In this article we present a neutron diffraction in-situ study of the thermal evolution and high-temperature structure of layered cobaltites Y(Ba, Sr)Co2 O5+δ. Neutron thermodiffractograms and magnetic susceptibility measurements are reported in the temperature range 20 K <= T <= 570 K, as well as high resolution neutron diffraction experiments at selected temperatures. Starting from the as-synthesized samples with δ ~ 0.5, we show that the room temperature phases remain stable up to 550 K, where they start loosing oxygen and transform to a vacancy-disordered "112" structure with tetragonal symmetry. Our results also show how the so-called "122" structure can be stabilized at high temperature (around 450 K) in a sample in which the addition of Sr at the Ba site had suppressed its formation. In addition, we present the structural and magnetic properties of the resulting samples with a new oxygen content δ ~ 0.25 in the temperature range 20 K <= T <= 300 K.
Using muon spin spectroscopy we have found that, for both Na$_x$CoO$_2$ (0.6 $\leq x \leq$ 0.9) and 3- and 4-layer cobaltites, a common low temperature magnetic state (which in some cases is manifest as an incommensurate spin density wave) forms in the CoO$_2$ planes. Here we summarize those results and report a dome-shaped relation between the transition temperature into the low-$T$ magnetic state and the composition $x$ for Na$_x$CoO$_2$ and/or the high-temperature asymptotic limit of thermopower in the more complex 3- and 4-layer cobaltites. This behavior is explained using the Hubbard mode…
In this paper we have studied, by means of high-resolution neutron powder diffraction and magnetic susceptibility, the structural and magnetic features of selected samples of the HoBaCo2O5+delta layered cobaltite in the low oxygen content range (0.02<delta<0.22). The results shows a strong antiferromagnetic contribution at room temperature coupled to an intermediate spin state of the Co3+ ions.
A positive muon spin rotation and relaxation ($μ^+$SR) experiment on [Ca$_2$CoO$_3$]$_{0.62}$[CoO$_2$], ({\sl i.e.}, Ca$_3$Co$_4$O$_9$, a layered thermoelectric cobaltite) indicates the existence of two magnetic transitions at $\sim$ 100 K and 400 - 600 K; the former is a transition from a paramagnetic state to an incommensurate ({\sf IC}) spin density wave ({\sf SDW}) state. The anisotropic behavior of zero-field $μ^+$SR spectra at 5 K suggests that the {\sf IC-SDW} propagates in the $a$-$b$ plane, with oscillating moments directed along the c-axis; also the {\sf IC-SDW} is found to exist not…
Magnetism of a misfit layered cobaltite [Ca$_2$Co$_{4/3}$Cu$_{2/3}$O$_4$]$_x^{\rm RS}$[CoO$_2$] ($x \sim$ 0.62, RS denotes a rocksalt-type block) was investigated by a positive muon spin rotation and relaxation ($μ^+$SR) experiment. A transition to an incommensurate ({\sf IC}) spin density wave ({\sf SDW}) state was found below 180 K (= $T_{\rm C}^{\rm on}$); and a clear oscillation due to a static internal magnetic field was observed below 140 K (= $T_{\rm C}$). Furthermore, an anisotropic behavior of the zero-field $μ^+$SR experiment indicated that the {\sf IC-SDW} propagates in the $a$-$b$ …
In this article we study the effects of a partial substitution of Ba with the smaller cation Ca in the layered cobaltites YBaCo_2O_{5+δ} for δ\approx 0.5. Neutron thermodiffractograms are reported for the compounds YBa_{0.95}Ca_{0.05}Co_2O_{5.5} (x_{Ca}=0.05) and YBa_{0.90}Ca_{0.10}Co_2O_{5.5} (x_{Ca}=0.10) in the temperature range 20 K \leq T \leq 300 K, as well as high resolution neutron diffraction experiments at selected temperatures for the samples x_{Ca}=0.05, x_{Ca}=0.10 and the parent compound x_{Ca}=0. We have found the magnetic properties to be strongly affected by the cationic subst…
In this work we present the result of the first experimental investigation of the role of oxygen content on the properties of the HoBaCo2O5+delta layered cobaltite. We have measured the variation of oxygen content as a function of temperature and oxygen partial pressure by means of thermogravimetry coupled to chemical titration analysis. On selected samples of accurately known oxygen content we have undertaken a systematic investigation of their structural, thermal and magnetic properties by means of x-ray diffraction, differential scanning calorimetry and magnetometry. The overall results gai…
We have investigated cobaltite relatives of the layered perovskite cuprates and nickelates, Pr$_{2-x}$Ca$_x$CoO$_4$ ($0.39 \leq x \leq 0.73$) and La$_{2-x}$Sr$_x$CoO$_4$ ($x = 0.61$), using elastic neutron scattering. We have discovered doping-dependent incommensurate short-range ordering of charges and magnetic moments, which in cobaltites occur in the range of heavy doping, $ 0.5 \lesssim x \lesssim 0.75$. The charge order exists already at room temperature and shows no change on cooling. The incommensurability of its propagation vector, ${\bf Q}_c = (ε_c,0,l)$, roughly scales with the conce…
