Effect of copper doping on charge ordering in La1/3Ca2/3Mn1 ? y Cu y O3 (0 ≤ y ≤ 0.07)

The effect of copper doping on charge-orbital ordering in La_1/3Ca_2/3Mn_{1 − y} Cu _y O₃ (0 ≤ y ≤ 0.07) is studied by measuring the temperature dependences of the magnetization, the electrical resistivity, and the heat capacity in combination with an electron microscopic investigation of the structure. It is demonstrated that copper doping leads to a lowering of the charge ordering temperature T _CO and that this decrease is proportional to the decrease in the Mn³⁺ ion concentration. In the temperature range 5–300 K, the semiconducting pattern of the electrical resistivity persists for all values of 0 ≤ y ≤ 0.07. Electron microscope studies have shown that the presence of copper suppresses the formation of a regular superstructure, which is characteristic of the undoped starting compound, beginning already from low concentrations (y = 0.01). Differential scanning calorimetry revealed a substantial decrease in the transition entropy at the onset of charge ordering in copper-doped samples as compared to the starting compound. Doping with copper destroys long-range charge-orbital ordering and retains apparently only short-range order. Original Russian Text ? T.S. Orlova, J.Y. Laval, Ph. Monod, V.S. Zakhvalinskiĭ, V.M. Egorov, Yu.P. Stepanov, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 1, pp. 91–97.     

Transport properties of a and c axis oriented (Y1?xCax)Ba2Cu3Oy thin films

Anisotropy and Hall effect measurements have been performed in calcium-doped, i.e., overdoped YBa₂Cu₃O_y ((Y_1−xCa_x)Ba₂Cu₃O_y) thin films witha andc axis orientations. In highly overdoped films (x=0.4), the anisotropy of the normal resistivity decreases and a drastic change in Hall conductivity in the mixed state is observed. The change in Hall conductivity in the overdoped region is consistent with recent experimental results for La_2−xSr_xCuO₄ films and seems to be common in highT _c superconductors.     

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)     

Mechanism responsible for the modification of the band spectrum and superconducting properties in the Tl2Ba2Ca1 ? x Y x Cu2 ? y Co y O z system

The modification of the temperature dependences of the thermopower coefficient for the Tl₂Ba₂Ca_{1 − x} Y _x Cu_{2 − y} Co _y O _z system is investigated as a function of the dopant content. The model of an asymmetric narrow band is shown to be applicable to high-temperature superconductors in the thallium system. The parameters of the band spectrum and charge carrier system for samples of a close-to-optimum composition are determined by analyzing the temperature dependences of the thermopower coefficient within the narrow band model. The character and mechanism of their variation in the course of the transition to an underdoped regime are analyzed together with the dynamics of changes in the superconducting properties. The critical temperature T _c is found to correlate with the effective conduction-band width W _D . It was shown that the dependence T _c (W _D ) for Tl₂Ba₂Ca_{1 − x} Y _x Cu_{2 − y} Co _y O _z has a close-to-universal character, but the suppression of T _c upon the broadening of the band occurs faster than in the case of the yttrium system. Original Russian Text ? O.A. Martynova, V.é. Gasumyants, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 9, pp. 1537–1542.     

Analysis of the possible reasons for the suppression of superconductivity in the Y1−x PrxBa2Cu3Oy system on the basis of thermoelectric power data

The temperature dependence of the thermoelectric power in samples of Y_1−x Pr_xBa₂Cu₃O_y (x=0−0.6) is investigated. The principal parameters of the system of charge carriers are determined on the basis of an analysis of this dependence within a narrow-conduction-band model, and their variation with increasing praseodymium content is analyzed. It is found that an increase in x leads to a very weak increase in the electron filling and considerable broadening of the conduction band accompanied by strong localization of the charge carriers. It is concluded on the basis of a comparative analysis of the results obtained and data for the YBa₂Cu₃O_y system in the case of aliovalent substitutions in the barium and copper sites that the valence of praseodymium in Y_1−x Pr_xBa₂Cu₃O_y is very close to 3+. It is shown that there is a universal correlation between the effective width of the conduction band and the critical temperature following various cation substitutions in the Y-Ba-Cu-O system. It is concluded that the main reason for suppression of the superconducting properties of Y_1−x Pr_xBa₂Cu₃O_y is the strong modification of the band spectrum caused by praseodymium. Fiz. Tverd. Tela (St. Petersburg) 39, 1520–1525 (September 1997)     

