Electrical and thermal properties of bulk superconductors Eu0.95Pr0.05Ba2(Cu1−xMx)3O7−δ (M = Fe,Ni, Zn and Mn)

Measurements of transition temperature, magneto-resistance, thermal conductivity, thermo-electric power and specific heat have been carried out on co-doped samples of Eu_0.95Pr_0.05Ba₂(Cu_1?xM_x)₃O_7?δ (M = Fe, Ni, Zn and Mn) compounds. It is found that all samples exhibit metallic behavior, except the co-doped sample of Fe that shows semiconducting behavior. It is seen that the upper-critical field H_c2 decreases with Pr-doping. However, an increase in H_c2 for dopants like Fe and Mn is observed. Thermal conductivity for the pristine sample of EuBa₂Cu₃O_7?δ (Eu-123) exhibits a pronounced hump below the superconducting transition temperature T_C. However, the peak height of the hump decreases with Pr-doping and such a feature is further suppressed in the co-doped samples. The negative sign of the measured thermo-electric power of Eu-123 indicates that the dominant carrier in this sample is electron-like, whereas it turns to hole-like for all of the doped samples. A jump in specific heat C_P is detected in the pure sample of Eu-123 at T_C, while only a change in slope in C_P is seen around the transition temperature in the Pr-doped sample.     

First principles studies on the elastic,thermodynamic properties and electronic structure of Ti15−xMoxSn compounds

The structural, elastic, thermodynamic and electronic properties of the Ti_15−xMo_xSn compounds were systematically investigated by means of first-principles calculations based on the density functional theory (DFT). The calculated results demonstrate the Ti_15−xMo_xSn compounds still remain the stable β phase structure. The calculation of cohesive energy shows that the structural stability of the Ti_15−xMo_xSn compounds increases apparently with the increase of Mo content. According to Hooke's law, the single crystal elastic constants were obtained and show that all the calculated compounds keep mechanical stability. Then the bulk modulus B, shear modulus G, Young's modulus E and Poisson's ratio ν of polycrystalline aggregates were calculated at zero pressure. The calculated results show that among these Ti_15−xMo_xSn compounds, Ti₄Mo₁₁Sn exhibits the largest stiffness while Ti₁₂Mo₃Sn shows the greatest ductility. The compounds Ti₁₂Mo₃Sn and Ti₁₁Mo₄Sn with the two lowest elastic Young's modulus of 61.01 GPa and 65.59 GPa are expected to be promising metallic biomaterials for implant applications. Besides, the Debye temperature Θ_D and the electronic density of states (DOS) are also investigated and discussed.     

Electronic structure,spin polarization and high critical fields in Chevrel compounds

Results are presented of an extensive theoretical study of the origin of high field superconductivity and/or magnetism in a number of Chevrel phase ternary compounds, MMo₆X₈ (with M=Sn, Eu, Gd and X=S and/or Se) based on self-consistent linear muffin-tin orbital (LMTO) energy band calculations using the local density approach (Hedin et al. exchange correlation) for the paramagnetic structures and local spin density formalism (Gunnarsson and Lundqvist) for the ferromagnetic structures. All electrons and all 15 atoms/cell are included with the core electrons (including the 4f's) recalculated in each iteration in a fully relativistic representation and the conduction electrons treated semirelativistically (all relativistic terms except spin-orbit). Superconductivity is found to be due to the high Mo d-band density of states (DOS) at E_F resulting from the unusual large charge transfer of Mo electrons to the chalcogen sites. There is also a large charge transfer from the metal site to the cluster (≈2 electrons in Sn and Eu) giving essentially no occupied conduction bands, for example, at the Eu site and a divalent ion isomer shift in very good agreement with the experiments of Dunlap et al. The conduction-electron DOS at the Eu site is found to be reduced by an order of magnitude from its metallic state value - in close agreement with their spin - lattice relaxation rate measurements. This low conduction-electron DOS yields very weak coupling of the 4f electrons to the conduction electrons and only a very weak Ruderman-Kittel-Kasuya-Yosida magnetic interaction showing why all the Chevrel rare-earth compounds - except Ce and Eu - are superconducting despite their having large local magnetic moments. The unusually high upper critical fields, H_c2, in these materials is found to be due to the unusully flat energy bands near F_F. The ferromagnetic (spin polarized) results for the Eu- and Gd-compounds show a net small but positive magnetic moment on the metal site and a small but negative induced spin magnetic moment on the Mo site in the Eu compound. Fermi-contact contributions to the hyperfine field are calculated and found to be in good agreement with the Eu Mössbauer results and the negative NMR Knights shift results of Fradin et al. These results demonstrate theoretically for the first time the validity of the Fischer et al. and Fradin et al. conclusion that the Jaccarino-Peter mechanism is responsible for the large increase in the H_c2 when large concentrations of Eu magnetic impurities are substituted in SnMo₆S₈. Finally, calculated Stoner factors for the paramegnetic phase and spin magnetization densities for the ferromagnetic phase are used to discuss qualitatively the origin of the different behavior observed for GdMo₆S₈ and EuMo₆S₈.     

