57Fe and119Sn Mössbauer study of Ti-Containing highT c superconductors

⁵⁷Fe and¹¹⁹Sn Mössbauer spectroscopy as well as X-ray diffractometry were used to study Ti?Ca?Ba?Cu?O high T_c superconductors (T_c=106K) in the 4 to 300 K temperature range. X-ray diffractograms showed the dominant phase of these supercondutors to be 2-1-2-2 type. Three main iron sites were found and associalted with Fe in Cu sites in the real crystal. The dopublet with IS=0.25 mm/s and QS=0.7 mm/s at RT was attributed to the regular Cu site. No magnetic splitting was observed either in Sn or in Fe spectra taken even at 4 and 5K.     

The magnetic hyperfine field at Cu in Fe,Co and Ni and the magnetic moment of the 41 keV, 2+ state of62Cu

The magnetic hyperfine interaction of Cu in Fe, Co and Ni was studied by means of the γ-γ perturbed angular correlation method using⁶²Zn(⁶²Cu) as a probe. With the publishedg-factor (g=+0.661(12)) of the 41 keV, 2⁺ state hyperfine fields ofB _HF=16.95(51) T,B _HF=13.15(41) T andB _HF=4.05(30) T atT=0 K for Cu in Fe, Co and Ni are derived, respectively. The systematic discrepancy of these values with several independent measurements of these hyperfine fields is removed by deriving a new value ofg=0.55(5) for the 41 keV, 2⁺ state of⁶²Cu.     

Mössbauer emission study of57Co: YBa2Cu3O7−y HTSC

Mössbauer emission spectroscopy is performed on⁵⁷Co:YBa₂Cu₃O_7–y oxides in a temperature range from 300 K to 77 K. The spectra show, at least two different location for the⁵⁷Co(⁵⁷Fe) impurities. The isomer shift and quadrupole splitting values of the⁵⁷Fe daughter are coincident with those observed in⁵⁷Fe absorption experiments. From the analysis of theIS andQS values as well as from the relative location of Fe impurity levels in the HTSC matrix it is argued that:a) Co impurities enters into the lattice mainly in the Cu1 sites, but some of them have a higher coordination number.b) The daughter⁵⁷Fe exists as localized Fe⁴⁺ state.c) The parent⁵⁷Co enter as a localized Co³⁺ state. These conclusions appear consistent with the observed increase ofN(0) on doping with Fe or Co ions and with the existence of localized magnetic moments as determined from paramagnetic susceptibility measurements.     

Hyperfine magnetic fields in Fe−Co alloys and their tempera ture dependences

We obtained⁵⁷Fe hyperfine field parameters from Fe₁−x-Co _x alloys (0≤x≤0.6) from 77 K to 900 K. We first discuss the origin of the low temperature hyperfine fields in terms of the 3d and 4s electrons at⁵⁷Fe atoms. The⁵⁷Fe hyperfine magnetic field (hmf) of Fe-Co alloys depends more weakly on temperature than the hmf of pure Fe. This temperature dependence occurs because the alignment of the magnetic moments at both the Fe atoms and at the Co atoms depend on temperature in the same way as the bulk magnetization of Fe-Co alloys.     

Effect of doping on the magnetic properties of the low-dimensional antiferromagnet CuO

The effect of doping with Li⁺, Zn²⁺, Ni²⁺, and Ga³⁺ ions on the magnetic susceptibility of the low-dimensional antiferromagnet CuO (T _N=230 K) has been studied within a broad temperature range of 77–600 K. The solubility of impurity ions in the CuO lattice is low, ⩽3%. Impurity ions, similar to intrinsic defects, distort antiferromagnetic coupling and can shift the long-and short-range magnetic-order regions toward lower T. Fiz. Tverd. Tela (St. Petersburg) 40, 1876–1880 (October 1998)     

Fe-induced magnetic transition in YBa2(Cu1−x 57Fe x )3O6 by NQR and Mössbauer spectroscopy

