Novel technique for crystal growth of superconducting ErBa2Cu3O7

Millimeter-sized crystals of ErBa₂Cu₃O₇ were fortuitously grown while sintering a flat disk. It was possible to separate individual crystals from the sintered mass and measure their properties. The resistive transition and onset of magnetic transition of a single crystal was 93 K and the resistive transition width was < 1 K. Flux expulsion was observed and individual crystals could be levitated by a magnetic field. Crystals showed unusual growth features. They were heavily corrugated along the part of the crystal that grew parallel to the top surface of the disk and that coincided with thec axis of the unit cell. Crystals were characterized by X-rays, electron microscopy, and optical microscopy.     

Resistive upper critical field of single crystals of Tl2Ba2CuO6

We have measured the resistive upper critical field of overdoped single crystals of Tl₂Ba₂CuO₆ from the zero-field transition temperatureT _c (approximately 20 K) to temperatures as low as 12 mK, corresponding to less than 0.001T _c. In sharp contrast to the predictions of standard theories of superconductivity, the critical field is found to rise steeply with positive curvature as the temperature is reduced, and no sign of saturation is observed down to the lowest temperatures reached.     

Transport properties of textured Bi2Sr2CaCu2O8+y, thin films

Superconducting films of the high-T _c compound Bi₂Sr₂CaCu₂O_8+y , have been grown on (111)-oriented gadolinium gallium garnet substrates by a liquid-phase technique. The films show a very high degree of preferential orientation with thec-axis perpendicular to the substrates. The onset of the resistive transition was 85 K while zero resistance was obtained at 78 K. Results concerning the critical current properties of the films are described. Measurements of the paraconductivity effects on the electrical resistivity above the superconducting transition due to thermodynamic fluctuations are also reported.Supported by Ansaldo S.p.A Divisione Ansaldo Ricerche, Via Corso Perrone 25, I-16100 Genova, Italy.     

Luminescence properties of Sn2P2Se6 crystals

A large family of Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) semiconductor-ferroelectric crystals were obtained by the Bridgman technique. The photoluminescence properties of the Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) family crystals strongly depend on their chemical composition, excitation energy and temperature. The influence of the Pb → Sn and S → Se isovalent substitutions on the luminescence properties of a crystal with the Sn₂P₂Se₆ basic composition was investigated. A broad emission band observed in the Sn₂P₂Se₆ crystal with a maximum roughly at 600 nm (at T = 8.6 K) was assigned to a band-to-band electron-hole recombination, whereas broad emission bands, peaked near 785 nm (at T = 8.6 K) and 1025 nm (at T = 44 K) were assigned to an electron-hole recombination from defect levels localised within the bandgap. Possible types of recombination defect centres and specific mechanisms of luminescence in the Sn₂P₂Se₆ semiconductor-ferroelectric crystals were considered and discussed on the basis of the obtained results and the referenced data.     

HREM surface profile images of Bi2Sr2CaCu2O8

Surface profile images of Bi₂Sr₂CaCu₂O₈ have been obtained using high-resolution electron microscopy. The cleaved (001) surface of the crystals terminates with a single Bi-O atomic layer. The modulated structure developed in this surface atomic layer was observed directly. The (hk0) surfaces were found to decompose in air into an amorphous coating layer. This coating layer was unlikely recrystallized into the original structure under electron beam irradiation. The amorphous layer on the (hk0) surface formed in pure Ar atmosphere was relatively thin and could be recrystallized into some secondary phases in which a Bi loss was observed. The original (001) surface might also be covered by an amorphous-like layer. This disordered layer could be recrystallized under electron beam irradiation into BiSr₂Ca₂Cu₃O₉, BiSr₂CuO₅, etc. which intergrow with the parent crystal perfectly on the (001) planes.The author thanks the EPSRC for financial support.     

Study on structural phase transitions and relaxation processes of Cs2Co(SO4)2·6H2O and Cs2Zn(SO4)2·6H2O crystals

The structural phase transitions and relaxation processes of Cs₂Co(SO₄)₂·6H₂O and Cs₂Zn(SO₄)₂·6H₂O single crystals were investigated, with the phase transitions of both crystals being determined from NMR data. The spin–lattice relaxation time, T₁, of the ¹³³Cs nucleus in two crystals undergoes a significant change near the phase transition temperature, T_C, and these changes coincide with the changes in the splitting of the ¹³³Cs resonance lines. The variations in the temperature dependence for the splitting of the ¹³³Cs resonance lines and T₁ near T_C are related to changes in the symmetry of surrounding Cs⁺. In addition, the ¹³³Cs T₁ of Cs₂Co(SO₄)₂·6H₂O, which contains paramagnetic ions, was found to be shorter than that of Cs₂Zn(SO₄)₂·6H₂O. This relaxation time is inversely proportional to the square of the magnetic moment of the paramagnetic ions. The differences between the ¹³³Cs T₁ of these compounds are probably due to the differences between the electronic structures of their metal ions.     

