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A mixed-valence state, formally denoted as Fe 2 . 5 + , is observed in the 300 K Mössbauer spectra of the most reduced samples of SmBaFe 2 O 5 + w . Upon cooling below the Verwey-type transition temperature (TV≈ 200 K ) , the component assigned to Fe 2 . 5 + separates into a high-spin Fe 3 + state and an Fe 2 + state with an unusually low internal field. The separation of the mixed-valence state at TV is also confirmed by magnetic susceptibility measurements and differential scanning calorimetry. A model is proposed which accounts for the variation of the amount of the mixed-valence state with the oxygen content parameter w. © 1999 American Physical Society

In this paper, we report the correlation between the magnetic property and the local structure in BaY(Cu0.5Fe0.5)2O5+δ of the “0112” phase containing an unusually large amount of excess oxygen, δ of ∼0.2, when heat treated under a high pressure of 5 GPa. Magnetic susceptibility measurements showed that upon the high-pressure heat treatment, the lower-temperature magnetic transition which had been observed in normal-pressure synthesized, antiferromagnetic BaY(Cu0.5Fe0.5)2O5 disappeared and the higher-temperature transition, i.e., the Néel temperature, was lowered. According to a Rietveld analysis based on x-ray-diffraction data and space group P4/mmm, the distinction between Cu and Fe positions along the c axis inside the oxygen pyramid disappeared. Coulometric titrations and Mössbauer spectroscopy measurements strongly suggested the existence of excess oxygen in the yttrium plane.

The hyperfine interactions at the europium lattice sites in samples of the homologous (Fe,Cu)Sr2(Eu,Ce)nCu2O4+2n+z (n=2,3) series were studied by Eu151 Mössbauer spectroscopy. The work was motivated by the search for new superconducting phases. This homologous series is based on the YBa2Cu3O7−δ (1:2:3) structure. The samples used in the Mössbauer measurements consisted of crystallites with random orientation and grain oriented crystallites. The texture of oriented samples was analyzed by x-ray diffraction. The complete quadrupole Hamiltonian of the 21.5-keV γ-transition of Eu151 was successfully applied in the analyses of all the Mössbauer spectra. In samples having n≤2 the europium atoms occupy a single lattice site, whereas the spectra of the n=3 samples exhibit hyperfine interactions of the two different europium sites. Analyzing the hyperfine parameters of the latter samples was made possible by simultaneous fitting of three spectra, corresponding to three different crystal orientations of the same specimen. This fitting scheme also enables more precise determination of the hyperfine parameters in the n=2 samples. In these samples an electric field gradient (EFG), with a large negative-valued main component (Vzz) parallel with the crystal c axis, was found. In the n=3 samples, the two EFG’s of the europium sites were found to have Vzz components of opposite signs. The negative Vzz value was attributed to the rare-earth site adjacent to the CuO layer. This site, found in all samples of the series, corresponds to the rare-earth site of the 1:2:3 system.

Y1−xEuxBa2Cu4O8 powder samples, with x=0, 0.25, 0.5, 0.75, and 1.0, were synthesized at ambient pressure using either an acetate-tartrate sol-gel method or a LiF flux process. The lattice parameters and purity of the samples were checked using X-ray diffraction. The superconducting transition was monitored by magnetic-susceptibility measurements. Replacing yttrium with europium increased the unit-cell volume, decreased the orthorhombicity (b/a) and the critical temperature. The hyperfine interactions at the europium site were studied by Eu151 Mössbauer spectroscopy. The complete quadrupole Hamiltonian of the 21.5-keV γ transition of Eu151 was successfully applied in the analyses of the Mössbauer spectra. The Mössbauer parameters obtained were found to resemble those measured for the EuBa2Cu3Cu3O7−δ (1:2:3) system. It was demonstrated that magnetic alignment of the crystallites could not be obtained with an 11.7-T field, contrary to the 1:2:3 and other high-Tc systems. The magnetic susceptibility for 1:2:4 single crystals appears to be isotropic.

Simultaneous replacement of Sr by Ba and Y by Eu in the Pb-2213 system was found to yield single-phase Pb2Ba2EuCu3O8+δ samples, suitable for Eu151 Mössbauer measurements. The samples were synthesized by a solid-state reaction of metal oxides and carbonates under an inert atmosphere. An oxygen-rich sample corresponding to δ=1.79 was obtained by annealing the as-synthesized material (δ=0.16) in oxygen. The oxygen annealing increased the size of the lattice constants and led to an orthorhombic-to-tetragonal phase transition of the structure. The samples were also oriented in an 11.7-T magnetic field. The x-ray-diffraction spectra showed that the c axes tended to orient perpendicular to the applied field. The measured Mössbauer spectra exhibited an electric quadrupole interaction typical of the Eu site in high-Tc cuprates. The average orientation angles obtained from fittings of the Mössbauer spectra were in accordance with the results from the x-ray-diffraction measurements.