Phase transitions in La1−x CaxMnO3−x/2 manganites

The crystal structure parameters and magnetic and electrical properties of La_1?x Ca_xMnO_3?x/2 reduced manganites with 0≤x≤0.5 are established. These investigations contribute to the understanding of magnetic interactions in manganites without Mn⁴⁺ ions. It is found that these manganites show a long-range antiferromagnetic order up to x=0.09 and transform into spin glasses at 0.09<x≤0.35. The compositions in the range 0.35<x≤0.5 show a strong increase in the spontaneous magnetization and critical point associated with the appearance of spontaneous magnetization and can therefore be viewed as inhomogenious ferromagnets. The magnetic and crystal structure peculiarities of La_0.5Ca_0.5MnO_2.75 are established by the neutron diffraction method. The strongly reduced samples show a large magnetoresistance below the point where the spontaneous magnetization develops. The magnetic phase diagram of La_1?x Ca_xMnO_3?x/2 is established by magnetization measurements. The magnetic behavior is interpreted assuming that the Mn³⁺-O-Mn³⁺ magnetic interaction is anisotropic (positive-negative) in the orbitally ordered phase and isotropic (positive) in the orbitally disordered phase. Introduction of the oxygen vacancies changes the magnetic interaction sign from positive to negative, thereby leading to a spin glass state in strongly reduced compounds. The results obtained reveal unusual features of strongly reduced manganites such as a large ferromagnetic component, a high magnetic ordering temperature, and a large magnetoresistance despite the absence of Mn³⁺-Mn⁴⁺ pairs. In order to explain these results, the oxygen vacancies are supposed to be ordered.     

ВЛИЯНИЕ СОДЕРЖАНИЯ К ИСЛОРОДА НА ЭЛЕКТРИЧЕСКИЕ И ТЕ РМОЭЛЕКТРИЧЕСКИЕ СВОЙСТВА ТРОЙНОЙ СИС ТЕМЫ Вi2Те3−x Sе x

, Bi₂Te_3–x Se _x . , , . , , . .

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Influence of oxygen content on electric and thermoelectric properties of ternary system Bi₂Te_3–x Se _x

A study is made of the influence of oxygen, contained in the semi-conducting system Bi₂Te_3–x Sé _x , on the electric and thermoelectric properties. It is shown that the addition of oxygen to the prepared samples Bi₂Te_2.4Se_0.6 causes a decrease in electric conductivity while the thermoelectric force remains unchanged. This influence is connected with a decrease in the mobility of the electrons but their concentration is not influenced by the presence of oxygen. Conclusions are reached as to the influence of oxygen on the efficiency of the conversion of thermal energy into electric energy and vice versa.

     

Thermoelectric properties of the Nd2−x Ce x CuO4−y system

The temperature dependence of the Seebeck coefficient (in region 300–900 K) and the lattice constants of Nd_2–x Ce_xCuO_4–y (x=0, 0.05, 0.10, 0.15) with different oxygen content were measured. The value of S is always negative and it decreases with both Ce content and oxygen non-stoichiometry. At a certain concentration of Ce and oxygen in the material, the Seebeck coefficient becomes temperature-independent.The authors would like to thank Professor J. Horák of University of Chemical Technology, Pardubice for helpful discussions.     

LaAg x In1−x

The structures of LaAg _x In_1–x alloys withx=0.75, 0.89 are determined by neutron diffraction on powder samples. The space group isI4/mmm (D _4h ^/17 ). The lattice constants splitting, the order parameter and the mean square vibrational amplitudes of the atoms are given in the temperature range from 20 KT300 K.     

