arXiv subjects

M. Karppinen

Publications and source records attributed to M. Karppinen.

At least 37 records · Page 2Linked to original sources

arXiv2004

Micro-structure and Magnetization of the 80-K Superconductor, TbSr2Cu2.7Mo0.3O7+d

The results of micro-structural and detailed magnetization studies are reported here for our recently published TbSr2Cu2.7Mo0.3O7+d superconductor with a transition temperature (Tc) at as high as 80 K [1]. From XRD and EDX the sample was confirmed to be of single-phase and possess the nominal cation stoichiometry. The SEM images showed well-developed grains for this ceramic high-Tc superconductor. Magnetization measurements at various temperatures and fields revealed bulk superconductivity below 80 K. Magnetization versus applied field (M vs. H) loops at various temperatures below the Tc exhibited clear full penetration field HP. In normal state (> 100 K) the susceptibility follows the Curie-Weiss behavior with an effective paramagnetic moment of 9.83 mB.

cond-mat.supr-con↗

arXiv2004

Effect of Sr-for-Ba isovalent substitution on the local structure, hole distribution and magnetic irreversibility of Cu(Ba,Sr)2YbCu2O6.95(2)

The effect of Sr(II)-for-Ba(II) isovalent substitution on the magnetic irreversibility field (Hirr) of Cu(Ba1-ySry)2YbCu2O6.95(2) (Cu-1212) sample series (y = 0 ~ 0.4) is studied to reveal guiding rules for tailoring the intrinsic Hirr characteristics of high-Tc superconductors. It has been assumed that substitution of the larger alkaline earth cation, Ba(II), by the smaller, Sr(II), might improve the Hirr characteristics as a consequence of the decrease in the thickness of nonsuperconductive blocking block (BB). However, results of the present work show that Sr substitution rather depresses the Hirr characteristics of the Cu-1212-phase superconductors even though the thickness of BB decreases. Both the amount of excess oxygen and the overall positive charge are confirmed to remain constant upon the Sr substitution by wet-chemical and XANES analyses, respectively. However, from neutron diffraction data analysis it is found that Sr substitution breaks the conductive CuO chains in BB by shifting part of the excess oxygen atoms from the characteristic b-axis lattice site to the a-axis site. This is believed to decrease the concentration of mobile holes in the BB, as supported by the results of TEP measurements. The lower Hirr(T) lines of the Sr-substituted samples may thus be attributed to the lower concentration of mobile holes in BB.

cond-mat.supr-con↗

arXiv2004

Oxygen and Cation Ordered Perovskite, Ba2Y2Mn4O11

A three-step route has been developed for the synthesis of a new oxygen-ordered double perovskite, BaYMn2O5.5 or Ba2Y2Mn4O11. (i) The A-site cation ordered perovskite, BaYMn2O5+d, is first synthesized at d ~ 0 by an oxygen-getter-controlled low-O2-pressure encapsulation technique utilizing FeO as the getter for excess oxygen. (ii) The as-synthesized, oxygen-deficient BaYMn2O5.0 phase is then readily oxygenated to the d ~ 1 level by means of 1-atm-O2 annealing at low temperatures. (iii) By annealing this fully-oxygenated BaYMn2O6.0 in flowing N2 gas at moderate temperatures the new intermediate-oxygen-content oxide, BaYMn2O5.5 or Ba2Y2Mn4O11, is finally obtained. From thermogravimetric observation it is seen that the final oxygen depletion from d ~ 1.0 to 0.5 occurs in a single sharp step about 600 C, implying that the oxygen stoichiometry of BaYMn2O5+d is not continuously tunable within 0.5 < d < 1.0. For BaYMn2O5.5 synchrotron x-ray diffraction analysis reveals an orthorhombic crystal lattice and a long-range ordering of the excess oxygen atoms in the YO0.5 layer. The magnetic behavior of BaYMn2O5.5 (with a ferromagnetic transition at ~ 133 K) is found different from those previously reported for the known phases, BaYMn2O5.0 and BaYMn2O6.0.