Dependency of Flux Jump on Temperature and Field-Sweep Rate for Textured (Nd1/3Eu1/3Gd1/3)Ba2Cu3O7- δ Bulk Superconductor with Gd-211 Particles

Anisotropy flux jumps in the mixed state of a textured (Nd_0.33Eu_0.33Gd_0.33)Ba₂Cu₃O_7-δ bulk superconductor with Gd-211 doping particles have been studied by means of magnetization measurements in the model of the magnetic field paralleling and perpendicular to the c axis. A typical anisotropy flux jump was observed at a temperature ranging from 2.0 to 3.0 K. Under the magnetic field perpendicular to c axis, no flux jump was found at whole temperature range until the sweep rate of 200 Oe/sec. For the magnetic field paralleling to the c axis, the number of flux jumps decreased with the increase of temperature, and the third quadrant of the M–H curve is the most flux-instability quadrant. The magnetic field sweep rate dependences of flux jumps were also studied and the influence of flux creep on flux jumps was also discussed.     

Superconductivity and Ferromagnetism of the Ru-1232 Compounds in the (Ru1?xNbx)Sr2(GdCe1.8Sr0.2)Cu2Oz System

The Ru-1232 compounds have been synthesized in the (Ru_1–xNb _x )Sr₂(GdCe_1.8Sr_0.2)Cu₂O _z system, and effects of Nb substitution for Ru on superconductivity and ferromagnetism of the Ru-1232 compounds have been investigated. First, X-ray powder diffraction study shows that nearly the single 1232 phase samples can be obtained in the x composition range from 0.0 to 0.3. Then, from the electrical resistivity study, it is found that each of the samples shows resistivity dropping phenomenon at two temperatures of T _c ^l and T _c ^h, which originates from superconductivity of the Ru-1232 phase and the Ru-1222 one, respectively. Both of the starting temperatures are lowering with increasing Nb content x. Lastly, from the magnetic susceptibility study, it is found that superconducting transition temperature T _c is 20 K for the Ru-1232 sample with x = 0.0 and the ferromagnetic transition temperature T _m is about 90 K. This study also shows that both of the values of T _c and T _m become low with increasing x from 0.0 to 0.3.     

The Influence of Bi Doping on the In Situ Growth of TlBa2Ca2Cu3O9 High-Tc Films

The in situ process—laser ablation in combination with thermal evaporation of Tl₂O—has turned out to be a preparation method for single-phase and epitaxial TlBa₂Ca₂Cu₃O₉ (1223) thin films with T _c values up to 109 K. It was found by several groups that a partial substitution of Tl by Bi simplifies the phase development of the 1223 compound in the usual two-step process. We have investigated the influence of the Bi doping on the in situ growth. X-ray measurements show that the films consisted mainly of the 1223 compound. In 300-nm thin films there was no evidence of a Bi amount in the crystal structure, but thinner films (80 nm) show a small amount of Bi. We concluded that Bi doping supports the phase development of the 1223 compound only in an early stage of the film growth. The Bi-doped films have higher T _c values up to 114 K, higher j _c values up to 6 × 10⁵ A/cm² (77 K, 0 T), and lower surface resistances of 56 m (77 K, 87 GHz) than the undoped films.     

Effect of Cd Doping on Structure and Superconductivity in Mg0.5Cd0.5B2

The effect of Cd doping on structure and superconductivity in Mg_0.5Cd_0.5B₂ fabricated by a solid-state reaction at ambient pressure has been investigated. The resulting changes in crystal structure, superconducting transition temperature T _c and critical current density J _c are characterized by X-ray diffraction, dc magnetization, electrical resistance, and magnetic measurements. It reveals that Cd does not occupy the atomic Mg sites in the MgB₂ crystal structure, but merely reacts with Mg and forms a MgCd₃ phase. It is striking to note that although the nonsuperconducting phase MgCd₃ is as high as about 67 vol.% in Mg_0.5Cd_0.5B₂, the T _c of the doped sample drops only by about 1 K. Most important, a surprising improvement of J _c of 5.0 × 10⁵ A/cm² (5 K, 0 T) has been achieved in Mg_0.5Cd_0.5B₂. It is suggested that the improvement in J _c in Mg_0.5Cd_0.5B₂ is primarily due to pinning effects induced by MgCd₃. Also, it is thought that MgCd₃ may fill up gaps among grains in MgB₂ and produce better grain linkage, which may be another source of improvement in J _c in Mg_0.5Cd_0.5B₂.     

