Effect of local atomic phase separation in the x-ray absorption near edge structure spectroscopy of FeSexTe1−x

Ab initio X-ray absorption near edge structure (XANES) calculations for FeSe_xTe_1−x, using a structural model that combines FeSe and FeTe phases at the nanoscale, are compared with Fe K-edge XANES measurements in the “pre-edge” region. The important aspects of this model are (i) magnetic order in the FeTe phase; (ii) Se and Te atoms placed randomly in both FeSe and FeTe crystallographic positions and; (iii) the two distinct distances for Fe–Se and Fe–Te of the bulk phases. The calculated spectra reproduce the observed increase of spectral weight in the experiments on FeSe_xTe_1−x with Se concentration. This is consistent with an inhomogeneous local electronic structure of FeSe_xTe_1−x. Additionally, we have calculated projected electronic density of d-states for the Fe atom, revealing increased spectral weight in the “pre-edge” region of the XANES spectra, which correlates with the increase in Se concentration. The decrease of calculated Fe d-density of states for the Fermi level, N(ε_F), for high Te content is consistent with the suppression of superconductivity in the title system.     

Photoemission results of intermetallic superconductors: Nb3Al and MgB2

We study the superconducting electronic structures of Nb₃Al and MgB₂ using high-resolution spectroscopy. The obtained spectrum of Nb₃Al measured below T_c shows clear opening of the superconducting gap with a sharp pile up in the density of states and a shift of the leading edge. In addition, the spectrum shows a peak-dip-hump line shape expected from the strong-coupling theory. On the other hand, for MgB₂, the superconducting-state spectrum measured at 5.4 K shows a coherent peak with a shoulder structure, in sharp contrast to that expected from a single isotropic gap. The superconducting spectral shape of MgB₂ can be explained in terms of a multicomponent gap.     

Superconductivity and calorimetric studies of Pr1.85Ce0.15CuO4+δ under different annealing conditions

Polycrystalline samples of electron-doped Pr_1.85Ce_0.15CuO_4+δ have been prepared under different annealing conditions and investigated by means of X-ray-diffraction, oxygen content analysis, electrical resistivity, magnetic susceptibility and low temperature specific heat measurements. X-ray-diffraction patterns show that samples contain a single T′ phase. The superconducting transition temperatures T_cm taken with the onset of diamagnetism in magnetic-susceptibility measurements are 20 and 19.5 K for sample annealed in flowing Ar gas and in vacuum (∼10⁻³ torr), respectively. The data of the samples, which are annealed in flowing Ar gas, show clear evidence for an αT² term at zero magnetic field in superconducting electronic specific heat, and are consistent with d-wave superconductivity. However, this behavior is not observed in the other sample, which is annealed in vacuum. These results indicate that different heat treatments affect the oxygen content, homogeneity, superconducting transition temperature T_c, superconducting volume fraction, and the superconducting pairing symmetry of Pr_1.85Ce_0.15CuO_4+δ.     

Relationship between chemical bond parameters and superconducting temperature in HgBa2Can−1CunO2n+2+δ (n=1, 2, 3, 4)

Bond covalency and valence of elements in HgBa₂Ca_n−1Cu_nO_2n+2+δ (n=1, 2, 3, 4) were calculated and their relationship with T_c was discussed. For both oxygen and argon annealed samples, the results indicated that with the increase of n, the trend of bond covalency of Hg-O and Cu-O was the same or opposite compared with that of superconducting temperature. This may suggest that the magnitudes of Cu-O and Hg-O bond covalency are important in governing the superconducting temperature. For the highest T_c sample, Hg had the lowest valence, implying that lower valence of Hg was preferred in order to produce higher T_c. For fixed n, the valence of Cu in oxygen annealed samples was larger than that in argon annealed samples, indicating that oxygen annealed samples produced more carriers than argon annealed samples.     