Rare earth perovskite cobaltites are increasingly recognized as materials of importance due to rich physics and chemistry in their ordered-disordered structure for the same composition. Apart from colossal magnetoresistance effect, like manganites, the different forms of cobaltites exhibit interesting phenomena including spin, charge and orbital ordering, electronic phase separation, insulator-metal transition, large thermoelectric power at low temperature. Moreover, the cobaltites which display colossal magnetoresistance effect could be used as read heads in magnetic data storage and also in …
The layered perovskite PrBaCo2O5.5+x demonstrates a strong negative thermal expansion (NTE) which holds potential for being fabricated into composites with zero thermal expansion. The NTE was found to be intimately associated with the spontaneous magnetic ordering, known as magnetovolume effect (MVE). Here we report with compelling evidences that the continuous-like MVE in PrBaCo2O5.5+x is intrinsically of discontinuous character, originating from an magnetoelectric transition from an antiferromagnetic insulating large-volume (AFILV) phase to a ferromagnetic metallic small-volume (FMSV) phase.…
The doped perovskite cobaltite La1-xSrxCoO3 (LSCO) has been advanced as a model system for studying intrinsic magnetic phase separation. We have employed a first-order reversal curve (FORC) method to probe the amount of irreversible switching in bulk polycrystalline LSCO as a function of Sr doping, field cooling procedure, and temperature. The value of the FORC distribution, rho, is used as a measure of the extent of irreversible switching. For x < 0.18, the small values of rho and its ridge-like distribution along local coercivity (Hc) and zero bias (Hb), are characteristic of non-interacting…
A new nanoscale ordered perovskite cobaltite, which consists of 90 degree ordered domains of the layered-112 LaBaCo2O6 has been evidenced by high resolution- transmission electron microscopy. This new form, like the disordered La0.5Ba0.5CoO3 and ordered LaBaCo2O6, exhibits a ferromagnetic transition at TC around 179 K. However, it differs from the two previous forms by its strong magnetic anisotropy, and correlatively by its high value of coercivity (0.42 Tesla) at low temperature. We suggest that this behaviour originates from the locking of magnetic spins in the 90 degree oriented nano-domai…
We report here a discovery of electrically driven insulator to metal transition (IMT) and concomitant isostructural volume expansion in the layered cobaltates which otherwise do not exhibit temperature dependent IMT. These findings are demonstrated at macroscopic, microscopic and atomic scales. With application of voltage growth of metallic regions have been observed in the 2D layered La2-xSrxCoO4. Growth of metallic regions is associated with volume increase (strain as high as 0.3%). Non thermal IMT and electro-strain are proposed to be caused by electro-proliferation of the Co3+ high spin st…
We have investigated the systematic transport properties of the layered 112-type cobaltite LaBaCo2O5.5 by means of electrical resistivity, magnetoresistance, electroresistance and thermoelectric measurements in various conditions. In order to understand the complex conduction mechanism of LaBaCo2O5.5, the transport data have been analyzed using different theoretical models. The system shows semiconductor-semiconductor like transition (TSC) around 326K, corresponding to ferromagnetic transition and in the low temperature region resistivity data follows the Motts variable range hopping model. In…
We present first-principles studies on the orbital states of the layered perovskites Ca$_{2-x}$Sr$_x$RuO$_4$. The crossover from antiferromagnetic (AF) Mott insulator for $x < 0.2$ to nearly ferromagnetic (FM) metal at $x=0.5$ is characterized by the systematic change of the $xy$ orbital occupation. For the AF side ($x < 0.2$), we present firm evidence for the $xy$ ferro-orbital ordering. It is found that the degeneracy of $t_{2g}$ (or $e_g$) states is lifted robustly due to the two-dimensional (2D) crystal-structure, even without the Jahn-Teller distortion of RuO$_6$. This effect dominates, a…
High-Tc Cu oxides consist of the alternating stack of the superconductive CuO2 layer and the block layer, such as Bi2Sr2O4 or La2-xSrxO2. By changing the block layer, we can change their physical properties, such as transition temperature Tc. The thermoelectric Co oxides have a similar layered structure composed of the conductive CoO2 layer and the blocking layer. Thus, we propose that their thremoelectric properties can be finely tuned by modifying the block layer.
The magnetic and magnetotransport properties of the Sr3Fe2-xCoxO7-d system (0.2 <= x <= 1.0) were systematically investigated. This oxide system exhibits a giant magnetoresistance (GMR) effect at low temperatures, reaching up to 80% in 7 T at 5 K. Ac-susceptibility measurements show that there exists a strong competition between ferromagnetic (F) and spin glass states, and the balance between these two magnetic states can be controlled by varying cobalt (x) and/or oxygen contents (d). Importantly, the MR effect is closely related to the magnetic property: the development of magnetic disorderin…
