A new (Hg,V)-based 1212-type cuprate (Hg,V) Sr2(Y,Ca) Cu2Oz with Tc(onset) up to 110 K

We have successfully synthesized a new (Hg, V)-based 1212-type cuprate (Hg_1?x V _x )Sr₂(Y_1?y Ca _y )Cu₂O _z . The electrical resistance measurements showed that some of the as-synthesized materials with proper Hg/V and Y/Ca ratios exhibit weak superconductivity. Oxygen-annealing significantly improved their superconducting behavior, andT _c(onset) up to 110 K was observed. The lattice parameters of (Hg,V)-1212 were found to be in the order ofa=3.8415(1) Å andc=11.8514(6) Å. Substitu ting mercury atoms by vanadium ones results in an important increase of thea parameter and an important decrease of thec parameter compared to the known Hg-based Sr-bearing compounds. The crystal structure of (Hg, V)-1212 was refined by Rietveld refinement against X-ray powder data using the tetragonal symmetry of space groupP4/mmm. The V and Cu valence states and superconductivity in this new (Hg, V)-1212 cuprate are briefly discussed.     

Preparation,stoichiometry and magnetic properties of Cu y Cr2Se4−z Br x spinels with 0.5≲x≲2

The chemical composition of Cu _y Cr₂Se_4?z Br _x spinels depends strongly on the preparation parameters. Spinels with 0.8?y?1.2, 0.5?x?2, and 0?z?x?0.2 have been prepared. Whereas the lattice constanta _o of these spinels differs only by less than approximately 0.6%, their Curie temperatureT _c depends sensitively on the spinel composition. For Cu_1.1Cr₂Se_3.4Br_o.46,a _o=1.0410 nm andT _c=310 K were found to compared witha ₀=1.0447 nm andT _c=84 K of CuCr₂Se₂Br₂.     

Anomalous Zn- and Ni-substitution effects on superconductivity in the superconducting weak ferromagnets RuSr2RCu2O8 (R = Gd,Eu)

The effect of magnetic Ni and non-magnetic Zn impurities on superconducting transition temperature T_c in RuSr₂R(Cu_1?x(Ni, Zn)_x)₂O₈ with R = Gd or Eu (Ni- and Zn-substituted Ru1212Gd(Eu)) was extensively studied. It is found that the suppression rate dT_c/dx of RuSr₂R(Cu_1?x(Ni, Zn)_x)₂O₈ is comparable to that of underdoped YBa₂(Cu_1?x(Ni, Zn)_x)₃O_7?δ. The suppression of superconductivity in Ni-substituted Ru1212Eu samples is more significant than that in Zn-substituted ones, indicative of Ni being a more effective pair-breaker than Zn. In strong contrast, the magnetic Ni impurity atoms have a weaker effect on superconductivity than non-magnetic Zn atoms in Ru1212Gd, similar to what was observed in the high-T_c cuprates. These intriguing findings strongly suggest that the impurity-induced local disturbance of the 3d-spin correlation at Cu sites around Ni/Zn is distinctly different between Ru1212Gd and Ru1212Eu.     

Synthesis and superconductivity of a new 1222-type T1-based layered cuprate (T1, Nb) Sr2(Nd,Ce)2Cu2O z

Synthesis and superconductivity of a new 1222-type layered cuprate (Tl_1–x Nb _x ) Sr₂(Nd_1–y Ce _y )₂Cu₂O _z have been studied. The structure of this cuprate is directly related to that of Nb-1222 NbSr₂(Nd, Ce)₂Cu₂O _z with tetragonal body-center lattice. Partial substitution of Tl for Nb in Nb-1222 phase improves its superconductivity. (Tl_1–x Nb _x ) Sr₂(Nd_0.75Ce_0.25)₂Cu₂O _z samples prepared by the typical procedure exhibit superconductivity withT _c of 30–40 K. Effects of Tl and Nb on superconductivity of this cuprate are briefly discussed.     