Role of interstitial “caged” Fe in the superconductivity of FeTe1/2Se1/2

All samples are synthesized through a standard solid state reaction route and are quenched to room temperature systematically at 700 °C, 500 °C, 300 °C, and room temperature (RT); the samples are denoted 700Q, 500Q, 300Q, and RTQ, respectively. The structural, and magnetic properties are studied. Careful Rietveld analysis of the X-ray diffraction patterns revealed that all samples except 700Q crystallized in a single phase with space group P4/nmm; the amount of interstitial Fe (Fe_int) at the 2c site increased from 5% for RTQ to 8% for 500Q. Sample 700Q crystallized in the Fe₇Se₈ phase. The magnetization result revealed that RTQ and 300Q are superconducting at 10 K and 13 K, respectively, while 500Q and 700Q are not superconducting. Magnetic ordering was observed at around 125 K for all the samples. The prominence of in terms of effective moment is sufficiently higher for 500Q and 700Q than for RTQ and 300Q. Summarily, it is found that quenching-induced disorder affects the occupancy of interstitial Fe in FeTe_1/2Se_1/2 and thus both its superconducting and magnetic properties. Further, it clear that limited presence of interstitial Fe at 2c site is not completely contrary to the observation of superconductivity, because the 300Q sample possesses higher T_c (13 K) for higher Fe_int (6%) than the RTQ sample with relatively lower T_c (10 K) having lower Fe_int (5%). Further, the 500Q sample, with much higher Fe_int (8%), is non-superconducting.     

Coexistence of superconductivity and magnetism in the La0.87−xLnxSr0.13FeAsO (Ln=Sm, Gd, Dy) system

The interplay between the superconducting phase and spin density wave order phase was studied. We report the magnetic and superconducting properties of the hole-doped FeAs-based superconducting compound La_0.87−xLn_xSr_0.13FeAsO (Ln=Sm, Gd, Dy; 0≤x≤0.06). Both resistivity and magnetic susceptibility measurements show that the superconducting transition temperature decreases with increase in composition of magnetic ions. The hysteresis loop of the La_0.87−xLn_xSr_0.13FeAsO sample shows a superconducting hysteresis in addition to a paramagnetic background. The experiment demonstrates that the magnetism and superconductivity coexist in hole-doped FeAs-based superconducting compounds. Among these three magnetic rare-earth elements, the influence of Dy³⁺ doping on superconductivity is more evident than that of Gd³⁺ doping, while the influence of Sm³⁺ doping is the weakest. The trend is consistent with the variation of the lattice parameter along c-axis.     

Low field AC susceptibility study of intergranular critical current density in Mg-substituted CuBa2Ca3Cu4O12−y high temperature superconductors

Measurements of the a.c.susceptibility (χ=χ′+iχ″) have been made on the Mg substituted high T_C superconducting system, CuBa₂(Mg_xCa_1−x)₃Cu₄O_12−y (Cu-1234) with x=0, 0.10 & 0.20, at different values of the a.c.field amplitude. Estimates of the intergranular critical current density(J_C) made from the field dependent χ″-T curves show an improvement in the Mg-substituted Cu-1234 system. Results have been analysed in the light of the crystal structure and the superconducting anisotropy factor (γ=ξ_ab/ξ_c) of the Cu-1234 system. Lower superconducting anisotropy emanating from Mg substitution has been found to be significant, resulting in better superconducting properties.     

Local magnetization study of the first-order superconducting transition in CeCoIn5

We report local magnetization measurements on the heavy fermion superconductor CeCoIn₅ using a micro-Hall probe. Below a critical point T₀ (), the local magnetization shows a clear jump at the superconducting transition temperatures for both H∥a and H∥c, indicating that the phase transition at the upper critical field H_c2 becomes a first-order phase transition. In addition, we observed an undershoot behavior of magnetization jump above (H∥c), which suggests a rapid change of textured superconducting structure with vortices and the nodal planes expected in the Fulde-Ferrell-Larkin-Ovchinnikov state.     

Magnetism on Mg1−xZnxCyNi3

The magnetic phase diagram for Mg_1−xZn_xC_yNi₃ has been tentatively constructed based on magnetization and muon spin relaxation (μSR) measurements. The superconducting phase was observed to fade as x (y) increases (decreases). The low y samples show early stages of long-range ferromagnetism, or complete long-range ferromagnetism. In the phase diagram, the ferromagnetic phase exists in addition to the superconducting phase, suggesting that there is some correlation between superconductivity and ferromagnetism, even though the coexistence of ferromagnetism and superconductivity is not observed from the μSR measurements down to 20 mK for the superconducting sample (T_c=2.5 K, (x, y)=(0, 0.9)).     