An X-ray photoelectron spectroscopy study of volatile tin compounds

Core-level X-ray photoelectron spectra of fifteen compounds of tin have been measured in the gas phase. The compounds include various organo and halo compounds as well as tin(IV) nitrate and Sn{N[Si(CH₃)₃]₂}₂. The tin binding energies span a range of 4.4 eV and are well correlated by the “transition-state” point-charge potential model equation using atomic charges calculated by the CHELEQ electro-negativity equalization method. As expected, the empirically determined parameter k for tin is smaller than the k values obtained in previous work for carbon, silicon, and germanium. For Sn(NO₃)₄, and Sn{N[Si(CH₃)₃]₂}₂, the bonding can be described as a weighted average of several resonance structures. In these cases the binding energy data were used in conjunction with the CHELEQ method to determine the resonance structure weightings.     

Electronic, magnetic and transport properties of Co2TiZ (Z=Si, Ge and Sn): A first-principle study

We have studied the electronic structure, magnetic and transport properties of some Co based full Heusler alloys, namely Co₂TiZ (Z=Si, Ge and Sn), in the frame work of first-principle calculations. The calculations show that Co₂TiZ (X=Si, Ge and Sn) are to be half-metallic compounds with a magnetic moment of 2 μ_B, well consistent with the Slater-Pauling rule. The electronic structure results reveal that Co₂TiZ has the high density of states at the Fermi energy in the majority-spin state and show 100% spin polarization. Our results also suggest that both the electronic and magnetic properties in these compounds are intrinsically related to the appearance of the minority-spin gap. The origin of energy gap in the minority-spin states is discussed in terms of the electron splitting of Z (Z=Si, Ge and Sn) and 3d Co atoms and also the d-d hybridization between the Co and Ti atoms. The transport properties of these materials are discussed on the basis of Seebeck coefficients, electrical conductivity coefficients and thermal conductivity coefficients.     

Transferred hyperfine fields at 119Sn in Fe1−xMxSn [M≡Mn, Co and Ni]

The transferred hyperfine fields at ¹¹⁹Sn, using Mössbauer spectroscopy are reported for the hexagonal B-35 compounds with a general formula Fe_1?xM_xSn, where MMn, Co and Ni. In these compounds, Sn atoms occupy two crystallographically inequivalent sites. For FeSn the observed spectrum consists of a quadrupole doublet and a magnetic pattern corresponding to 2(d) and 2(a) sites respectively. The data have been analysed to resolve the controversy regarding hyperfine parameters. On replacing Fe by Mn atoms, additional lines appear in the higher velocity region of the Mössbauer spectrum and the intensity of the nuclear Zeeman pattern increases at the expense of quadrupole doublet. The resulting Mössbauer spectra have been analysed by taking only the nearest neighbour interactions into account. This analysis shows that on replacing each Fe atom by a Mn atom, the hyperfine field at 1(a) Sn site increases by about 40 kOe and a field of about 35 kOe is produced at the 2(d) Sn sites. Further, from the nuclear Zeeman pattern for 2(d) sites, the sign of quadropole splitting for these sites could also be determined and was found to be positive. However, the substitution of Co and Ni in place of Fe atoms results in a broad unresolved pattern suggesting that the hyperfine field at the 1(a) sites decreases and a finite field develops at the 2(d) site. The origin of transferred hyperfine fields at the two inequivalent Sn sites is discussed, the magnetic transition temperatures of these compounds have been estimated and the magnetic moments of M-atoms have been inferred.     