The magnetic moments and halflives of the 5/2− states in199Hg and197Hg and the discrepancies in the experimental hyperfine fields at Hg in Fe

The Larmor-precession frequencies for¹⁹⁷Hg in Fe have been determined to beω _L = 1291 ±25 MHz at 293 K andω _L = 1334±25 MHz at 105 K. For¹⁹⁹Hg in Feω _L =1372±50 MHz has been measured at 293 K. The half-lives of the 5/2^? states in¹⁹⁷Hg and¹⁹⁹Hg have been remeasured asT _1/2(¹⁹⁷Hg)=8.1±0.16 nsec andT _1/2(¹⁹⁹Hg)=2.45±0.05 ns, respectively. The magnetic moment of the 5/2^? 158keV state in¹⁹⁹Hg was redetermined by the integral perturbed angular correlation method in an external magnetic field of 47kG asμ(5/2 ^? ) = 0.905±0.091 nm. With this new value consistency for the magnetic hyperfine fields at Hg in Fe measured with the TDPAC-method and with the NMR/ON-method is obtained. This fact is used to determine theg-factors of the 5/2^? states in¹⁹⁷Hg and¹⁹⁹Hg more precisely fromω _L -values given above:g(¹⁹⁷Hg)=0.342(6);g(¹⁹⁹Hg)=0.352(13). The magnetic moments of the first excited 2⁺ states in^198–204Hg isotopes which rely on calibrations with the¹⁹⁹Hg-g-factor, are revised.     

Superconductivity in the Nb3 (Al,Ge) compound system

Superconducting samples of the nominal composition Nb _x (Al_1?y , Ge _y )_1?x withx reaching from 0.72 to 0.78 andy from 0.175 to 0.30 were prepared and the superconducting transitions of as-cast and of annealed samples were measured. The onset of superconductivity for samples with a suitable composition and annealing procedure has been observed to be at about 21.05 K. By the help of anodic oxydation process and by multichannel semiconductor x-ray spectroscopy with scanning electron microscope it has been possible to carry out the phases distribution and detailed phase-analysis in the samples.     

151Eu Mössbauer effect study of T′- and T*-phase superconductors

The (La,Eu(₂ CuO ₄ system shows superconductivity by dopingCe orSr. Carriers inT′-phase doped withCe are electrons and those inT ^*-phase doped withSr are holes. In this work,¹⁵¹ Eu Mössbauer analysis is applied for theT′-phase(La _1?x Eu _x)_2?y Ce _y CuO ₄ and theT ^*-phase(La _1?x Eu _x)_2?y Sr _y CuO ₄ in order to compare the electronic state and the lattice vibration ofEu in these superconductors. In addition, correlations betweenT _c and Mössbauer parameters are examined. The isomer shift of¹⁵¹ Eu is 0.784–0.840 mm/s in theT ^*-phase and 0.689–0.733 mm/s in theT′-phase, which shows that the lanthanide in these superconductors is tri-valent. The Debye temperature of¹⁵¹ Eu is 180–208 K in theT ^*-phase and 160–192 K in theT′-phase. The difference of isomer shift between these two phases is explained by theEu?O distance. For(La _1?x Eu _x)_2?y Ce _y CuO ₄, a light correlation betweenT _c and the Debye temperature is observed, which means the importance of the lattice vibration in high-Tc superconductivity.     

A new 1223-type high Tc cuprate (Tl,V) Sr2Ca2Cu3O9

A new 1223-type (Tl, V)-based superconducting layered cuprate (Tl_1–x V _x ) Sr₂Ca₂Cu₃O₉ withx=0.25 and 0.50 has been successfully synthesized in the nearly-pure form and identified by powder X-ray diffration analyses. An excessive quantity of Tl is necessary for the preparation of the (Tl, V)-based 1223-type compound. Resistance and ac susceptibility measurements showed that the new (Tl, V)-based 1223 cuprate exhibits T_c above 110 K.     