Nuclear quadrupole resonance spectroscopy (around 30 MHz) on the chain site Cu(1) nuclei in oxygen deficient YBa₂(Cu_1?x Fe _x )₃O₆ doped with different amounts of⁵⁷Fe (x≤0.01) reveal an onset of magnetic order at low temperatures represented by a symmetrical doublet contribution to the nuclear quadrupole resonance (NQR) spectrum. The onset temperatureT _N2 depends on the concentration of Fe reaching 130 K forx=0.01. The splitting forx=0.01 at 100 K corresponds to a net internal field of 0.09 T with a distribution of ≈0.08 T representing about 70 percent of the Cu(1) nuclei.⁵⁷Fe and⁵⁷Co Mössbauer spectroscopy at 4.2 K with and without an external magnetic field of 5 T revealed that belowx=0.00015 Fe spins are decoupled from the Cu(2) moments in the antiferromagnetic state. Results are interpreted in terms of the magnetic model structure suggested by Kadowaki et al. [1].     

Magnetization and Mössbauer studies of 57Fe doped SrCoO3

⁵⁷Fe (1%) doped SrCoO₃ obtained by high-pressure method, has been investigated by magnetization and Mössbauer spectroscopy studies (MS) in the temperature range 4.2 K to 300 K. The ferromagnetic ordering temperature T _C obtained is 272(2) K. Isothermal magnetization curves have been measured at various temperatures, from which the saturation moments (M _sat) have been deduced. The ⁵⁷Fe MS spectra display standard six-line patterns with an isomer shift typical of Fe^3?+? and a very small quadrupole splitting (QS = 0.14(1) mm/s above T _C). The magnetic hyperfine field at 4.2 K is 276(1) kOe. The temperature dependencies of the iron hyperfine field and M _sat (1.83 µ _B at 5 K) are almost identical. This shows that the Fe^3?+? is replacing Co^4?+?, both of the same electronic configuration. They also interact similarly, namely the Fe–Co exchange is almost identical to the Co–Co exchange.     

Spin exchange polarization and hfs anomaly measurement of β-active37K

Rf-spectroscopic measurements in the atomic ground state of the 1.2 sec-isotope³⁷K yielded independent values of magnetic moment μ _I (³⁷K)=0.20320 (6) nm (diamagnetically corrected), hfs separation ΔW(³⁷K)=240.2672 (7) MHz and the resulting hfs anomaly³⁷Δ³⁹=(0.249±0.035) · 10^?2. The³⁷K was polarized by spin exchange scattering with optically pumped⁸⁷Rb; as a detector for rf transitions the asymmetry of the β-decay of the polarized³⁷K nuclei was used. A detailed analysis of the spin exchange mechanism under the conditions of experiments of this type was performed. This led to an explanation for the observed strong enhancement of the resonance signal heights by the spin bath. Furthermore the dependence of the nuclear polarization and relaxation time constants on the strength of the hfs coupling could be demonstrated.     

Precision measurement of the hyperfine structure of Lu175 with the atomic beam magnetic resonance method

The hyperfine structure separations of both doublet states² D _3/2 and² D _5/2 of the ground state configuration 6s ² 5d of Lu¹⁷⁵ have been remeasured with high precision using the atomic beam magnetic resonance method. Magnetic dipole transitions between Zeeman components of the hfs levels were induced applying Ramsey's technique of separated oscillatory fields whenever the field dependence of the resonances was small enough. The hfs intervals at zero field and hfs interaction constants were derived from the measurements. The constants were then corrected for hfs perturbations between the two levels of the doublet. Configuration interaction has been taken into account for the calculation of the dipole matrix elements. The corrected hfs constants are:J=3/2:A=194.332921 (300) MHzB=1511.396 267 (320) MHzC=?70 (19) HzJ=5/2:A=146.776 472 (138) MHzB=1860.656132 (840) MHzC=913 (162) HzD=?16 (24) Hz A quadrupole hfs anomaly between Lu¹⁷⁵ and Lu^176m was not found when comparing the following two ratios: Lu¹⁷⁵:B(5/2)/B(3/2)=1.2310850 (16) Lu^176m :B(5/2)/B(3/2)=1.2310818 (30). So far we have not succeeded in computing an octopole moment from the twoC-factors for the terms² D _3/2,5/2 because the influence of higher configurations could not sufficiently be considered.     

