

Ferroelectric properties of SrTiO3-PbTiO3 solid solutions

Dielectric properties of ceramic samples of Sr_1−x Pb_xTiO₃ solid solutions for x varying from 0 to 0.3 have been studied. The ferroelectric phase transition in this system has been established to persist down to x=0.005. Within the x values of 0.002 to 0.05, the ferroelectric transition temperature is shown to follow the relation T _c=A(x−x _c)^1/2, with A=440 K and x _c=0.002. Fiz. Tverd. Tela (St. Petersburg) 39, 714–717 (April 1997)     

Ferroelectric phase stabilization, phase transformations and?thermal properties in (1? x )PbZrO3– x Pb(Co1/3Nb2/3)O3 solid solution

The solid solution between the antiferroelectric PbZrO₃ (PZ) and relaxor ferroelectric Pb(Co_1/3Nb_2/3)O₃ (PCoN) was synthesized by the columbite method. The phase structure and thermal properties of (1−x)PZ–xPCoN, where x=0.0–0.3, were investigated. With these data, the ferroelectric phase diagram between PZ and PCoN has been established. The crystal structure data obtained from XRD indicates that the solid solution PZ–PCoN, where x=0.0–0.3, successively transforms from orthorhombic to rhombohedral symmetry with an increase in PCoN concentration. The AFE→FE phase transition was found in the compositions of 0.0≤x≤0.10. The AFE→FE phase transition shift to lower temperatures with higher compositions of x. The width of the temperature range of FE phase was increased with increasing amount of PCoN. It is apparent that the replacement of the Zr⁴⁺ ion by (Co_1/3Nb_2/3)⁴⁺ ions would decrease the driving force for antiparallel shift of Pb²⁺ ions, because they interrupt the translational symmetry. This interruption caused the appearance of a rhombohedral ferroelectric phase when the amount of PCoN was more than 10 mol%.     

Comparative analysis of the effect of La and Co on the superconductivity and energyband spectrum of YBa2Cu3Oy for different oxygen contents

Temperature dependences of the resistivity and Seebeck coefficient of Y(Ba_1−x La_x)₂Cu₃O_y and YBa₂Cu_3−x Co_xO_y samples (x=0–0.25) have been measured under maximum sample saturation with oxygen, as well as following their anneal in an oxygen-deficient atmosphere. The T _c (x) dependences for as-prepared samples were found to pass through a maximum at x=0.05, which persists after annealing for Y(Ba_1−xLa_x)₂Cu₃O_y and disappears for YBa₂Cu_3−x Co_xO_y. A phenomenological model of the band spectrum in normal phase has been used to determine the parameters of the conduction band and of the carrier system, and to analyze their variation with the dopant type and content, as well as with annealing. Despite the differences observed in the T _c (x) dependence, the critical temperatures for all the sample series studied were found to correlate with the conduction-band effective width. The mechanism of the effect of impurities on the band-structure parameters and the reasons for the different influence of annealing on the properties of Y(Ba_1−x La_x)₂Cu₃O_y and YBa₂Cu_3−x Co_xO_y are discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 389–394 (March 1997)     

The superconducting properties of YBa2(Cu1−xMx)3O7 for M=Zn and Ni

Transverse and zero-field μSR measurements were made on YBa₂(Cu_1−xNi_x)₃O_7−y withx=0.1 and 0.2, and YBa₂(Cu_1−x Zn _x )₃O_7−y withx=0.03, 0.06, 0.1, and 0.16, wherey≈0.1. Since doping may lead to magnetic ordering this was searched for with both zero and transverse field μSR, but no evidence was found over the temperature range studied: 10–100 K. However, depolarization rates as functions of temperature were obtained, and the low temperature values of these are σ=3.2 μs⁻¹.1.6μs⁻¹, and 1 μs⁻¹ forx=0.01, and 0.2 Ni, respectively, and σ=0.8 μs⁻¹, 0.75 μs⁻¹, 0.65 μs⁻¹, and 0.4 μs⁻¹ forx=0.03, 0.06, 0.1, and 0.16 Zn, respectively. Estimates for the effect of decreasing electron concentration for Zn are made, but these alone do not account for the drop in σ. Estimates for the effect of scattering on λ and hence σ are made. The reduction in σ for Ni dopant is in surprisingly good agreement with these estimates. For Zn the order of magnitude is correct, but the relative lack of further change in σ after the effect of the first 0.03 addition seems to imply a saturation of the effect of scattering.     