Coexistence of superconductivity and magnetic order in YBa2Cu4O8

⁵⁷Fe Mössbauer spectroscopy, magnetic susceptibility and powder x-ray-diffraction measurements were used to study superconductivity and magnetic order in YBa₂(Cu_1?xFe_x)₄O_8+δ. T_c is decreasing with x, disappearing for x>x_c≈0.04. For xc iron substitutes Cu, predominantly in the Cu(1) site exhibiting a single quadrupole Mössbauer spectrum at 90 K. For x>x_c magnetic order is observed in the Cu(2) site, T_N=380 (5) K for x=0.1 and H_eff (Cu(2), 4.2 K)=510(2) kOe. However, the most surprising discovery is that for x=0.025, for which T_c=27(2) K, the Fe in the Cu(1) site orders magnetically at T_N=30(2) K and H_eff (Cu(1), 4.2 K)=461(2) kOe. The coexistence and competition between superconductivity and magnetic order in the Cu(1) and Cu(2) sites in YBa₂Cu₄O₈ are discussed in terms of the previously observed phase diagrams for Y_1?xPr_xBa₂(Cu_1?yFe_y)₃O_z.     

Synthesis, structural and physical properties of new Terbium containing Tb-Hg-Sr-Ca-Cu-O superconducting system

Samples with various nominal compositions in the Tb-Hg-Sr-Ca-Cu-O system were prepared and studied by EDX, powder X-ray diffraction including the Rietveld refinement, electrical resistivity, magnetic susceptibility and thermoelectric power measurements. EDX and powder X-ray diffraction studies showed that Tb is required for the stabilization of the 1212, (Hg_1−yTb_y)Sr₂TbCu₂O_6+δ; y≈0.5 phase. Electrical resistivity and magnetic susceptibility measurements indicated that substitution of Tb by Ca is necessary to induce superconductivity in the 1212, (Hg_0.5Tb_0.5)Sr₂(Tb_1−xCa_x)Cu₂O_6+δ samples. The Rietveld refinements of the X-ray data of two samples with x=0.0 and 0.5 were carried out on the basis of tetragonal symmetry (space group P4/mmm) and the results indicated that the phase with x=0.5 has less puckered Cu-O planes than the Ca-free (Hg_0.5Tb_0.5)Sr₂TbCu₂O_6+δ phase. Syperconductivity is observed only for samples with x>0.2 and T_c increases with increasing Ca content, x. The results of thermoelectric power measurements suggest that the samples with x<0.8 are located in the underdoped region and the x=0.8 sample is optimally doped and exhibits the highest T_c of 88 K.     

Nucleic acid conformation: Crystal and molecular structure of deoxyguanosine (5′) phosphate (disodium salt)—Agauche-trans (gt) conformation about the C(4′)-C(5′) bond and O(1′) puckering of the furanose ring

The crystal structure of deoxyguanosine (5′) phosphate, disodium salt, (5′-dGMP Na₂ 4H₂O) has been determined from three dimensional single crystal x-ray data collected by multiple film, equi-inclination, Weissenberg method using CuK_a radiation. The crystal belongs to the monoclinic space groupP2₁ witha=16.002±0.003 Å,b=10.730±0.003 Å,c=5.575±0.005 Å andβ=101.9°. The structure was solved by symbolic addition method using the program Multan, the reliability index being 0.090. The guanine base is in the usualanti conformation about the C (1′)-N (9) bond withx _CN=52.3°. The structure shows two unique conformational features not observed in any nucleotide structure reported so far. The deoxyribose moiety shows O (1′)endo puckering with respect to the best four atom plane defined by C(1′)-C(2′)-C(3′)-C(4′). The conformation about the C(4′)-C(5′) bond isgauche-trans with ø₀₀=62.5° and ø_oc=174.8°. This is the first nucleotide structure where agt conformer similar to that found in the Watson-Crick double helical DNA model has been experimentally observed. These two conformational features have also direct relevance to the concept of ‘a conformationally rigid nucleotide unit’ developed by Sundaralingam. The nine membered guanine ring is essentially planar. Bases of molecules related by a ‘c’ cell translation tend to overlap, the shortest distance being 3.51 Å between the atoms N (3) and C(8). One of the sodium atoms Na(1) has an octahedral coordination with four water oxygens and O(6) and O(3′) atoms occupying the corners at distances ranging from 2.35 Å to 2.55 Å.     