Theoretical prediction of the structural,elastic, electronic and thermodynamic properties of V3M (M = Si,Ge and Sn) compounds

Density functional theory (DFT), is used in our calculations to study the V₃M (M = Si, Ge and Sn) compounds, we are found that V₃Sn compound is mechanically unstable because of a negative C₄₄ = −19.41 GPa. For each of these compounds considered, the lowest energy structure is found to have the lowest N(E_f) value. Also there is a strong interaction between V and V, the interaction between M (M = Si, Ge, Sn) and V (M and M) is negative, not including Si [Sn]. In phonon density of states PDOS, the element contributions varies from lighter (high frequency) to heaviest (low frequency).     

Electrochemical properties of Ti-Ni-Sn materials predicted by <Superscript>119</Superscript>Sn Mössbauer spectroscopy

The electrochemical activity of TiNiSn, TiNi ₂Sn and Ti ₆Sn ₅ compounds considered as negative electrode materials for Li-ion batteries has been predicted from the isomer shift- Hume-Rothery electronic density correlation diagram. The ternary compounds were obtained from solid-state reactions and Ti ₆Sn ₅ by ball milling. The ¹¹⁹Sn Mössbauer parameters were experimentally determined and used to evaluate the Hume-Rothery electronic density [e _av]. The values of [e _av] are in the region of Li-rich Li-Sn alloys for Ti ₆Sn ₅ and outside this region for the ternary compounds, suggesting that the former compound is electrochemically active but not the two latter ones. Electrochemical tests were performed for these different materials confirming this prediction. The close values of [e _av] for Ti ₆Sn ₅ and Li-rich Li-Sn alloys indicate that the observed good capacity retention could be related to small changes in the global structures during cycling.     

119Sn Mössbauer characterization of self assembled organotin(IV) complexes with Schiff bases containing amino acetate skeletons

Several organotin(IV) compounds, viz., diorganotin(IV) compounds of the types Ph₂SnLH (monomer), ⁿBu₂SnLH·OH₂ (monomer), [Me₂SnLH·OH₂]₂ (centrosymmetric dimer), [ⁿBu₂SnLH]₃ (cyclic trinuclear), [Ph₂SnLH] _n (polymer), {[ⁿBu₂Sn(LH)]₂O}₂ (centrosymmetric tetranuclear), dinuclear di-/tri-mixed organotin(IV) compounds Ph₂SnLH·Ph₃SnCl (monomer) and triorganotin(IV) compounds of the types [Bz₃SnLH]₂ (centrosymmetric dimer) and [Me₃SnL¹H] _n (Polymer) (LH = Schiff base carboxylate) have been studied in the solid state at liquid nitrogen temperature using ¹¹⁹Sn Mössbauer spectroscopy. The tin coordination geometry of the compounds determined from crystallography was correlated with the ¹¹⁹Sn Mössbauer results.     

C 1s NEXAFS study of rare-earth’s (La,Eu)-graphite intercalation compounds

Electronic structure of unoccupied states of Eu- and thin surface layer of La-intercalation compounds was studied by light polarization dependent NEXAFS at the C 1s threshold in a bulk sensitive (E_kin=1–2 eV) and a more surface sensitive (E_kin=265 eV) partial electron yield mode. It was shown that the C 1s spectra in both cases are mainly characterized by the π*- and σ*-symmetry graphite-derived features. For both systems the π*-derived peak was found at similar energies of exciting photons as for pristine graphite. A decrease of relative intensity of the π*-originated structure in intercalation compounds can be understood by partial occupation of the π*-derived states upon intercalation due to a charge transfer from rare-earth (RE) atoms. NEXAFS features found on both sides of the π* response may be related to pd hybrids forming as a result of chemical interaction between RE atoms and graphite layers.     

Magneto-crystalline properties of BaFe12−2x M x Sn x O19 (M = Sn, Ni, Zn) ferrite powders

BaFe_12?2x M _x Sn _x O₁₉ compounds, where M?=?Sn²⁺, Ni²⁺ or Zn²⁺ ions, were synthesized by mechanical milling and partially by citrate precursor methods. Analysis of magneto-crystalline structure has been carried out by Mössbauer spectroscopy. The Sn⁴⁺ ions replace Fe³⁺ ions on 2b and slightly on 2a?+?4f₁ sites, Zn²⁺ ions strongly prefer 4f₁ sites, Sn²⁺ ions prefer 4f₁ sites too and Ni²⁺ ions occupy 4f₂ and 12k or 2a sites. The magnetic properties were evaluated by the vibrating sample magnetometry and the thermomagnetic analysis. A large variation of the intrinsic coercivity H _c (330 to 78 kA/m) and of temperature coefficient of coercivity of ΔH _c /Δ? (0.39 to 0.22 kA/m°C) were achieved as a function of the (Zn–Sn) and (Sn–Sn) substitutions, respectively. The Curie temperature T _c decreased with the (Ni–Sn) substitution from 447 to 399°C.     