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arXiv2003

Structural and magnetic properties of MSr2Y1.5Ce0.5Cu2Oz (M-1222) compounds with M = Fe and Co

MSr2Y1.5Ce0.5Cu2Oz (M-1222) compounds, with M = Fe and Co, have been synthesized through a solid-state reaction route. Both compounds crystallize in a tetragonal structure (space group I4/mmm). A Rietveld structural refinement of room-temperature neutron diffraction data for Fe-1222 reveals that nearly half the Fe remains at the M site, while the other half goes to the Cu site in the CuO2 planes. Existence of Fe at two different lattice sites, is also confirmed by 57Fe Mossbauer spectroscopy from which it is inferred that nearly 50% of the total Fe occupies the Cu site in the CuO2 planes as Fe3+, whereas the other 50 % is located at the M site with nearly 40 % as Fe4+ and around 10% as Fe3+. For the M = Co compound, nearly 84 % of Co remains at its designated M site, while the rest occupies the Cu site in the CuO2 planes. The oxygen content, z, based on oxygen occupancies refined from the neutron diffraction data, comes close to 9.0 for both the samples The ZFC and FC magnetization curves as a function of temperature show a complex behavior for both Fe-1222 and Co-1222 compounds.

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arXiv2003

Kinetics and thermodynamics of the degree of order of the B cations in double-perovskite Sr2FeMoO6

Here we show that the B-site cation (Fe/Mo) ordering in the double-perovskite magnetoresistor, Sr2FeMoO6, is controlled by either kinetics or thermal equilibrium depending on the temperature range. In order to enhance the ordering, long synthesis periods at moderate temperatures are thus required. Employment of a special oxygen-getter-controlled low-O2-pressure encapsulation technique for the sample synthesis enabled us to use long heating periods without evident evaporation of Mo, and thereby reach the thermal equilibrium state and a high degree of B-site cation order. For samples fired at 1150C for long periods (> 36 hours), record-high Ms values of 3.7 ~ 3.9 muB were obtained.

cond-mat.str-el↗

arXiv2003

Iron and molybdenum valences in double-perovskite (Sr,Nd)2FeMoO6: electron-doping effect

Double perovskite, (Sr1-xNdx)2FeMoO6, was doped with electrons through partial substitution of divalent Sr by trivalent Nd (0 < x < 0.2). The Fe valence and the degree of B-site order were probed by 57Fe Mossbauer spectroscopy. Replacing Sr by Nd increased the fraction of Fe and Mo atoms occupying wrong sites, i.e. antisite disorder. It had very little effect on the Fe valence: a small but visible increase in the isomer shift was seen for the mixed-valent FeII/III atoms occupying the right site indicating a slight movement towards divalency of these atoms, which was more than counterbalanced by the increase in the fraction of antisite Fe atoms with III valence state. It is therefore argued that the bulk of the electron doping is received by antisite Mo atoms, which - being surrounded by six MoV/VI atoms - prefer the lower IV/V valence state. Thus under Nd substitution, the charge-neutrality requirement inflicts a lattice disorder such that low-valent MoIV/V can exist.

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arXiv2003

The valence state of iron in the Sr2Fe(Mo,W,Ta)O6.0 double-perovskite system: An Fe K-edge and L2,3-edge XANES study

Here we employ both Fe K and L2,3 edge x-ray absorption near-edge structure (XANES) spectroscopy techniques to clarify that iron in the B-site ordered double-perovskite halfmetal, Sr2FeMoO6.0, possesses a mixed-valence state, FeII/III, and accordingly molybdenum a mixed MoV/VI valence state. A reliable interpretation of the spectral features has been made possible by using a series of samples of the Sr2Fe(Mo,W/Ta)O6.0 system. Replacing MoV/VI gradually with WVI causes increasing amount of Fe to adopt the FeII state, whereas TaV substitution shifts the valence of iron towards FeIII. As the valence of Fe increases from II to III in the Sr2Fe(Mo,W/Ta)O6.0 system, the absorption energy at the Fe K-edge gradually shifts towards the higher energy side. Similarly, in the L2,3-edge XANES spectra intermediate spectral features are revealed for the Sr2FeMoO6.0 sample in comparison with those for samples heavily substituted with either W or Ta.