Superconductivity and magnetism in Y1−x Ca x Sr2GaCu2O7−δ

Samples of Y_1–x Ca _x Sr₂GaCu₂O_7– (x=0, 0.4) doped with⁵⁷Fe, prepared under various oxygen pressures, have been studied by magnetometry and Mössbauer spectroscopy. Most of the iron ions (Fe³⁺) enter the Ga(Cu(1)) site. For thex=0 sample, the Mössbauer spectra of the iron nuclei in the Cu(2) sublattice display magnetic order of Cu,T _N=370 K. The iron ions in the Ga site display magnetic order only at low temperatures. At temperatures above 90 K, these iron ions display a pure quadrupole doublet Mössbauer spectrum. The samplex=0.4 also displays magnetic order of the Cu(2) site,T _N370 K. A sharp drop in the hyperfine field is observed atT _N, probably associated with a first-order phase transition or two-dimensional ordering. The iron nuclei in the Ga site display paramagnetic long spin relaxation time phenomena at 4.2 K. Thex=0.4 sample prepared under 110 atm oxygen pressure, displays superconductivity,T _c50 K. The Mössbauer spectra give evidence of the presence of two phases. One displays magnetic order, the other is paramagnetic, the last is probably associated with the superconducting phase.     

High-Moment-Low-Moment Description of Magnetovolume Effects in Y(Mn x Al 1− x ) 2 and Y x Sc 1− x Mn 2

Based on the assumption of a high-moment-low-moment instability of the Mn atom, we construct a simple spin model with coupled magnetic and spatial degrees of freedom to describe the Laves phase systems Y(Mn x Al 1 m x ) 2 and Y x Sc 1 m x Mn 2 . Monte Carlo simulations of this model qualitatively reproduce anomalies observed in these materials like a discontinuous giant volume change and anomalous thermal expansion behavior.     

Negatron effects in CdSe1 − x Te x and ZnS1−x Se x films

Various negatron effects in films of alloys of II–VI compounds deposited from solutions as a function of the deposition mode and heat treatment are studied. It is found that the negative photocapacitance effect, which was first discovered in ZnS_1?x Se _x films, and the slowly relaxing negative photoelectric effects, which are caused by the transition of electrons located in a nanoscale surface layer from the shallow energy levels of trapping centers to deeper levels with a lower polarizability and by the presence of nanoscale clusters in these materials, which play the role of a “reservoir” for minority charge carriers, occur according to a single mechanism. A model to explain the basic laws of negative photoconductivity in CdSe_{1 ? x} Te _x films deposited from a solution is proposed. Negative residual conductivity is explained in terms of double-barrier relief model, while negative differential photoconductivity is attributed to the presence of nanoscale electric domains.     

Magnetic hyperfine fields in Y2Fe17−x Si x compounds

Y₂Fe_17–x Si _x compounds withx=0, 0.5, 1.0, 1.5, 2.0, 2.5 and3.0 were investigated by magnetic measurement andNMR. It is found that with increasing Si content the Curie temperatureT _C increases while the average Fe magnetic moment _Fe decreases. NMR study indicates that Si preferentially substitute the Fe atoms at 4f sites, which is responsible for the increase ofT _C.     

Introduction of bismuth into the highT c superconductor La2−x Sr x CuO4−y

Novel high-T _c superconductors La_2–x Bi _x Sr _x–x CuO_4–y have been isolated and studied. The influence of the experimental conditions of synthesis on the superconductivity has been especially studied for the composition La_1.7Bi_0.1Sr_0.2CuO_4–y ; it is shown thatT _c decreases as oxygen is introduced into the matrix, likely due to the partial oxidation of Bi(III) to Bi(V). The highT _c value observed for one sample (T _c 42 K), as compared withT _c 38 K of La_1.8Sr_0.2CuO_4–y suggests that bismuth is also a potential candidate for improving the superconducting properties in these oxides.     

Calcium doping effects in57Fe : La2−x Ca x CuO4−y oxides

La_2–x Ca _x Cu_0.99Fe_0.01O_4–y samples with 0.00 x 0.30 were studied by X-ray diffraction and Mössbauer spectroscopy after heat treatment under different atmospheres (air, oxygen and helium). The variation of the relative population and the hyperfine interactions of the sites as well as the change in the lattice parameters were obtained.On leave from National Center for Scientific Research, PO Box 6990, Havana, Cuba.     