Crystal structure and magnetic ordering of manganites La0.7Ca0.3Mn1 ? y Fe y O3

The influence of the replacement of Mn ions in the La_0.7Ca_0.3Mn_{1 − y} Fe _y O₃ compounds (0 ≤ y ≤ 0.09) by another transitional metal, Fe, was studied. The radii of both ions are almost identical, which makes the effect of the transitional metal on the physical properties of manganites more transparent. The crystal structure of three samples (with y = 0, 0.03, 0.09) is studied in the temperature range T = 1.5–300 K by neutron powder diffraction. All investigated samples belong to the orthorhombic space group Pnma (62). It is confirmed that Fe ions occupy the Mn positions in the unit cell. As the Fe concentration increases, the saturation value of the spontaneous magnetic moment and the Curie temperature decrease, but the ground state remains ferromagnetic for 0 ≤ y ≤ 0.1. The saturation values of the magnetic moments at T = 1.5 K are m _FM = 3.72(3), 3.40(3), and 3.27(3) μ _B /Mn for the samples with an Fe concentration y = 0, 0.03, and 0.09, respectively. Original Russian Text ? A.I. Kurbakov, V.S. Zakhvalinskii, R. Laiho, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 4, pp. 691–695.     

Magnetism and candidate muon-probe sites in RBa2Cu3O y

Key results of zero-field (ZF) and transverse-field (TF) muon-spin-relaxation (μSR) experiments on superconducting and insulating RBa₂Cu₃O _y (R123 _y , with R=Eu, Gd, Pr and Pr/Y:y=6, 7) are examined. The chemical behavior of the positive muon probe is addressed, and muon-oxygen bonding is shown to occur in all these cuprates. To explain magnetic fields at muon-probe sites in Pr _x Y_1−x Ba₂Cu₃O _y (0<=x<0.5,y=7 andx=0,y=6) samples, improvements on the reported magnetic structures from neutron diffraction are necessary. Cu magnetism in Pr123y (y=6,7) is observed belowT _N1, which is near RT. The magnetism seen belowT _N2 can be interpreted assuming an additional ordering in the Cutt-O chain layers. Alternatively, Pr ordering is also considered as the cause of the second phase transition. Considering the specific muon-probe location, a more detailed interpretation can be provided for the μSR parameters, measured in the normal and mixed states of these unconventional superconductors.     

Band spectrum modification and dynamics of superconducting properties in the Y1?xCaxBa2Cu3?xZnxOy system

Temperature dependences of the electrical resistivity and Seebeck coefficient have been studied on a series of samples of the Y_1−x Ca_xBa₂Cu_3−x Zn_xO_y system (x = 0–0.25). The effect exerted by a combination of the impurities under study on the properties of the normal phase was established. The experimental data obtained were analyzed quantitatively in terms of a phenomenological model of electron transport. The parameters of the band responsible for conduction in the normal phase and of the carrier system were calculated for all the samples studied. A mechanism of zinc doping-induced band structure modification in the yttrium system is proposed that accounts for the transformation of the temperature dependence of the Seebeck coefficient and the dynamics of superconducting properties in this compound. __________ Translated from Fizika Tverdogo Tela, Vol. 47, No. 3, 2005, pp. 422–426. Original Russian Text Copyright ? 2005 by Elizarova, Martynova, Potapov, Gasumyants, Mezentseva.     