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arXiv2003

Enhanced thermoelectric properties of NaxCoO2 whisker crystals

Single-crystalline whiskers of thermoelectric cobalt oxide, NaxCoO2, have been grown by an unconventional method from potassium-containing compositions, and their transport properties, and chemical compositions were determined. The growth mechanism was analyzed and interpreted by means of thermogravimetric analysis. At 300 K, electrical resistivity r and thermoelectric power S of the whisker are 102 u ohm cm and 83 uV/K, respectively. The power-factor, S2/r, thus is enhanced up to ~ 68 uW/K2 cm.

cond-mat.str-el↗

arXiv2003

Iron valence in double-perovskite (Ba,Sr,Ca)2FeMoO6: Isovalent substitution effect

In the Fe-Mo based B-site ordered double-perovskite, A2FeMoO6.0, with iron in the mixed-valence II/III state, the valence value of Fe is not precisely fixed at 2.5 but may be fine-tuned by means of applying chemical pressure at the A-cation site. This is shown through a systematic 57Fe Mossbauer spectroscopy study using a series of A2FeMoO6.0 [A = (Ba,Sr) or (Sr,Ca)] samples with high degree of Fe/Mo order, the same stoichiometric oxygen content and also almost the same grain size. The isomer shift values and other hyperfine parameters obtained from the Mossbauer spectra confirm that Fe remains in the mixed-valence state within the whole range of A constituents. However, upon increasing the average cation size at the A site the precise valence of Fe is found to decrease such that within the A = (Ba,Sr) regime the valence of Fe is closer to II, while within the A = (Sr,Ca) regime it is closer to the actual mixed-valence II/III state. As the valence of Fe approaches II, the difference in charges between Fe and Mo increases, and parallel with this the degree of Fe/Mo order increases. Additionally, for the less-ordered samples an increased tendency of clustering of the anti-site Fe atoms is deduced from the Mossbauer data.

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arXiv2003

Superconductivity of up to 80 K for Tb-123 - TbSr2Cu2.7Mo0.3O7

The Tb-123 phase has been synthesized in single-phase form with the composition TbSr2Cu2.7Mo0.3O7 by solid-state reaction route and its phase purity is confirmed by neutron powder diffraction experiments. As-synthesized sample does not show superconductivity down to 5 K. An unusually high antiferromagnetic ordering temperature (TN) of around 7 K is seen for Tb. After 120-atm-O2 post-annealing, bulk superconductivity is achieved in the compound at around 30 K, without any significant effect on TN. To achieve higher oxygen content and higher Tc, the as-synthesized sample is subjected to high-pressure oxygenation (HPO) carried out in a closed cell at 5 GPa and 400 oC in the presence of AgO as an excess-oxygen source. This sample exhibited superconductivity onset at around 80 K with a Meissner fraction of larger than 10 % at 5 K. Our observation of superconductivity at 80 K is the highest Tc to-date among the Tb-123 compounds.

cond-mat.supr-con↗

arXiv2003

Superconductivity in CoSr2(Y1-xCax)Cu2O7+d

The roles of aliovalent Ca(II)-for-Y(III) substitution and high-pressure-oxygen annealing in the process of "superconducterizing" the Co-based layered copper oxide, CoSr2(Y1-xCax)Cu2O7+d (Co-1212), were investigated. The as-air-synthesized samples up to x = 0.4 were found essentially oxygen stoichiometric (-0.03 <= d <= 0.00). These samples, however, were not superconductive, suggesting that the holes created by the divalent-for-trivalent cation substitution are trapped on Co in the charge reservoir. Ultra-high-pressure heat treatment carried out at 5 GPa and 500C for 30 min in the presence of Ag2O2 as an excess oxygen source induced bulk superconductivity in these samples. The highest Tc was obtained for the high-oxygen-pressure treated x = 0.3 sample at ~40 K.