Interlayer exchange coupling: Preasymptotic corrections

In the asymptotic limit, the interlayer exchange coupling decays as D^-2, where D is the spacer thickness. A systematic procedure for calculating the preasymptotic corrections, i.e., the terms of order D^-n with ,is presented. The temperature dependence of the preasymptotic corrections is calculated. The results are used to discuss the preasymptotic corrections for the Co/Cu/Co(001) system. Received 7 January 1999     

Measurement of local magnetic fields in the CuO2 planes of CuBa2YCu2O7-delta superconductors

A fully oxygenated Cu(1)Ba2YCu(2)2O7-delta sample having 0.167 at % of the Cu atoms replaced by enriched 57Fe was synthesized. As confirmed by 57Fe M?ssbauer spectroscopy approximately 16% of the Fe atoms entered the superconducting Cu(2)O2 planes. M?ssbauer spectra recorded at various temperatures between 77 and 373 K exhibited the presence of a weak magnetic hyperfine interaction in the Fe atoms entering the CuO2 planes. The nonzero internal field obtained from the M?ssbauer data increased following a Brillouin-type behavior, from the estimated Néel-like temperature of approximately 400 K down to 96 K where it reached approximately 1.5 T. Upon further cooling below T_{c} the internal field decreased fast down to approximately 0.4 T at 77 K. The presence of the internal field is believed to be related to magnetic correlations among the CuO2-plane atoms, i.e., to reflect local antiferromagnetic coupling between the Cu atoms.     

Mössbauer spectra and electronic structure of nonequilibrium Fe-Cu alloys produced by vapor quenching

Mössbauer spectra have been observed for nonequilibrium bcc and fcc Fe–Cu alloys sputter-deposited at several Ar gas pressures,P _Ar. These alloys are ferromagnetic at low temperatures and show sextet spectra. The fcc alloys which are paramagnetic at 290 K show asymmetric doublet spectra, indicating no serious segregation. In the alloys deposited at highP _Ar, the weak intensity ratios of the second and fifth lines of the sextet indicate a tendency of perpendicular magnetic anisotropy, while a large magnetic hyperfine field component of about 40 MA/m (500 kOe) at 4.2 K and a large quadrupole splitting component of about 0.7 mm/s at 290 K imply CuFeO₂ formation. The nonequilibrium, bcc and fcc Fe–Cu, alloys are maintained below 500 K and the phase separation is detected above 550 K. X-ray photoemission spectroscopy studies of these alloys reveals individual Fe- and Cu-d bands. The concentration dependence of peak intensities and peak positions indicate that Fe and Cu electronically intermix.     

Stress‐induced Curie temperature increase in the Fe64Ni36 invar alloy

Structural and magnetic changes on invar Fe₆₄Ni₃₆ alloy (T_C = 500 K) produced by mechanical milling followed by heating up to 1073 K, were investigated by neutron diffraction, magnetization measurements, X‐ray diffraction under high pressures and X‐ray absorption at both Fe and Ni K‐edges. We argue that the strain induced in the Fe₆₄Ni₃₆ material after this treatment mainly affects the Fe sites due to the magnetovolume coupling, the most notorious feature being the increase of the Curie temperature (ΔT_C = 70 K). (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Phase separation and rapid solidification of liquid Cu<Subscript>60</Subscript>Fe<Subscript>30</Subscript>Co<Subscript>10</Subscript> ternary peritectic alloy