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)     

Electronic phase separation in a low-temperature tetragonal phase of lanthanum-strontium cuprates according to 139La NQR data

A nonuniform electron density distribution is observed in La_{1−x− y} Nd_ySr_xCuO₄ and La_1−x−y Eu_ySr_xCuO₄, and long-lived magnetic fluctuations in these compounds are studied. The dynamics of the magnetic fluctuations depends strongly on the magnetic properties of the rare-earth ions, which stabilize the low-temperature tetragonal phase. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 5, 344–349 (10 March 1998)     

Superconductivity, Seebeck coefficient, and band structure transformation in Y1−x CaxBa2Cu3−x CoxOy (x=0–0.3)

The temperature dependences of the resistivity and of the Seebeck coefficient S is studied in three series of Y_1−x Ca_xBa₂Cu_3−x Co_xO_y samples (x=0–0.3) differing in oxygen content. It was found that the critical temperature decreases for y≈7.0, and S(T=300 K) increases with doping, whereas oxygen deficiency results in a nonmonotonic variation of these quantities with increasing x. The band structure parameters have been determined from an analysis of the S(T) relations using a phenomenological theory of electron transport. It was found that an increase in x results in a gradual increase in band asymmetry, which is caused by calcium-induced creation of additional states in the band responsible for conduction in the normal phase. An analysis has shown that high impurity concentrations in oxygen-deficient Y_1−x Ca_xBa₂Cu_3−x Co_xO_y samples bring about an additional ordering of the structure, which may be caused by formation of a cobalt superlattice. It has also been shown that, in the case of Ca and Co codoping, the dependence of critical temperature on effective conduction-band width coincides with the universal correlation relation observed in the YBa₂Cu₃O_y system with single substitutions in various lattice sites. Fiz. Tverd. Tela (St. Petersburg) 41, 1363–1371 (August 1999)     

Local structure and electrochemistry of LiNi y Mn y Co1 − 2y O2 electrode materials for Li-ion batteries

A series of LiNi _x Mn _y Co _z O₂ (x = y, z = 1 − 2y) oxides have been synthesized by “chimie douce” and investigated as positive electrodes in rechargeable lithium batteries. Layered LiNi _y Mn _y Co_1 − 2y O₂ materials with high homogeneity and crystallinity were synthesized using the wet-chemical method assisted by carboxylic acid as the polymeric agent. The long range and local structural properties are investigated with experiments including X-ray diffraction, Fourier transform infrared spectroscopy, and electron paramagnetic resonance spectroscopy. The evolution of the structure is discussed as a function of the cobalt content that confers layer-like behavior on the framework. Electrochemical performance of LiNi _y Mn _y Co_1 − 2y O₂ oxides is tested in cells using nonaqueous 1 M LiPF₆ dissolved in ethylene carbonate–diethyl carbonate. Charge–discharge profiles are investigated as a function of the rate capability and the voltage window. A relation is found between the gravimetric capacity and the cation disorder of the positive electrode as indicated by structural analysis. Fast lithium extraction attributed to the larger interslab space has been observed in the cobalt-rich oxides. Paper presented at the 11th Euro-Conference on Science and Technology of Ionics, Batz-sur-Mer, France, 9–15 Sept. 2007.     

