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Register a new userIodine intercalation in Bi/Ca/Co/O layered cobaltites
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Single crystals of the Bi-Ca-Co-O system have been grown using the flux method with cooling from 900$celsius$ and 950$celsius$, respectively. The single crystals are characterized by transmission electron microscopy and X-ray diffraction. The misfit cobaltite [Ca$_2$Bi$_{1.4}$Co$_{0.6}$O$_4$]$^{RS}$[CoO$_2$]$_{1.69}$ single crystals with quadruple ($n$=4) rocksalt (RS) layer are achieved with cooling from 900$celsius$. Such crystal exhibits room-temperature thermoelectric power (TEP) of 180$mu$V/K, much larger than that in Sr-based misfit cobaltites with quadruple RS layer. However, intergrowth of single crystals of quadruple ($n$=4) and triple ($n$=3) RS-type layer-based misfit cobaltites is observed with cooling from 950$celsius$. Both of TEP and resistivity were obviously enhanced by the intergrowth compared to [Ca$_2$Bi$_{1.4}$Co$_{0.6}$O$_4$]$^{RS}$[CoO$_2$]$_{1.69}$ single crystal, while the power factor at room temperature remains unchanged.
Properties of complex oxide thin films can be tuned over a range of values as a function of mismatch, composition, orientation, and structure. Here, we report a strategy for growing structured epitaxial thermoelectric thin films leading to improved Seebeck coefficient. Instead of using single-crystal sapphire substrates to support epitaxial growth, Ca$_3$Co$_4$O$_9$ films are deposited, using the Pulsed Laser Deposition technique, onto Al$_2$O$_3$ polycrystalline substrates textured by Spark Plasma Sintering. The structural quality of the 2000 AA thin film was investigated by Transmission Electron Microscopy, while the crystallographic orientation of the grains and the epitaxial relationships were determined by Electron Back Scatter Diffraction. The use of a polycrystalline ceramic template leads to structured films that are in good local epitaxial registry. The Seebeck coefficient is about 170 $mu$V/K at 300 K, a typical value of misfit material with low carrier density. This high-throughput process, called combinatorial substrate epitaxy, appears to facilitate the rational tuning of functional oxide films, opening a route to the epitaxial synthesis of high quality complex oxides.
The layered misfit cobaltate Ca$_3$Co$_4$O$_9$, also known as Ca$_2$CoO$_3$[CoO$_2$]$_{1.62}$, is a promising p-type thermoelectric oxide. Employing density functional theory, we study its electronic structure and determine, on the basis of Boltzmann theory within the constant-relaxation-time approximation, the thermoelectric transport coefficients. The dependence on strain and temperature is determined. In particular, we find that the $xx$-component of the thermopower is strongly enhanced, while the $yy$-component is strongly reduced, when applying 2% tensile strain. A similar anisotropy is also found in the power factor. The temperature dependence of the conductivity in the $a$-$b$ plane is found to be rather weak above 200 K, which clearly indicates that the experimentally observed transport properties are dominated by inhomogeneities arising during sample growth, i.e., are not intrinsic.
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 ($mu^+$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 $mu^+$SR experiment indicated that the {sf IC-SDW} propagates in the $a$-$b$ plane, with oscillating moments directed along the c axis. These results were quite similar to those for the related compound [Ca$_2$CoO$_3$]$_{0.62}^{rm RS}$[CoO$_2$], {sl i.e.}, Ca$_3$Co$_4$O$_9$. Since the {sf IC-SDW} field in [Ca$_2$Co$_{4/3}$Cu$_{2/3}$O$_4$]$_{0.62}^{rm RS}$[CoO$_2$] was approximately same to those in pure and doped [Ca$_2$CoO$_3$]$_{0.62}^{rm RS}$[CoO$_2$], it was concluded that the {sf IC-SDW} exist in the [CoO$_2$] planes.
We have examined an isovalent Rh substitution effect on the transport properties of the thermoelectric oxide Ca$_3$Co$_{4}$O$_9$ using single-crystalline form. With increasing Rh content $x$, both the electrical resistivity and the Seebeck coefficient change systematically up to $x=0.6$ for Ca$_3$Co$_{4-x}$Rh$_{x}$O$_9$ samples. In the Fermi-liquid regime where the resistivity behaves as $rho=rho_0+AT^2$ around 120 K, the $A$ value decreases with increasing Rh content, indicating that the correlation effect is weakened by Rh $4d$ electrons with extended orbitals. We find that, in contrast to such a weak correlation effect observed in the resistivity of Rh-substituted samples, the low-temperature Seebeck coefficient is increased with increasing Rh content, which is explained with a possible enhancement of a pseudogap associated with the short-range order of spin density wave. In high-temperature range above room temperature, we show that the resistivity is largely suppressed by Rh substitution while the Seebeck coefficient becomes almost temperature-independent, leading to a significant improvement of the power factor in Rh-substituted samples. This result is also discussed in terms of the differences in the orbital size and the associated spin state between Co $3d$ and Rh $4d$ electrons.
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