Physical properties of a new cuprate superconductor Pr2Ba4Cu7O15−δ

We present studies of the thermal, magnetic, and electrical transport properties of reduced polycrystalline Pr₂Ba₄Cu₇O_15−δ (Pr247) showing a superconducting transition at T_c=10–16 K, and compare them with those of as-sintered non-superconducting Pr247. The electrical resistivity in the normal state exhibited T² dependence up to approximately 150 K. A clear specific heat anomaly was observed at T_c for Pr247 reduced in a vacuum for 24 h, proving the bulk nature of the superconducting state. By the reduction treatment, the magnetic ordering temperature T_N of Pr moments decreased from 16 to 11 K, and the entropy associated with the ordering increased, while the effective paramagnetic moments obtained from the DC magnetic susceptibility varied from 2.72 to 3.13μ_B. The sign of Hall coefficient changed from positive to negative with decreasing temperature in the normal state of a superconducting Pr247, while that of the as-sintered one was positive down to 5 K. The electrical resistivity under high magnetic fields was found to exhibit T^α dependence (α=0.08–0.4) at low temperatures. A possibility of superconductivity in the so-called CuO double chains is discussed.     

Microstructural and superconductive studies of Ag-YBa2Cu3O7?x composites

Composites of Ag-YBa₂Cu₃O_7–x were synthesized and carefully characterized for crystal structure and microstructure by X-ray diffraction, optical microscopy, SEM, TEM, and EDAX techniques in order to investigate the effect of Ag additions on the superconducting properties of 123 compounds. The a.c. susceptibility data show thatT _c (onset) of 123+Ag composites vary between 90.2 and 91.8 K. TheJ _c values we measured for 123 material without silver were in the range of earlier reported values for the pure 123 material. Whereas there is a relatively small increase in the critical current for the YBCO/Ag₂O ratio of 3, the variation of the grain size of the composites shows that theseJ _c changes are due to slight variations in the grain size rather than any dramatic effect of Ag inclusions as speculated earlier.     

Effect of chromium substitution on structure and magnetic properties of Bi2Fe4O9

Orthorhombic Bi₂Fe_4 − xCr_xO₉ (x = 0.0, 0.25, and 0.75) nanoplatelets were synthesized by a simple hydrothermal method. The structure, morphology, and magnetic properties of the obtained powders have been characterized. Calculation of the lattice parameters of Bi₂Fe_4 − xCr_xO₉, as well as bond lengths and angles, was carried out by X-ray diffraction Rietveld refinement. The volumes of the metal-oxygen tetrahedra and octahedra were calculated to be sequentially increasing as the Cr doping level increases. The samples undergo an antiferromagnetic transition at 250 ± 5 K. The magnetic moments of the samples increase with higher Cr doping level. The 3d electron spin state for Fe³⁺ in the as-prepared samples is different, which is possibly due to the distortion of Fe-O tetrahedra and octahedra in the crystal structure after chromium substitution.     

Superconductivity at differentTc in CdBa2Ca2Cu3Oy

A Cd analogue of the Tl and Hgn =3 series with nominal composition CdBa₂Ca₂Cu₃O_y has been synthesized. The samples were superconducting according to magnetic susceptibility measurements. The critical temperature was 103 or 107 K depending on the preparation conditions. The EDX analysis revealed the presence of Cd-1111, Cd-1121, and Cd-2333 as minor phases. The observed diamagnetic effects were attributed to the differentT _c of these phases.     

Synthesis and Magnetic Properties of L0.5Sr0.5Mn0.5M0.5O3 (L = Y, Pr; M = Cu, Ru)

A new Mn-containing material with nominal composition L_0.5Sr_0.5Mn_0.5M_0.5O₃ (L = Y or Pr; M = Cu or Ru), as well as Y_0.5Sr_0.5MnO₃ for comparison, were synthesized. The results of the XRD and EDX analyses show that the obtained samples are single-phased and isostructural, with L_1–xA_xMnO₃. The L_0.5Sr_0.5Mn_0.5Cu_0.5O₃ material displays a PM behavior down to 8 K where paramagnetic–antiferromagnetic transition begins. The Pr_0.5Sr_0.5Mn_0.5Cu_0.5O₃ sample has a broad transition at 210 K and a magnetoresistance of 34% at 128 K. The Pr_0.5Sr_0.5Mn_0.5Ru_0.5O₃ material has a paramagnetic–ferromagnetic transition beginning at 330 K and a ferromagnetic–antiferromagnetic one at about 160 K. The obtained value of T _c is the highest for the Pr-containing manganites. The roles of Pr/Sr ratio, anisotropy, and intergranular effects in the samples are discussed.     