cond-mat.supr-con↗

arXiv2003

Sodium and oxygen nonstoichiometry and thermoelectric properties of NaxCoO2+d

The sodium-cobalt oxide NaxCoO2+d is a promising candidate for thermoelectric applications since it may possess simultaneously large thermoelectric power and low resistivity. It is difficult to understand the simultaneous appearance of the two properties within the framework of conventional one-electron models. It has been suggested that the spin state of cobalt ions plays a crucially important role in enhancing the thermoelectric power. In order to study the relationship between the cobalt spin state and thermoelectric properties, NaxCoO2+d samples with precisely controlled sodium and oxygen contents are indispensable. Recently, we established an uncon-ventional sample-synthesis method that enables us to precisely control the Na content in NaxCoO2+d samples. In this article, we discuss the effects of sodium and oxygen nonstoichiometry on the thermoelectric properties of NaxCoO2+d.

cond-mat.str-el↗

arXiv2003

Layered-specific hole concentrations in Bi2Sr2(Y1-xCax)Cu2O8+d as probed by XANES spectroscopy and coulometric redox analysis

Induction of holes not only in the superconductive CuO2 plane but also in the Bi2O2+d charge reservoir of the Bi2Sr2(Y1-xCax)Cu2O8+d superconductor upon CaII-for-YIII substitution is evidenced by means of two independent techniques, i.e., high-resolution x-ray-absorption near-edge structure (XANES) spectroscopy measurements and coulometric redox titrations. The absolute values derived for the CuO2-plane hole concentration from the Cu L2,3-edge XANES spectra are in good agreement with those obtained from the coulometric redox analysis. The CuO2-plane hole concentration is found to increase from 0.03 to 0.14 concomitantly with the increase in the BiO1+d/2-layer hole concentration from 0.00 to 0.13 as the Ca-substitution level, x, increases from 0 to 1. The threshold CuO2-plane hole concentration for the appearance of superconductivity is determined at 0.06, while the highest Tc is obtained at the hole concentration of 0.12. In the O K-edge XANES spectrum, the increases in the CuO2-plane and BiO1+d/2-layer hole concentrations with increasing x are seen as enhancement in the relative intensities of the pre-edge peaks at ~528.3 and \~530.5 eV, respectively.

cond-mat.supr-con↗

arXiv2002

Unconventional magnetic transition and transport behavior in Na0.75CoO2

Here we report an unconventional magnetic and transport phenomenon in a layered cobalt oxide, NaxCoO2. Only for x = 0.75, a magnetic transition of the second order was clearly detected at Tm ~ 22 K where an apparent specific-heat jump, an onset of extremely small spontaneous magnetization, and a kink in resistivity came in. Moreover large positive magnetoresistance effect was observed below Tm. These features of the transition strongly indicate the appearance of an unusual electronic state that may be attributed to the strongly-correlated electrons in Na0.75CoO2.

cond-mat.str-el↗

arXiv2002

Magneto-superconductivity of 100-atm O2-annealed RuSr2Gd1.5Ce0.5Cu2O10

Studied 100-atm O2-annealed RuSr2Gd1.5Ce0.5Cu2O10 (Ru-1222) compound crystallized in a tetragonal I4/mmm space group crystal structure. Thermo-gravemetric (TG) analysis of the compound showed the release of oxygen and breaking to metallic constituents in two distinct steps at around 350 and 500 0C. The DC magnetization data (M vs. T) revealed magnetic transition at 100 K followed by superconducting transition at 40 K. Low field M vs. H hysteresis loop showed a lower critical field (Hc1) value of around 25 Oe. Ferromagnetic component is evidenced at 5, 10, 20 and 40 K. Near saturation field of above 5 Tesla is observed at 5 K. Zero-field returning moment (Mr) and zero-moment coercive field (Hc) values at 5 K are 0.35mB and 250 Oe. The resistance vs. temperature (R vs. T) behaviour of the sample confirmed superconductivity at around 43 K. Superconductivity transition (Tc) is broadened under magnetic field with strong granularity like steps.