Metal-insulator transition and superconductivity in Hg-doped BaPb0.75Bi0.25O3

The effects of mercury doping on the superconductivity, crystal structure, and electronic structure have been investigated in Hg-doped BaPb_0.75Bi_0.25O₃ (BaPb_0.75−xHg_xBi_0.25O₃, BPHBO) by magnetic measurement, powder X-ray diffraction (XRD), and X-ray photoemission spectroscopy (XPS). At lower doping levels, the system is metallic and superconducting. However, the superconductivity is fully suppressed by Hg doping at x>0.25 and recovered with further increase in Hg content at x>0.3, showing a superconductivity reentrant phenomenon. XPS analysis reveals that BPHBO experiences dual metal-insulator transitions (MITs) at these two superconductivity points, which are accompanied by lattice distortions, suggesting that they may be driven by Peierls transitions. The first MIT may be a Mott-transition, while the second may be due to competition between the band filling effect and modification of the charge-disproportionate state.     

Near EF electronic structure of heavily boron-doped superconducting diamond

We have performed soft X-ray angle-resolved photoemission spectroscopy (SXARPES) of a heavily boron-doped superconducting diamond film (T_c=7.2 K) in order to study the electronic structure near the Fermi level (E_F). Careful determination of measured momentum space that across Γ point in the Brillouin zone (BZ) and increase of an energy resolution provide further spectroscopic evidence that E_F is located at the highly dispersive diamond-like bands, indicating that holes at the top of the diamond-like valence band play an essential role for the conducting properties of the heavily boron-doped superconducting diamond for this boron-doping region (effective carrier concentration of 1.6%). The SXARPES intensities at E_F were also mapped out over BZ to obtain experimental Fermi surface sheets and compared with calculations.     

Increase of Tc in the 1:2:3 superconductors YBCO and (CaxLa1−x)(LauBa1−u)2Cu3Oy after slow cooling or low temperature annealing

The well known phenomenon of the increase of T_c of YBCO after slow cooling or low temperature annealing without change of the oxygen content, was found also for the YBCO like tetragonal superconductors of (Ca_xLa_1−x)(La_uBa_1−u)₂Cu₃O_y (this compound has been previously denoted as CLBLCO, CLBCO or CaLaBaCuO). It has been observed at 150 and 100 °C for oxygen underdoped, optimally- and overdoped ceramics. The products retain their tetragonal unit cells. The possible reasons of this phenomenon are discussed.     

FeTe as a candidate material for new iron-based superconductor

Tetragonal FeSe is a superconductor with a transition temperature T_c of 8 K and shows a huge enhancement of T_c with applying pressure. Tetragonal FeTe has a structure very analogous to superconducting FeSe, but does not show superconducting transition. We investigated the pressure effect of resistivity on FeTe. The resistivity at room temperature decreased with increasing pressure. An anomaly in resistivity around 80 K shifted towards a lower temperature with increasing pressure.     

Possible coexistence of superconductivity and magnetism in intermetallic NiBi3

NiBi₃ polycrystals were synthesized via a solid state method. X-ray diffraction analysis shows that the main phase present in the sample corresponds to NiBi₃ in a weight fraction of 96.82 % according to the refinement of the crystalline structure. SEM - EDS and XPS analysis reveal a homogeneous composition of NiBi₃, without Ni traces. The powder superconducting samples were studied by performing magnetic measurements. The superconducting transition temperature and critical magnetic fields were determined as , Oe and Oe. The superconducting parameters were , , and κ=5.136. Isothermal measurements below the transition temperature show an anomalous behavior. Above the superconducting transition the compound presents ferromagnetic characteristics up to 750 K, well above the Ni Curie temperature.     

Comprehensive study of high-Tc interface superconductivity

Using ALL-MBE technique, we have synthesized different heterostructures consisting of an insulator La₂CuO₄ (I) and a metal La_1.56Sr_0.44CuO₄ (M) layer neither of which is superconducting by itself. The M-I bilayers were superconducting with a critical temperature T_c≈30-36 K. This highly robust phenomenon is confined within 1-2 nm from the interface and is primarily caused by the redistribution of doped holes across the interface. In this paper, we present a comprehensive study of the interface superconductivity by a range of experimental techniques including transport measurements of superconducting properties.     

High-resolution photoemission study of FeSr2YCu2O7+δ

We have performed high-resolution photoemission spectroscopy (PES) on FeSr₂YCu₂O_7+δ, of which superconductivity of T_c=49 K was recently reported. We clearly observed opening of a d-wave-like superconducting gap and estimated the maximum gap value (Δ_max) to be 10 meV at 15 K. This gap value gives 2Δ_max/k_BT_c∼5, suggesting a strong-coupling nature of superconductivity in FeSr₂YCu₂O_7+δ. Comparative PES study with superconducting and insulating samples shows that the valence band is rigidly shifted as a function of doping without evolution of additional states within the insulating gap.     