Phase equilibria in the La-Me-Co-O (Me=Ca, Sr, Ba) systems

The phase equilibria of the La-Me-Co-O systems (Me = Ca, Sr and Ba) were studied in air at 1100 °C. Two types of solid solution of general composition La_1−xMe_xCoO_3−δ and (La_1−y Me_y)₂CoO₄ were found to exist in the systems. The limiting composition of La_1−xMe_xCoO_3−δ lies at x=0.8 for Me = Sr, Ba and between 0.3–0.5 for Me = Ca. It is shown that the rhombohedral distortion of the perovskite type La_1−xMe_xCoO_3−y decreases while x increases. La_1−xMe_xCoO_3−δ (Me = Sr, Ba) shows an ideal cubic structure at x=0.5. The stability range of (La_1−yMe_y)₂CoO₄ was found to be 0.25≤y≤0.35 for Me = Ca, 0.3≤y≤0.55 for Me = Sr and 0.3≤y≤0.375 for Me = Ba. All phases have tetragonal K₂NiF₄-type crystal structure. Based on the XRD and neutron diffraction patterns of quenched samples, the phase diagrams (Gibbs triangles) are constructed for all systems. The phase equilibrium at low oxygen pressure is shown for the example of the La-Sr-Co-O system. The decomposition mechanism of La_1−xSr_xCoO_3−δ at 1100 °C for the samples with 0.5<x<0.8 within the oxygen pressure range −0.678>log(Po₂)>−2.25 can be written as follows: La_1−x′ Sr_x′CoO_3−δ′=n La_1−x″Sr_x″CoO_3−δ″+m SrCoO_2.5+q/2 O₂ where x′>x″. The decomposition mechanism of La_1−xSr_xCoO_3−δ for the samples with x < 0.5 within the oxygen pressure range −2.25>log(Po₂)>−3.55 changes and can be written as follows: La_1−xSr_xCoO_3−δ′=r La_1−x′Sr_x′CoO_3−δ″+w (La_1−y′Sr_y′)₂CoO₄+v CoO+f/2 O₂. The results are shown in “logPo₂-composition” diagrams. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Weak exchange interactions in the heteronuclear crystal CuPr2(CCl3COO)8·6H2O

The new heteronuclear crystal CuPr₂(CCl₃COO)₈·6H₂O, constructed of chains containing copper and praseodymium atoms, has been synthesized and investigated by EPR at 9.3 GHz at temperatures ranging from room temperature down to 10 K. At temperatures T∼300–130 K, EPR spectra are observed which are characteristic of isolated polyhedra of copper ions with g _z=2.330±0.005, g _x,y =2.053±0.005, A _z=139×10⁻⁴ cm⁻¹, and A _x,y <26×10⁻⁴ cm⁻¹. At temperatures T<130 K a complex spectrum is observed, associated with the appearance of weak exchange interactions between the copper ions in the chain (J _Cu-CuΣS _i·S _i+1), comparable in magnitude with the hyperfine interactions J _Cu-Cu=0.015 cm⁻¹ at T=10 K. The magnitude of the exchange interaction decreases smoothly as the temperature is raised. It is conjectured that orbitals of the praseodymium ions participate in the process of indirect exchange between the copper ions. Fiz. Tverd. Tela (St. Petersburg) 41, 2154–2157 (December 1999)     

Carrier mobility in nonstoichiometric n-Bi2Te3−x Sex solid solutions

A study has been made of the thermoelectric and galvanomagnetic properties of n-Bi₂Te_3−x Se_x solid solutions (x=0.3 and 0.36) in the temperature range 80–300 K. The lowest carrier concentrations, (0.8–1)×10¹⁸ cm⁻³, were obtained by displacing the solid solution from the stoichiometric to a Te-rich composition. At such carrier concentrations, the second subband in the conduction band of n-Bi₂Te_3−x Se_x is not filled, which results in a growth of mobility because of the absence of interband scattering, and brings about an increase of thermoelectric efficiency in the 80–120-K range. Fiz. Tverd. Tela (St. Petersburg) 39, 483–487 (March 1997)     

Structure, electrical properties and temperature characteristics of?Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3–Bi0.5Li0.5TiO3 lead-free piezoelectric ceramics