Structure and magnetic properties of Ca1−x−yMgxCu2+yO3 influenced by isoelectronic substitution x

Phases of the composition Ca_1−x−yMg_xCu_2+yO₃ have been prepared for the first time. The compounds are isostructural with the known end-members CaCu₂O₃ and MgCu₂O₃ showing a two-leg spin-ladder-like connection of copper and oxygen atoms within the Cu₂O₃-layer. Opposite the spin ladders this layer is folded, which results in a long-range antiferromagnetic ordering of these phases. The Néel temperature can be adapted by variation of x in Ca_1−x−yMg_xCu_2+yO₃ between 24 and 80 K. Several structural features, which influence the magnetic ordering, are discussed.     

Photoluminescence properties of Eu3+-doped Gd2MoB2O9 phosphors for LED-based solid-state-lighting

Investigation was performed on luminescent properties of novel Gd_2−x Eu _x MoB₂O₉ (0.02≤x≤2.0) phosphors. The excitation spectra consist of broad band and intense narrow lines. The 4f-4f transitions are situated in a favorable position for excitation by GaN chip emission. The emission spectra consist of transitions from the ⁵D₀ level to the lower ⁷F manifold, and the emission shows no concentration quenching at higher doping level. The decay time spectra of the ⁵D₀ → ⁷F₂ emission are recorded. Under 395 nm excitation, the intensity of ⁵D₀ → ⁷F₂ transition of GdEuMoB₂O₉ is 1.2 times stronger than that of commercial Eu³⁺:Y₂O₂S phosphor. Gd₂MoB₂O₉:Eu³⁺ phosphors are promising candidates for near-UV-based solid-state-lighting (SSL).     

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)     

Effect of isovalent doping of manganite (La1?xPrx)0.7Ca0.3MnO3 films (0≤x≤1) on their optical, magnetooptical, and transport properties near the metal-insulator transition

The optical, magnetooptical, and electric properties of epitaxial (La_1−x Pr_x)_0.7Ca_0.3MnO₃ films (0≤x≤1) grown by MOCVD on LaAlO₃ and SrTiO₃ substrates were studied. It is shown that the decrease in the average cation radius resulting from isovalent substitution of the Pr for La ions brings about a lowering of the Curie temperature, the metal-insulator transition temperature, and the temperatures of the maxima in magnetotransmission (MT) and magnetoresistance (MR). These temperatures depend only weakly on the substrate type. Substitution of La by Pr does not change the shape of the spectral response of the transverse Kerr effect. For concentrations x≤0.50, the maximum values of the Kerr effect and of the MT vary insignificantly, which should be assigned to the existence of a singly connected ferromagnetic metallic region at low temperatures. In films with x=0.75, the presence of ferromagnetic metallic drops in an antiferromagnetic insulating matrix was revealed. The totality of the experimental data obtained suggest that nanoscopic magnetic and electronic nonuniformities exist both in films with a singly connected metallic region and in an x=1 film, which is an antiferromagnetic insulator. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 7, 2004, pp. 1203–1213. Original Russian Text Copyright ? 2004 by Sukhorukov, Loshkareva, Gan’shina, Kaul’, Gorbenko, Mostovshchikova, Telegin, Vinogradov, Rodin.     

The behavior of thermopower in the YBa2−x LaxCu3Oy system. Correlation between the band parameters in normal state and critical temperature

The thermopower in the YBa_2−x La_xCu₃O_y system (x=0–0.5) has been studied. An analysis made in terms of the narrow-band model revealed trends in the variation of the main band parameters with increasing lanthanum concentration. The dependence of the conduction band width on lanthanum concentration was found to pass through a weak minimum at x=0.05–0.1, which correlates in position with the maximum in the concentration dependences of the critical temperature and degree of sample orthorhombicity. The results obtained and their comparison with Fe, Co→Cu substitution data permit a conclusion that the main factor affecting the properties of the YBa₂Cu₃O_y system under nonisovalent substitution of various cations is the increasing disorder in the chain-oxygen subsystem caused by increasing impurity content. Fiz. Tverd. Tela (St. Petersburg) 40, 17–22 (January 1998)     