Pseudodipole interaction in exchange-frustrated antiferromagnets

It is shown that the pseudodipole interaction explains the experimentally observed noncollinear magnetic structure of the compounds U₂Pd₂X (X=In, Sn) and PrBa₂Cu₃O_6+x , which consist of two spin subsystems which are noninteracting in the mean-field approximation if there is only isotropic exchange between them.     

Superconducting thin films of MxMo6S8 type

Thin films of M_xMo₆S₈, where M=Pb, Sn, Sn-Al and Cu, known as the Chevrel phases have been prepared by d.c. getter sputtering method and the optimal conditions of their preparation have been determined. The transition temperatures reached: 10.16, 13.66, 11.74 and 12.86 K for thin films with M=Cu, Sn, Sn-Al and Pb respectively. The highest critical fields H_c²(0) of 428 kG were obtained for Pb compounds.     

Magnetic measurements on Heusler alloys Ni2(Ti,Mn)Sn and Co2(Ti,Mn)Sn

Magnetic measurements (temperature and field dependence) on Heusler alloys Ni₂(Ti, Mn)Sn and Co₂(Ti, Mn)Sn were performed in the ferro- and para-magnetic region. In both systems the composition range was from x = 0 to x = 1. All the Co₂(Ti, Mn)Sn samples are ferromagnetic; in the system Ni₂Ti_1?xMn_xSn for x ? 0.2. Our interpretation of the magnetic data differs from that of previous authors.     

Nanostructural inhomogeneity of EuBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6 + δ</Subscript> superconductors

Samples of high-temperature superconducting oxide EuBa₂Cu₃O_{6 + δ} (Eu-123) with total cationic composition Eu: Ba: Cu = 1: 2: 3 are investigated by means of local X-ray microanalysis and high-resolution transmission electron microscopy. The cationic nonstoichiometry of Eu-123 oxide is revealed. The particles of the studied samples are inhomogeneous in structure on the nanoscale, with two types of inhomogeneities: one with typical sizes of one to several nanometers, and one with typical sizes of 10 to 20 nm, respectively.     

Transition probabilities and energy levels in heavy odd-mass isotopes of Sn (A=119–125)

The de-excitation of levels in^119–125Sn populated in the decay of In isotopes has been studied using on-line isotope separators. Level half-lives have been measured in^119–123Sn. a near cancellation of the matrix element for B(E2; g_7/2→ d_3/2) is observed to occur in¹²¹Sn and is probably due to pairing effects. Very low lying 9/2^? levels have been observed in^121–125Sn and are suggested in^{127, 129}Sn. These levels have been interpreted as three quasi-particle states based on the unique parity h_11/2 level. A possible mixing of theg _7/2 level with a close lying 7/2⁺ three quasi-particle state in¹²³Sn is discussed. Radioactivity.^119–125In from²³⁵U(n, f) and²³⁸U(α, f), isotope separated sources; measuredE _γ ,I _γ , E_ce, I_ce,γγ-coin,Βγ-delay, deduced multipolarities.^119–123Sn deduced levels,I, π, B(λ). Ge(Li), Si(Li), NaI(Tl) and plastic detectors, Ge(Li)-Ge(Li) coin, plastic detector — NaI(Tl) delay.     

Low temperature CEMS of Sn-implanted SiO2

Conversion electron Mössbauer spectroscopy (CEMS) at room and low temperature has been used to study thin SiO₂ films implanted with Sn atoms and annealed at 900°C. This work focuses on the determination of the Debye temperature (θ _D) and Debye–Waller factors (f) of the Sn oxidized phases formed in this system. The Sn²⁺ oxidation state is the predominant one, even if a small percentage of the Sn atoms is in the Sn⁴⁺ oxidation state. The real Sn-oxides fractions are calculated by normalizing the resonant areas to the f values, as calculated from the temperature dependence of the related resonant areas within a Debye model. The Sn⁴⁺ oxidation state, possibly related to Sn atoms close to the SiO₂ surface, represents less than 20% of the Sn atoms. For the Sn²⁺ oxidation state, two different electronics configurations a and b, having different Debye temperature and hyperfine parameters are identified. The component a, with a lower θ _D (137 K), is the predominant one and might be related to small (2–3 nm) amorphous SnO _x clusters in the SiO₂ matrix. The component b could be related to substitutional Sn atoms in the SiO₂ network forming a local Sn environment similar to the SnO amorphous compound.     