(1−x−y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃– yBi_0.5Li_0.5TiO₃ lead-free piezoelectric ceramics have been prepared by an ordinary sintering technique, and their structure, electrical properties, and temperature characteristics have been studied systematically. The ceramics can be well-sintered at 1050–1150 °C. The increase in K⁺ concentration decreases the grain-growth rate and promotes the formation of grains with a cubic shape, while the addition of Li⁺ decreases greatly the sintering temperature and assists in the densification of BNT-based ceramics. The results of XRD diffraction show that K⁺ and Li⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a solid solution with a pure perovskite structure. As x increases from 0.05 to 0.50, the ceramics transform gradually from rhombohedral phase to tetragonal phase and consequently a morphotropic phase boundary (MPB) is formed at 0.15≤x≤0.25. The concentration y of Li⁺ has no obvious influence on the crystal structure of the ceramics. Compared with pure Bi_0.5Na_0.5TiO₃, the partial substitution of K⁺ and Li⁺ for Na⁺ lowers greatly the coercive field E _c and increases the remanent polarization P _r of the ceramics. Because of the MPB, lower E _c and large P _r, the piezoelectricity of the ceramics is improved significantly. For the ceramics with the compositions near the MPB (x=0.15–0.25 and y=0.05–0.10), the piezoelectric properties become optimum: piezoelectric coefficient d ₃₃=147–231 pC/N and planar electromechanical coupling factor k _P=20.2–41.0%. In addition, the ceramics exhibit relaxor characteristic, which probably results from the cation disordering in the 12-fold coordination sites. The depolarization temperature T _d shows a strong dependence on the concentration x of K⁺ and reaches the lowest values at the MPB. The temperature dependences of the ferroelectric and dielectric properties at high temperatures may imply that the ceramics may contain both the polar and non-polar regions at temperatures above T _d.     

Relation between T c and the defect structure of neodymium cerium cuprite Nd2−x CexCuO4−y

Neutron powder diffraction has been used to study the defect structure of neodymium cerium cuprite Nd_2−x Ce_xCuO_4±y (x=0.15). It has been shown that in addition to oxygen vacancies, O2 sites in superconducting samples may also contain a small quantity of implanted oxygen atoms positioned between copper ions and neodymium/cerium, which control the electrical charge in the Cu-O planes. The oxygen distribution among crystal lattice sites in Nd_2−x Ce_xCuO_4±y (x=0.15) as determined, the average charge of the copper ions was calculated by the method of valence sums, and a correlation was established between the charge of the copper-oxygen plane and T _c. Fiz. Tverd. Tela (St. Petersburg) 40, 177–183 (February 1998)     

Effect of Li doping on the critical temperature and glass formation in the Bi-Sr-Ca-Cu-O system

A study has been made of the glass-forming ability, structure, and superconducting properties of Bi_2.2Sr_1.8Ca_1.05Cu_2.15Li_xO_y and Bi_2.2Sr_1.8Ca_1.05Cu_2.15−x Li_xO_y (x=0;0.3;0.5;0.7). The compounds were melted by rf at T=1300–1500 °C. Rapid quenching produces glassy alloys whose glass-forming ability is the highest when lithium is substituted for copper. Glass annealing at 700–800 °C results in the formation of the HTSC phase 2212 with a critical temperature of up to 91 K. In lithium-doped samples the HTSC phase forms at lower temperatures and shorter anneals and it depends on the cooling rate following the anneal. The composition and properties of the 2212 phase depend nonmonotonically on the anneal time. The lattice parameter C of the 2212 phase increases with increasing lithium content. Fiz. Tverd. Tela (St. Petersburg) 41, 18–21 (January 1999)     

Measurement of the differential and integral distribution of diffuse x-ray scattering intensity from defects in thin strained layers

Double-and triple-crystal diffractometry have been used to study structural perfection of a ∼1 μm-thick Ga_1−x In_xSb_1−y As_y epitaxial film (x=0.9, y=0.8) on GaSb. It is shown that scattering from samples of this system can be divided into coherent and diffuse. The arrangement of reciprocal-lattice points of the film and substrate in the two-dimensional intensity distribution for asymmetrical reflections argues for the absence of elastic-strain relaxation. No dislocation networks are formed, and the diffuse scattering is produced by Coulomb-type defects. Localization of diffuse scattering in reciprocal space suggests that these defects reside in the epitaxial film. The diffuse-scattering distribution in asymmetrical reflections is shown to be anomalous; namely, it extends in a direction parallel to the surface and is split into two maxima. Schemes have been proposed and realized for measuring integral distributions of diffracted intensity along the surface and perpendicular to it, and their potential for studying diffuse scattering from defects is explored. Fiz. Tverd. Tela (St. Petersburg) 39, 1188–1193 (July 1997)