Effect of the percentage of yttrium oxide on the phase composition of annealed samples of YzBa5Cu7Oy and YzBa3Cu5Oy composition

The phase composition of Y _z Ba₅Cu₇O _y (1) and Y _z Ba₃Cu₅O _y (2) samples with a variable percentage of yttrium up to the stoichiometric composition of the Y _n Ba _m Cu _{m + n} O _y series is investigated by X-ray phase and elemental analyses, electron diffraction, and high resolution imaging in a transmission electron microscope at a temperature of 930°C in the crystallization field of a matrix oxide (Ba: Cu) of 5: 6 composition on the phase diagram of the BaO-CuO _x system at P(O₂) = 21 kPa. The substantial effect of yttrium oxide’s presence on the phase composition of both objects is found, providing evidence of a complex ionic equilibrium within the melt. The fine-domain oxide structure of the YBa₂Cu₃O₆ tetragonal form, which is due to the coexistence of oxides of an Y _n Ba _m Cu _m+n O _y homologous series of (Y: Ba: Cu) 235, 123, and 257 composition is revealed. The domain size for these phases is 20–50 ?. The domains are joined coherently along axis c.     

Y1-xPrxBa2Cu3O7+δ的红外反射谱

测量了温度范围为4.2—300K的Y_1-xPr_xBa₂Cu₃O_7+δ(x=0,0.1,0.2,0.4,0.5,0.61.0)的红外反射谱,发现在低温下Ba模有双模行为,随着x值增大双模强度反转,在YBa₂Cu₃O_7+δ中已被判定为Y模的位于194cm^-1的反射峰的位置与Pr的含量无关,即用Pr部份或全部替代Y时此峰不发生频移。建议Pr在Y_1-xPr_xBa₂Cu₃O_7+δ,中是正4价,Pr的替代使原来可移动的空穴被定域在Pr的周围,使超导电性受到压制。 关键词：     

PrBa2Cu3O6+x(x=1,0.3)中Pr价态随氧含量的变化

报道了陶瓷和c轴取向薄膜 PrBa₂Cu₃O_6+x(x=1,0.3)材料的红外反射光谱，通过比较区分出该材料的沿着c轴振动和沿着a-b平面振动的声子模，PrBa₂Cu₃O_6+x和RBa₂Cu₃O_6+x(x=1-0,R=Y和稀土元素)有类似的晶体结构，分析和比较它们的声子谱，其中尤其是Pr和Y,Pr和其它稀土元素 关键词：     

Evolution of the ferroelectric phase in ?001?-oriented (100 ? x )PbMg1/3Nb2/3O3- x PbTiO3 single crystals

The effect of a dc electric field on the nucleation and evolution of the phase with long-range order in a cubic nonpolar matrix in 〈001〉-oriented (100 − x)PbMg_1/3Nb_2/3O₃-xPbTiO₃ single-crystal relaxors as the content of PbTiO₃ is gradually increased (6 ≤ x ≤ 20, where x is the PbTiO₃ content given in molecular percent) is investigated. The optical properties of these solid solutions are studied in different modes of application of an electric field. It is shown that an applied electric field with a strength above a threshold value induces a first-order ferroelectric phase transition with a temperature hysteresis occurring between measurements performed under cooling and heating of the crystal in the electric field. As the PbTiO₃ content or electric field strength increases, the hysteresis becomes less pronounced and the first-order phase transition is suppressed. At x ∼ 20, the induced transition resembles a second-order rather than first-order transformation. It is assumed that, for compositions with x > 10 in electric fields higher than 4 kV/cm, the formation of the rhombohedral phase is accompanied by the appearance of another (possibly, monoclinic) phase associated with the rotation of the polarization vector from the [111] direction of the rhombohedral phase to the [001] direction of the tetragonal phase. Original Russian Text ? L.S. Kamzina, E.V. Snetkova, I.P. Raevskiĭ, A.S. Emel’yanov, Jiayue Xu, Weidong Xiang, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 4, pp. 725–730.     