The metastable liquid phase separation and rapid solidification of Cu₆₀Fe₃₀Co₁₀ ternary peritectic alloy were investigated by using the drop tube technique and the differential scanning calorimetry method. It was found that the critical temperature of metastable liquid phase separation in this alloy is 1623.5 K, and the two separated liquid phases solidify as Cu(Fe,Co) and Fe(Cu,Co) solid solutions, respectively. The undercooling and cooling rate of droplets processed in the drop tube increase with the decrease of their diameters. During the drop tube processing, the structural morphologies of undercooled droplets are strongly dependent on the cooling rate. With the increase of the cooling rate, Fe(Cu,Co) spheres are refined greatly and become uniformly dispersed in the Cu-rich matrix. The calculations of Marangoni migration velocity (V _M) and Stokes motion velocity (V _S) of Fe(Cu,Co) droplets indicated that Marangoni migration contributes more to the coarsening and congregation of the minor phase during free fall. At the same undercooling, the V _M/V _S ratio increases drastically as Fe(Cu,Co) droplet size decreases. On the other hand, a larger undercooling tends to increase the V _M/V _S value for Fe(Cu,Co) droplets with the same size. Supported by the National Natural Science Foundation of China (Grant Nos. 50121101 and 50395105) and the Scientific and Technological Creative Foundation of Youth in Northwestern Polytechnical University of China (Grant No. W016223)     

Magnetic coupling in Gd(Fe6−x Cr x )Al6: A57Fe Mössbauer study

⁵⁷Fe Mössbauer measurements have been made on the ternary ThMn₁₂-type intermetallic compounds Gd(Fe_6–x Cr _x )Al₆ withx=0, 0.5, 1.0, 1.5 and 2.0, at temperatures of 4.2 and 77 K. The principal effect of the Cr substitution is to reduce the⁵⁷Fe magnetic hyperfine field at 4.2 K in this series. The analysis of the⁵⁷Fe Mössbauer spectra is consistent with a ferromagnetic coupling between the Gd and Cr magnetic moments. These results are in agreement with previous studies by Felner et al. on GdCr₆Al₆, in which a ferromagnetic ordering withT _C=170 K was observed.On leave from Applied Acoustics Institute, Shaanxi Teachers University, Xian, PR China.     

Magnetic properties of the cyclic spincluster Fe6:bicine

The magnetic properties of the cyclic compound [Fe₆(bicine)₆] LiClO₄ ^. 2MeOH are reported. The cluster Fe₆(bicine)₆ forms an antiferromagnetically coupled ring structure of Fe ^III ions. The magnetic susceptibility is measured between 2 and 300 K and yields the exchange coupling of J/k _B = - 27.5±0.5 K. The field dependence of the magnetic moment is studied at 3 and 6 K in magnetic fields up to 5 T. The zero-field splitting of the first excited spin states with S = 2 and 3 are determined by ESR at 94 GHz. The intra-molecular interactions of the Fe ^III ions are analyzed and the on-site anisotropy of the Fe ^III due to the ligand-configuration is determined to d /k _B = - 0.633±0.008K. Received 28 October 2002 / Received in final form 22 February 2003 Published online 20 June 2003 RID="a" ID="a"e-mail: bernd@piobelix.physik.uni-karlsruhe.de     

Mössbauer study of the magnetic and electric hyperfine interaction of dilute57Fe impurities in rare earth metal hosts

The hyperfine interaction of dilute⁵⁷Fe in the rare earth (RE)metals Gd to Lu was investigated by Mössbauer measurements with⁵⁷Co doped RE sources. In all hosts well split, 2-lines spectra were observed at room temperature, with slight asymmetries of the line intensities in some cases. The quadrupole splitting eQV_zz/2 increases from 0.29 mm/sec for Gd to 0.50 mm/sec for Tb, and decreases by less than 10 % between Tb and Lu. Only about 10 % of the corresponding electric fieldgradient (EFG) can be accounted for by the ionic EFG on a substitutional RE site. The temperature dependence of the EFG was measured in the case of Tb. No variation within 3 percent was found between 300 K and 700 K. Measurements of the magnetic hyperfine interaction at low temperatures were carried out in Tb. The saturation field of⁵⁷Fe in this host is H_hf(FeTb;4.2 K)=25(2) KOe. The temperature dependence of the magnetic hyperfine field does not follow the host magnetization (T_c=220K) but vanishes at about 80 K. Similar anomalies of H_hf(T) have previously been observed for other transition element impurities in the RE ferromagnets.     