Synthesis of the intermetallic clathrate Na2Ba6Si46 by oxidation of Na2BaSi4 with HCl

A new preparation route to the intermetallic clathrate-I compound Na₂Ba₆Si₄₆ is introduced, which allows one to make large amounts of product with standard laboratory equipment. The precursor Na₂BaSi₄ is oxidized with gaseous HCl at 673 K to Na₂Ba₆Si₄₆, NaCl and BaCl₂. Full-profile refinement of the crystal structure from the X-ray powder diffraction data revealed a composition close to Na₂Ba₆Si₄₆ (Na_1.94(1)Ba_6.06(1)Si₄₆, space group , a=10.281(1) Å). Differential scanning calorimetry showed an exothermic effect at 874 K, indicating that Na₂Ba₆Si₄₆ is metastable. The product was additionally characterized by scanning electron microscopy. The electronic structure of Na₂Ba₆Si₄₆ was investigated by a first-principles, all-electron full-potential method, predicting metallic conductivity. Na₂Ba₆Si₄₆ obtained by oxidation with HCl shows Pauli paramagnetism; no bulk superconductivity was found down to 1.8 K in a magnetic field of 20 Oe.     

Bi2Te3纳米结构的制备、磁性掺杂和结构表征

通过液相法制备Bi2Te3纳米管,设计并优化了Co离子的掺磁方案。通过扫描电镜、透射电镜、X射线衍射、红外光谱和能量色散X射线光谱对制备的样品进行了结构表征。实验结果表明,液相法可制备出晶相良好的Bi2Te3纳米管、Co离子均匀掺杂的Bi2Te3纳米结构样品。     

Growth and characterization of Bi2Sr2Ca1Cu2O8+x single crystals

High-quality single crystals are well suited to the investigation of some intrinsic material properties. A modified Bridgman method using a sharp temperature gradient (300°C/cm) was used to grow Bi₂Sr₂Ca₁Cu₂O_8+x single crystals. Although the samples were contained in alumina ampoules, no aluminium contamination of the samples was detected. Blade-shaped crystals up to 7–8 mm length and 3–4 mm width could be grown by this method, although extraction from the matrix was difficult. Electron diffraction patterns of the [001] zone axis revealed a high degree of crystallinity. The narrowness of the superconducting transition temperature, as determined by ac susceptibility, also suggests the existence of well-formed crystalline domains. In order to determine the relative orientation of the crystalline domains, electron channeling patterns were recorded from several consecutive growth steps from a fracture surface. The poor contrast of these and Kikuchi patterns suggests the presence of a stacking structure. The results showed a [100] growth direction and (001) cleavage plane. Reversible oxygen loss at the peritectic decomposition temperature of 863°C was observed. Knoop indentation measurements showed that the crystals were quite soft, having a microhardness of 0.44 GPa.     

Salt-assistant combustion synthesis of nanocrystalline Nd2(Zr1 − xSnx)2O7 (0 ≤ x ≤ 1) solid solutions

Nanocrystalline Nd₂(Zr_{1 − x}Sn_x)₂O₇ series solid solutions were prepared by a convenient salt-assisted combustion process using glycine as fuel. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, transmission electron microscopy and high-resolution transmission electron microscopy. The results showed the Zr ion can be partially replaced by Sn ion. The partial substituted products were still single-phase solid solutions and the crystal form remained unchanged. TEM images reveal that the products are composed of well-dispersed square-shaped nanocrystals. The method provides a convenient and low-cost route for the synthesis of nanostructures of oxide materials.     

The Underdoped Region of the Phase Diagram of YBa2Cu3O6+x

Here we present a reviewed phase diagram of the high-T _c superconducting YBa₂Cu₃O_{6+ x} compound, finely mapped in the strongly underdoped region (0 < x < 0.5), from the pure antiferromagnetic state to the superconducting regime. The Neèl and spin freezing temperatures have been measured by μSR experiments while the hole density per Cu atom in the CuO₂ planes has been determined from the resistive T _c and from Seebeck coefficients at 290 K. The phase diagram is discussed in comparison to those of La_{2− x} Sr _x CuO₄ and Y_{1− x} Ca _x Ba₂Cu₃O₆ cuprate systems.