Anion height as a controlling parameter for the superconductivity in iron pnictides and cuprates

Both families of high T_c superconductors, iron pnictides and cuprates, exhibit material dependence of superconductivity. Here, we study its origin within the spin fluctuation pairing theory based on multiorbital models that take into account realistic band structures. For pnictides, we show that the presence and absence of Fermi surface pockets is sensitive to the pnictogen height measured from the iron plane due to the multiorbital nature of the system, which is reflected to the nodeless/nodal form of the superconducting gap and T_c. Surprisingly, even for the cuprates, which is conventionally modeled by a single orbital model, the multiorbital band structure is shown to play a crucial role in the material dependence of superconductivity. In fact, by adopting a two orbital model that considers the d_z² orbital on top of the d_x²−y² orbital, we can resolve a long standing puzzle of why the single layered Hg cuprate have much higher T_c than the La cuprate. Interestingly, here again the apical oxygen height measured from the CuO₂ plane plays an important role in determining the relative energy difference between d_x²−y² and d_z² orbitals, thereby strongly affecting the superconductivity.     

Magnetization study of mercurocuprate (Hg,Re)Sr2CuO4+δ

The nominal (Hg_1−x Re _x )Sr₂CuO_4+δ (x=0.10 and 0.20) samples were synthesized at ∼ 920°C in partial vacuum. The compound with x=0.10 exhibits superconductivity at ∼ 54 K while the composition x=0.20 is non-superconducting down to 5 K. On cooling below 10 K in an applied field of 4 kOe, the former causes a noticeable upturn in the field cooled (FC) magnetization signal. Such a change in magnetic response is also reflected in the magnetic hysteresis loop generated at 9 K. We attribute this effect to a paramagnetic contribution arising from Re in (Hg,Re)-1201 phase.     

Investigation of203, 205Hg with the (d,pγ) reaction — Identification of thei 13/2 neutron hole state in205Hg

Low lying levels in²⁰³Hg and²⁰⁵Hg were studied with the (d, p) deuteron break-up reaction atE _d=14 and 18 MeV. Gamma-rays and conversion-electrons were measured in coincidence with protons. In addition delayed spectra were recorded with us and ms beam pulsing. Thei _13/2 neutron hole state was identified in²⁰⁵Hg and confirmed in²⁰³Hg. The known level structure of²⁰⁵Hg below 2 MeV is confirmed and extended. For²⁰³Hg we observe theγ-decay of several levels below 1.5 MeV, which were previously known from transfer reactions.     

Unusual Pr antiferromagnetic ordering in high-Tc cuprates

The anomalous Pr antiferromagnetic order with high Néel temperature T_N(Pr) are reported throughout the whole Pr_1+xBa_2−xCu₃O_7−y or 1212-type Cu(Ba_2−xPr_x)PrCu₂O_7−y system (−0.2<x<1; −0.4<y<1), where three distinct crystal structures were observed: orthorhombic 1212-chain O(I) (space group Pmmm), tetragonal T (P4/mmm), and orthorhombic O(II) (Cmmm). Systematic variation of T_N(Pr) in this system as well as in other 1212 and 2212 cuprates M_nA₂PrCu₂O₇ (n=1, 2, M=Hg, Tl, Pb/Cu, Bi, Nb, Cu; A=Sr, Ba, Ba/Pr) was discussed through the correlation of T_N(Pr) with Pr–O bond length. The importance of quasi-two-dimensional Pr–O–Pr superexchange magnetic coupling through strong wave function overlap between the overextended Pr-4f orbital with eight O-2p_π orbitals in the adjacent CuO₂ bi-layer is discussed. No superconductivity was observed in the present study.     

An analysis of the thermoelectric efficiency of n-(Bi,Sb)2(Te,Se,S)3 solid solutions within an isotropic scattering model

A study is reported on the thermoelectric properties of n-type solid solutions Bi₂Te_3?y Se_y (y=0.12, 0.3, 0.36), Bi_2?x Sb_xTe_3?y Se_y (x=0.08, 0.12; y=0.24, 0.36), and Bi₂Te_3?z S_z (z=0.12, 0.21) as functions of carrier concentration within the 80-to 300-K range. It has been established that the highest thermoelectric efficiency Z is observed in the Bi₂Te_3?y Se_y (y=0.3) solid solution containing excess Te at optimum carrier concentrations (0.35×10¹⁹ cm^?3) and at temperatures from 80 to 250 K. The increase in Z in the Bi₂Te_3?y Se_y solid solution compared with Bi_2?x Sb_xTe_3?y Se_y and Bi₂Te_3?z S_z is accounted for by the high mobility μ₀, an increase in the effective mass m/m ₀ with decreasing temperature, the low lattice heat conductivity κ_L, and the weak anisotropy of the constant-energy surface in a model assuming isotropic carrier scattering.     