Mössbauer spectroscopy in highT c superconductors

Mossbauer spectroscopy has recently been applied to study the new high T_c superconducting compounds RBa₂Cu₃O_z, using isotopes of rare earths mainly¹⁵⁵Gd and¹⁵¹Eu, and⁵⁷Fe, with different amounts of Fe ions replacing Cu. It was shown that magnetic moments on the rare earth site do not interfere with superconductivity. Fe at low concentrations (<1%) was found to replace Cu mainly in the Cu(1) site, and the Mossbauer spectra reveal different quadrupole doublets-fol lowing the different oxygen coordination around the Fe ion. The change of the relative intensities of the different doublets with z can easily be followed. For higher iron concentrations, it seems that increasing amounts of iron replace Cu in the Cu(2) site. For z<6.5, the iron reflects the magnetic ordering of Cu in this site, and the ordering temperature as function of z can be obtained. The agreement between neutron diffraction and Mossbauer measurements prove that Fe is a good probe for the magnetic behaviour of the Cu(2) ions. At low temperatures, Fe Mossbauer spectra of Fe in the Cu(1) site are also magnetically broadened, for all z. Superconducting-magnetic phase diagrams are also obtained in Y_1−x Pr_x Ba₂ Cu₃O_z as function of x and z. For z=7.1, T_N changes sharply with x. T_N=300, 230 and 35 K for x=0.8, 0.6 and 0.4 respectively, whereas for z=6.1 T_N changes very little with x. Mossbauer measurements performed on 5 at %⁵⁷Fe doped in CalaBaCu₃O_z show that most of the la occupy the Ba site. For z=7 about half the iron in the Cu(2) sites are magnetically ordered, with H_eff=520 kOe and T_N=400 K, even though the sample is superconducting with T_c=35 K. The possibility of coexistence between superconductivity and magnetic order in these systems will be discussed.     

Magnetic ordering of Fe atoms in YBa2(Cu1−x Fe x )3O3 in superand semiconducting states

Magnetic behavior of Fe atoms in YBa₂(Cu_1−x Fe _x )₃O _y system in superconducting (SC) and non-SC states is studied. In SC region one magnetic ordering point T_m1 is observed for all Fe atoms in Cu1 sites: T_m1=10 K and 16 K for x=0.05 and x=0.10, respectively. In the non-SC state for x=0.05 Cu1 and Cu2 sublattices are magnetically independent and two magnetic ordering points are found: T_m1=20 K and T_m2=405K. For x=0.10 a strong magnetic interaction between Cu1 and Cu2 sublattices appears and only one ordering point T_m2=435 K is observed.     

Growth and photorefractive properties of near-stoichiometric In:Fe:Cu:LiNbO3 crystals

The near-stoichiometric LiNbO₃ crystal co-doped with In₂O₃, Fe₂O₃, and CuO has been grown from a Li-rich melt (Li/Nb = 1.38, atomic ratio) by the Czochralski method in air atmosphere for the first time. The OH⁻ absorption spectra were characterized to investigate the structure defects of the crystals. The appearance of the 3506 cm⁻¹ absorption peak manifests that the composition of the grown crystal is close to the stoichiometric ratio. The photorefractive properties were also measured by the two-wave coupling experiments. The results show that the near-stoichiometric In:Fe:Cu:LiNbO₃ crystal has a larger refractive index change, higher recording sensitivity and larger two-wave coupling gain coefficient than those obtained in the congruent In:Fe:Cu:LiNbO₃ crystal under the same experimental conditions. The material of near-stoichiometric In:Fe:Cu:LiNbO₃ crystal is a promising candidate for blue photorefractive holographic recording.