cond-mat.supr-con↗

arXiv2002

Oxygen non-stoichiometry in Ru-1212 and Ru-1222 magnetosuperconductors

Here we report the results of thermogravimetric (TG) analysis on the oxygen non-stoichiometry of RuSr2GdCu2O8 (Ru-1212) and RuSr2(Gd0.75Ce0.25)2Cu2O10(Ru-1222) samples. With TG annealings carried out in O2 and Ar atmospheres it was found that the oxygen content in Ru-1212 remains less affected upon various annealings, while for Ru-1222 wider-range oxygen-content tuning is possible. When heated in H2/Ar atmosphere the both phases release oxygen upon breaking down to mixtures of metals (Ru and Cu) and binary oxides (CeO2, Gd2O3, and SrO) in two distinct steps around 300 and 450 oC. This reductive decomposition reaction carried out in a thermobalance was utilized in precise oxygen content determination for these phases. It was found that the 100-atm O2-annealed Ru-1212 sample was nearly stoichiometric, while the similarly treated Ru-1222 sample was clearly oxygen deficient. X-ray absorption near-edge (XANES) spectroscopy was applied to estimate the valence of Ru in the samples. In spite of the fact that the Ru-1212 phase was shown to possess less oxygen-deficient RuO2 layer, the valence of Ru as probed with XANES was found to be lower in Ru-1212 than that in Ru-1222.

cond-mat.supr-con↗

arXiv2002

Oxygen Stoichiometry in Co-1212, Co-1222 and Co-1232 of Homologous Series Co-12s2 of Category-B Layered Copper Oxides

Here results of a systematic study on oxygen stoichiometry are reported for the first three members of the novel CoSr2(Y,Ce)sCu2O5+2s or Co-12s2 homologous series, i.e. Co-1212, Co-1222 and Co-1232 phases with a SrO-CoO1-SrO-CuO2-(Y,Ce)-[O2-(Y,Ce)]s-1-CuO2 layered structure. The oxygen content was precisely determined by two independent chemical techniques: coulometric Cu+/Cu2+ titration and iodometric titration. Furthermore, oxygen stability/tunability was investigated by means of oxygenative and reductive an-nealings carried out in a thermobalance. It was revealed that all the three phases are rather stoichiometric in oxygen content and stable against both oxygenative and reductive an-nealings. The present results for the Co-12s2 homologous series suggest that not only the CoO1 charge reservoir but also the nominally oxygen-stoichiometric B-[O2-B]s-1 fluo-rite block, that is the characteristic structural element for the Co-12s2 (s > 1) phases and all other layered copper oxides of category-B [H. Yamauchi and M. Karppinen, Superlatt. Microstructr. 21A (1997) 128] is non-tunable in terms of the oxygen content.

cond-mat.supr-con↗

arXiv2002

Glass component induced hysteresis/memory effect in magnetoresistance of ferromagnetic Pr0.9Sr0.1CoO2.99

Pr0.9Sr0.1CoO2.99 sample exhibits magnetoresistivity (MR) of up to 40 % at 5 K with a strong hysteresis/memory effect. Magnetisation measurements on Pr0.9Sr0.1CoO2.99 in an applied field of 100 Oe show that, as temperature decreases, the zero-field-cooled (ZFC) and field-cooled (FC) magnetisation curves branch clearly at 50 K, and a cusp appears in the ZFC branch at Tcusp 20 K. Magnetisation measurements in various fields between 100 and 10,000 Oe show that both the ZFC-FC branching temperature and, Tcusp, decrease with increasing field. The magnetization-field isotherms at 5 and 10 K show hysteresis loops typical of ferromagnets. No appreciable MR is seen in this compound at 50 K, i.e. at a temperature close to ZFC-FC branching temperature. At 20 K, negative MR of above 16% is observed without any hysteresis effect. We believe that the appearance of a ferromagnetic component at 5 K and 10 K (i.e. at temperatures below Tcusp) within the spin glass state of Co spins is responsible for both large MR and the prominent hysteresis/memory effect in MR.

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