Phase stability,electronic, magnetic and elastic properties of Ni2CoZ(Z = Ga,Sn): A first principles study with GGA method and GGA+U approach

First principles calculations based on density functional theory are used to investigate the phase stability, electronic, magnetic and elastic properties of ferromagnetic metallic full-Heusler Ni₂CoZ(Z = Ga, Sn) alloys via the FP-LAPW method by the generalized gradient GGA and GGA+U approximations for the exchange and correlation energy, within the Perdew–Burke–Ernzerhof (PBE 96) parameterization. The results of calculating electronic structures and magnetic properties reveal that the both Ni₂CoGa and Ni₂CoSn crystallize in L2₁ phase with regular cubic structure. The two investigated compounds exhibit metallic ferromagnetic behaviors for the GGA+U calculation. The computation of elastic constants with GGA+U approach shows that our compounds are mechanically stable.     

Magnetic hyperfine interactions and compositional short range order in the Heusler alloys Cu2MnIn1-xSnx

A comprehensive study of the magnetic hyperfine interactions and the processes of crystallographic ordering in the Heusler alloy system Cu₂MnIn_1-xSn_x has been made. We report the results of Mössbauer effect experiments, X-ray diffraction studies, electrical transport, and Curie temperature measurements. By a rapid quenching, low temperature annealing technique we have been able to extend the ordered L2₁ structure to high Sn concentration. Observations of inequivalent Sn sites and nonunique ¹¹⁹Sn hyperfine field values in these alloys are shown to be due to difficulties in ordering the L2₁ structure and a basic instability of this phase for high Sn concentrations. The compositional variation of ¹¹⁹Sn hyperfine fields in the ordered L2₁ phase of the Cu₂MnIn_1-xSn_x system reveals a systematic increase with Sn composition. Calculations of these fields based on a homogeneously spin polarized electron gas model reproduce the observed field systematics quite well. The implications of these results on the nature of magnetic interactions in Heusler alloys are discussed.     

Exploring the photoexcited triplet states of aluminum and tin corroles by time-resolved Q-band EPR

The photoexcited triplet states of three 5,10, 15-tris(pentafluorophenyl)corroles (tpfc), hosting Sn(IV) and Al(III) in their core, namely, Sn(Cl)(tpfc), Al(pyr)₂(tpfc) and Al(pyr)₂(tpfc-Br₈), were studied by time-resolved electron paramagnetic resonance (TREPR) spectroscopy in the nematic liquid crystal E7. Only two of these metallocorroles, namely, Sn(Cl)(tpfc) and Al(pyr)₂(tpfc-Br₈), exhibit TREPR spectra following pulsed laser excitation. This result is rationalized in terms of a very low quantum yield of triplet formation in Al(pyr)₂(tpfc). Analysis of the spin polarized Q-band (34 GHz) EPR spectra of Sn(Cl)(tpfc) and Al(pyr)₂(tpfc-Br₈) provides detailed information on the magnetic and kinetic parameters of the triplet states as well as on the molecular ordering of the complexes in the liquid crystal. With the assignment of the zero-field splitting parameterD<0 for the Sn(Cl)(tpfc) and Al(pyr)₂(tpfc-Br₈), one can evaluate the dominant intersystem crossing path for these metallocorroles. Analysis reveals that in Sn(Cl)(tpfc) the in-plane triplet sublevels are preferentially populated, i.e.,A _X, A_Y?A _Z. This can be rationalized in terms of weak electronic interactions between the Sn(IV) ion and the corrole π-system, consistent with the domed structure of Sn(Cl)(tpfc). In Al(pyr)₂(tpfc-Br₈), however, the out-of-plane triplet sublevel is predominantly populated, i.e.,A _Z>A _X, A_Y, which is attributed to a large increase in the spin-orbit coupling strength arising from the peripheral bromine atoms on the corrole skeleton.