Measurement ofK-electron capture probability (P k ) in the decay of197Hg (64.1 h)

TheK-electron capture probability (P _K ) for the 268.7 and 77.3 keV states of¹⁹⁷Au in the decay of¹⁹⁷Hg (64.1h) have been determined from theKX-ray gamma ray summing in a HPGe X-ray detector. The measured values,P _k (268.7)=0.746±0.033 andP _k (77.3)=0.774±0.036 are found to be in good agreement with the theoretical results.     

Effect of 3d metal ion doping on the structure and superconductivity of (Tl0.5Pb0.5)Sr2CaCu2O7

(Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ (M=Co, Ni and Zn) have been synthesized and investigated by means of X-ray diffraction, scanning electron microscope, electrical resistivity and magnetic susceptibility measurements. X-ray diffraction patterns show that all studied samples contain the nearly single ‘1212’ phase. They crystallize in a tetragonal unit cell with a=3.8028-3.8040 Å and c=12.0748-12.1558 Å. In (Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ system (M=Co or Ni), the superconducting critical temperature T_c decreases linearly with both Co and Ni concentrations and the rate of T_c decrease is around −6.5 and −7.0 K/at%, respectively. For (Tl_0.5Pb_0.5)Sr₂Ca (Cu_2−xZn_x)O₇ system, the dependence of T_c on the Zn dopant concentration deviates from a linear behavior and the Zn substitution suppresses T_c much less (−2.5 K/at%) than the Co and Ni substitutions. The suppression in T_c in Co and Ni doped samples are attributed to the magnetic pair-breaking mechanism and the reduction in the carrier concentration. The suppression of T_c in Zn doped samples is not caused by the reduction in carrier concentration which should remain constant, but rather due to nonmagnetic pair-breaking mechanism induced by disorder as well as the filling of the local Cu d_x²−y² state due to the full d band of Zn ions.     

Magnetic and structural investigations of GdMn2-GdNi2 intermetallic compounds

Magnetic and structural properties of the intermetallic system Gd(Mn_1-xNi_x)₂ were investigated. The 0?x?0.4 and 0.7<x?1 compounds are Laves phases of the MgCu₂ type. The remaining compounds 0.4?x?0.7. crystallize with the hexagonal structure. For single crystal GdMn_0.8Ni_1.2 the P6₃/mmc space group and the lattice parameters a=5.175 Å and c=16.731 Å are obtained. The magnetic properties of investigated series are investigated in stationary and in pulsed magnetic fields in the temperature range 2.6–700 K. For 0.4?x?0.8 two magnetic transitions are observed. In the paramagnetic range the χ^-1_M (T) is described by a Néel type variation and the molecular field coefficients N_{i j} are calculated. The localized character of the magnetic moment of Mn is observed.     

Superconducting and normal state properties of Ag1−xSn1 + xSe2−y

The occurrence of superconductivity in a new ternary non-transition element compound with the cubic NaCl structure is reported. The composition of this compound is Ag_1?xSn_{1 + x}Se_2?y, with a maximum homogeneity range given by ?0.02 ?x?0.24 and 0 ? y ?0.1. The superconducting transition temperature (T_c) ranges from a minimum of 4.5 K for x = ?0.02, y = 0 to a maximum of 6.9 K for x = 0.24,y = 0. These T_c's are higher than previously observed in nontransition element NaCl structure compounds. Electrical resistivity data show a positive temperature coefficient, and room temperature magnetic susceptibility measurements reveal a rapidly increasing density of states at the Fermi level with increasing x. Two ionic models for calculating the carrier concentration of Ag_1?xSn_{1 + x}Se_2?y are discussed, and a third model based on the band picture is proposed. The composition dependence of the magnetic susceptibility was used to test the validity of each of the models.