Diffusion and point defects in TiO2−x

The self-diffusion of ⁴⁴Ti has been measured both parallel to and perpendicular to the c axis in rutile single crystals by a serial-sectioning technique as a function of temperature (1000–1500°C) and oxygen partial pressure (10^?14 ? 1 atm). The oxygen-partial-pressure dependence of. D¹_Ti indicates that cation selfdiffusion occurs by an interstitial-type mechanism and that both trivalent and tetravalent interstitial titanium ions may contribute to cation self-diffusion. At p_o2 = 1.50 × 10^?7 atm where impurity-induced defects are unimportant,

$\text{D}{}^1{}_{\mathrm{<mtext>Ti</mtext>}}\text{(∥c)=}\text{6.50}\text{+1.33}\text{?1.11}\text{exp}\text{?}\text{(66.11±0.56}\text{kcal}\text{mole}\text{RT}\text{cm}{}^2\text{S}$

and

$\text{D}{}^1{}_{\mathrm{<mtext>Ti</mtext>}}\text{(⊥c)=}\text{4.55}\text{+1.78}\text{?1.28}\text{exp}\text{?}\text{(64.08±0.99)}\text{kcal}\text{mole}\text{RT}\text{cm}{}^2\text{S}\text{.}$

In the intrinsic region, the ratio D¹_Ti (⊥c)/D¹_Ti(∥c) was found to increase from 1.2 to 1.6 as the temperature decreased from 1500 to 1000°C. Computations based upon the defect model of Kofstad (involving the atomic defects Ti^..._iTi^...._iand V^.._o), of Marucco etal. (Ti^...._i and V^.._o), and of Blumenthal etal. (Ti^..._i and Ti^...._i) are compared with the experimental data on deviation from stoichiometry, electrical conductivity, cation self-diffusion and chemical diffusion in TiO_2?x. These comparisons provide values of the defect concentrations, cation-defect diffusivities, electron mobility and reasonable values of the correlation factor for cation diffusion by the interstitialcy mechanism. Only the model of Kofstad is inconsistent with the data.     

Vibrational spectra of CuAl x Ga1−x S2 solid solutions

Investigations of the IR reflection and Raman spectra in polarized light are carried out on single crystals of the ternary compounds CuAlS₂ and CuGaS₂ and solid solutions based on them grown by the method of chemical transport reactions. The frequencies of longitudinal and transverse phonons are determined, the IR intensities and damping factors of phonons (ε₀, ε_∞) are calculated, and their concentration dependences are constructed. It is established that optical vibrations in the solid solutions manifest a mixed behavior. Belarusian State University of Information Science and Radioelectronics 6 P. Brovka Str., Minsk, 220072, Belarus; e-mail: kafchim@gw.bsuir.unibel.by. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 6, pp. 800–803, November–December, 1999.     

Magnetic and structural transition of Ni50+xMn25−x/2Ga25−x/2 (x=2–5) alloys

Magnetic and structural transitions of non-stoichiometric Ni_50+xMn_25−x/2Ga_25−x/2 (x=2–5) alloys are systematically investigated. Differential scanning calorimetry and modified thermogravimetry (TG) are used to measure magnetic and structural transitions simultaneously. The structural transition temperatures increase monotonically with increasing Ni substitution for Mn and Ga. Different magnetic transition sequences on heating were observed from ferromagnetic martensite to ferromagnetic autensite, then to paramagnetic autensite, from ferromagnetic martensite to paramagnetic austensite or from ferromagnetic martensite to paramagnetic martensite, respectively. Three kinds of NiMnGa alloys were obtained according to the sequence of the structural and magnetic transition, whose structural transition temperatures are lower, equal to or higher than the magnetic transition temperatures.     