The impact of Y substitution on the 110 K high Tc phase in a Bi (Pb):2223 superconductor

The structural and superconducting properties of Bi_1.7Pb_0.3Sr₂Ca_2−xY_xCu₃O_y superconducting samples are investigated by X-ray diffraction (XRD), resistivity and thermoelectric power (TEP) measurements. XRD results reveal that the volume percentage of the 2223 high T_c phase decreases with an increase in Y content. The replacement of the Ca²⁺ ion by the Y³⁺ ion does not influence the tetragonal structure of the pure Bi (Pb): 2223 system and the lattice parameters vary with Y content. The results of resistivity indicate that the critical temperatures T_c of the samples decrease monotonically with an increase in Y content. Further, the critical concentration of Y to completely suppress superconductivity in the Y-doped Bi (Pb):2223 system is higher (0.60) than that reported (0.20) for the other rare-earth elements. On the other hand, the values of TEP at room temperature are found to be negative for Y=0.00 and 0.10 samples, and it changed to positive with further increase in Y content. The hole-carrier concentration per Cu ion (P) is deduced by using two different ways: the first in terms of T_c values in the superconducting state and the other in terms of TEP values in the normal state. Interestingly, it is found that the values of P deduced from the formal way are not consistent with the reported parabolic behavior for superconducting systems in the under-doped region, and consequently disagree with the general roles of substitution. However, the vice versa is recorded for the values of P deduced from the latter way. The results are discussed in terms of the possible reasons for the suppression of superconductivity in the considered system.     

Superconducting properties of SmFeAsO1−x prepared under high-pressure condition

Synthetic conditions such as stoichiometries, temperature and pressure are optimized to achieve a high quality oxygen deficient SmFeAsO_0.6 superconductor. Both electric and magnetic measurements show a sharp superconducting transition at about 55 K. Several important physical parameters are deduced. The apparent superconducting gap observed in heat capacity with 2Δ_o/k_BT_c of 4.57 larger than that of previous fluorine replaced samples indicate that this superconductivity will not strongly conflict with the phonon-mediated BCS mechanism. The mean free length ?=18.8 nm and the coherent length ξ=2.3-3.3 nm show that the superconductivity is in the clean limit.     

The role of substitution-induced micro-structural defects on the redox behavior and catalytic activity of LaxTh1−x(VO3−δ)4 mixed oxide catalysts

The catalytic properties and reduction behavior of mixed metal oxides with nominal compositions of La_xTh_1−x(VO_3−δ)₄, where 0.0 ≤ x ≤ 1.0, have been investigated as a function of the value of x. These compositions were synthesized by ceramic route and characterized using powder X-ray diffraction, differential thermal analysis, and temperature-programmed reduction/oxidation/desorption techniques. The substituted samples were comprised of two distinct phases, one corresponding to tetragonal thorium metavanadate with partial substitution at A-sites, i.e. La_xTh_1−x(VO_3−δ)₄, and the other a new phase identified as LaV₄O_11+δ. Both these phases exhibited considerable oxygen non-stoichiometry, depending upon the extent of substitution. Nevertheless, no significant change was observed in their respective crystal symmetry. Further, the substituted samples showed more reproducible redox behavior and also an improved catalytic activity for CO oxidation reaction. A definite correlation is found to exist between the micro-structural defects generated in the above-mentioned two phases because of the oxygen ion vacancies, resultant enhancement in thermal diffusitivity of lattice oxygen, and finally the catalytic activity of the substituted mixed oxides. It is envisaged that a kind of synergism between the micro-structural defects existing in the two inter-grown phases generated simultaneously during the synthesis may control the catalytic properties of composite metal oxide systems.     

Local structure of Mn in (Ga,Mn)As probed by X-ray absorption spectroscopy

Local structure of Mn atoms in Ga_1−xMn_xAs epilayers was studied using the X-ray absorption fine structure (XAFS) at Mn K-edge. X-ray near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) techniques were used. XAFS spectra for different Mn sites has been calculated and compared with the experimental data. Multi-parameter fitting of the EXAFS data indicates that 15-25% of Mn atoms are in interstitial sites in the as grown films. The Mn-As bond length has been found longer than Ga-As bond length in GaAs for both substitutional (Mn_Ga) and interstitial (Mn_I) sites.