Superconductivity and magnetism of La2Cu1−xZnxO4+δ chemically oxidized by NaClO

The structural, superconducting and magnetic properties of La₂Cu_1−xZn_xO_4+δ (0≤x≤0.1) chemically oxidized by NaClO at room temperature were studied. All the samples before and after oxidation are single phase with orthorhombic structure, as indicated by their powder X-ray diffraction analysis. The iodometric titration results indicate that Zn-substituted La₂Cu_1−xZn_xO₄ is more favorable for the insertion of the excess oxygen, as compared to the Zn-free La₂CuO₄. The T_c suppression rate resulting from Zn substitution in La₂Cu_1−xZn_xO_4+δ is −12.4 K/%. The effective magnetic moment induced by the non-magnetic Zn ion is the order of one Bohr magneton, which decreases with increasing the Zn concentrations in the range examined. The latter two results are qualitatively well consistent with those obtained in La_2−xSr_xCu_1−yZn_yO₄ with the Sr optimal doping. This reveals that the non-magnetic Zn ions play the same role in both of the La₂Cu_1−xZn_xO_4+δ with the excess oxygen content of about 0.1 and the La_2−xSr_xCu_1−yZn_yO₄ with the Sr optimal doping.     

Primary crystallization field of YnBamCum + nOy oxides with YBa2Cu3O6 tetragonal structure

The phase composition of specimens in the primary crystallization field of the Y _n Ba _m Cu _{m + n} O _y oxide series with compositions of (Y:Ba:Cu) 235, 123, and 257 was investigated by means of X-ray powder diffraction, X-ray microprobe analysis, electron diffraction, and high resolution imaging in a transmission electron microscope. Y _n Ba _m Cu _{m + n} O _y oxides have the YaBa₂Cu₃O₆ tetragonal structure and can be represented in the general form as 123 oxides. It was found that the crystallization field of 123 oxides corresponds to the crystallization fields of the Ba _m Cu _{m + n} O _y oxide series with the BaCuO₂ cubic structure. These crystallization fields are located in the matrix phase diagram of the BaO-CuO _x system at P(O₂) = 21 kPa in the range of 50–90 mol % CuO and 910–1000°C. The 123 oxides are formed according to an intercalation mechanism with the participation of barium-copper oxide matrices with the composition (Ba: Cu) 3: 5, 2: 3, and 5: 7     

Subsolidus phase relation and crystal structure in the Pr<Subscript>1+x-y</Subscript>Ba<Subscript>2-x-z</Subscript>Ca<Subscript>y+z</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7±δ</Subscript> system

The Pr_1+xBa_2-xCu₃O_7± solid solution was investigated by means of X-ray powder diffraction combined with Rietveld analysis. A Pr123 single phase could be synthesized under Pr-rich conditions by sintering at 950 °C in air. The solubility range of Pr_1+xBa_2-xCu₃O_7± solid solution is 0.08x0.80. The structure of Pr_1+xBa_2-xCu₃O_7± for 0.08x<0.30 is orthorhombic. The structure transforms into tetragonal for 0.30x0.80. To form the Pr123 single phase, the Ba sites in the Pr123 structure must have partial Pr ions, and the least amount is x=0.08. Ba ions cannot occupy the sites of Pr ions. In the Pr123 structure, Ca ions can replace Pr ions; the highest value is x=0.4 in the PrBa_2-xCa_xCu₃O_7± system under our experimental conditions. However, Ca ions cannot replace Ba ions. The ionic radius plays a more important role than the chemical properties in the substitution between Pr, Ba and Ca ions in the Pr123 structure. PACS 61.50.Ah; 64.70.Kb; 61.72.Ff