A study of Ba x Mg1 − x F2 optical films

Ba _x Me_{1 ? x} F₂ binary fluoride films (“Me” denotes calcium or magnesium fluoride) are studied. A method of processing the reflection and transmission spectra is proposed to determine the optical constants. The dispersion dependences of the refractive indices and absorption coefficients of films in the range of 1.3–12 μm are found. Dispersion in films in the regions of additional absorption bands, which are absent in single crystals, is observed for the first time. It is shown that the films of binary fluorides have a higher packing density, a lower absorption, and better operating characteristics than do films of pure fluorides. The films are promising for application as optical interference coatings in the mid-IR spectral region.     

Vortex structure in BaFe2(As1 − x P x )2 single crystals

Single crystals of iron-containing Ba(FeAs)₂ superconductors doped with phosphorus have been studied. The vortex structure has been studied by means of the decoration method. Large domains of the triangular vortex structures have been observed in the phosphorus-doped single crystals of iron-containing superconductors. The effect of doping on pinning in iron-containing superconductors has been discussed.     

Thermoelectric power of Ba(Fe1−x Co x )2As2 (0 ≤ x ≤ 0.05) and Ba(Fe1−x Rh x )2As2 (0 ≤ x ≤ 0.171)

Temperature-dependent, in-plane, thermoelectric power data are presented for single crystals of Ba(Fe_1?x Co _x )₂As₂ (0?≤?x?≤?0.05) and Ba(Fe_1?x Rh _x )₂As₂ (0?≤?x?≤?0.171). Given that previous thermoelectric power and angle resolved photoemission spectroscopy studies of Ba(Fe_1?x Co _x )₂As₂ delineated a rather large Co-concentration range for Lifshitz transitions to occur, and the underdoped side of the phase diagram is poorly explored, new measurements of thermoelectric power on tightly spaced concentrations of Co, 0?≤?x?≤?0.05, were carried out. The data suggest evidence of a Lifshitz transition, but instead of a discontinuous jump in thermoelectric power in the range 0?≤?x?≤?0.05, a more gradual evolution in the S(T) plots as x is increased was observed. The thermoelectric power data of Ba(Fe_1?x Rh _x )₂As₂ show very similar behavior to that of Co substituted BaFe₂As₂. The previously outlined T–x phase diagrams for both systems are further confirmed by these thermoelectric power data.     

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.     

Structure and phase stability of nanocrystalline Ce1−x Ln x O2−x/2−δ (Ln = Yb, Lu) in oxidizing and reducing atmosphere

The structure and phase evolution of nanocrystalline Ce_{1− x} Ln _x O_{2− x/2−δ} (Ln = Yb, Lu, x = 0 − 1) oxides upon heating in H₂ was studied for the first time. Up to 950 °C the samples were single-phase, with structure changing smoothly with x from fluorite type (F) to bixbyite type (C). For the Lu-doped samples heated at 1100 °C in the air and H₂, phase separation into coexisting F- and C-type structures was observed for ~0.40 < x < ~0.70 and ~0.25 < x < ~0.70, respectively. It was found also that addition of Lu³⁺ and Yb³⁺ strongly hinders the crystallite growth of ceria during heat treatment at 800 and 950 °C in both atmospheres. Valency of Ce and Yb in Ce_0.1Lu_0.9O_1.55−δ and Ce_0.95Yb_0.05O_1.975−δ samples heated at 1100 °C was studied by XANES and magnetic measurements. In the former Ce was dominated by Ce⁴⁺, with small contribution of Ce³⁺ after heating in H₂. In the latter, Yb existed exclusively as 3+ in both O₂ and H₂.     

A simple statistical phenomenological model for cation substitutions in Nd1+ x Ba2− x Cu3O7−δ+ x /2

The first results are presented of calculations using a quite simple phenomenological model developed to simulate the cationic substitutions in Nd_{1+ x} Ba_{2? x} Cu₃O_{7+ x /2?δ} (Nd123). Although elementary concepts from statistical mechanics are used in the model, significant results have been obtained, such as the reconstruction of the substitution region limits and their dependence on temperature. Particularly interesting is the prediction of strong temperature dependence for the minimum substitution parameter, x _min.