arXiv subjects

Z. Jirák

Publications and source records attributed to Z. Jirák.

4 recordsLinked to original sources

arXiv2015

Spin-entropy contribution to thermopower in the [Ca$_2$CoO$_{3-t}$]$_{0.62}$(CoO$_2$) misfits

Two samples of the [Ca$_2$CoO$_{3-t}$]$_{0.62}$(CoO$_2$) misfit cobaltate, often denoted as the Ca$_{3}$Co$_{3.93}$O$_{9}$ phase, were prepared from the same ceramic material by the oxygen and argon annealing, resulting in different carrier concentrations in the conducting CoO$_{2}$ layers, n=0.31 and 0.19 hole/Co, respectively. Electrical and thermal transport properties were studied in dependence of magnetic field up to 140 kOe. The magnetothermopower data reveal an extra spin-entropy contribution to Seebeck coefficient that is not expected for carriers of Fermi liquid character. Its magnitude is unprecedentedly large and makes at zero field up to 50$\%$ of the theoretical limit k$_B$/$e$ ln2$ = 59 μVK^{-1}$. This spin-entropy contribution is gradually suppressed with increasing magnetic field, and the saturation is even observed when temperatures are low enough. To understand the results, the thermopower is treated in terms of purely thermodynamic Kelvin formula, and so-called Spin liquid model is evoked, providing a reason for the spin-entropy manifestation in the [Ca$_2$CoO$_{3-t}$]$_{0.62}$(CoO$_2$) misfits.

cond-mat.mtrl-sci↗

arXiv2014

Effect of Ising-type Tb$^{3+}$ ions on the low-temperature magnetism of La, Ca cobaltite

Crystal and magnetic structures of the $x=0.2$ member of La$_{\rm 0.8-x}$Tb$_{\rm x}$Ca$_{0.2}$CoO$_3$ perovskite series have been determined from the powder neutron diffraction. Enhancement of the diffraction peaks due to ferromagnetic or cluster glass ordering is observed below $T_C=55$ K. The moments evolve at first on Co sites, and ordering of Ising-type Tb$^{3+}$ moments is induced at lower temperatures by a molecular field due to Co ions. The final magnetic configuration is collinear F$_x$ for cobalt subsystem, while it is canted F$_x$C$_y$ for terbium ions. The rare-earth moments align along local Ising axes within \textit{ab}-plane of the orthorhombic $Pbnm$ structure. The behavior in external fields up to $70-90$ kOe has been probed by the magnetization and heat capacity measurements. The dilute terbium ions contribute to significant coercivity and remanence that both steeply increase with decreasing temperature. A remarkable manifestation of the Tb$^{3+}$ Ising character is the observation of a low-temperature region of anomalously large linear term of heat capacity and its field dependence. Similar behaviours are detected also for other terbium dopings $x=0.1$ and 0.3.

cond-mat.mtrl-sci↗

arXiv2013

Non-collinear magnetic structures of TbCoO$_3$ and DyCoO$_3$

The orthoperovskites TbCoO$_3$ and DyCoO$_3$ with Co$^{3+}$ in a non-magnetic low-spin state have been investigated by neutron diffraction down to 0.25 K. Magnetic ordering is evidenced below $T_N=3.3$ K and 3.6 K, respectively, and the ordered arrangements are of canted type, A$_x$G$_y$ for TbCoO$_3$ and G$_x$A$_y$ for DyCoO$_3$ in Bertaut's notation. The experiments are confronted with the first-principle calculations of the crystal field and magnetism of Tb$^{3+}$ and Dy$^{3+}$ ions, located in the $Pbnm$ structure on sites of $C_s$ point symmetry. Both these ions exhibit an Ising behavior, which originates in the lowest energy levels, in particular in accidental doublet of non-Kramers Tb$^{3+}$ ($4f^8$ configuration) and in ground Kramers doublet of Dy$^{3+}$ ($4f^9$) and it is the actual reason for the non-collinear AFM structures. Very good agreement between the experiment and theory is found. For comparison, calculations of the crystal field and magnetism for other systems with Kramers ions, NdCoO$_3$ and SmCoO$_3$, are also included.

cond-mat.mtrl-sci↗

arXiv2012

Stabilization of the high-spin state of Co$^{3+}$ in LaCo$_{1-x}$Rh$_{x}$O$_3$

The rhodium doping in the LaCo$_{1-x}$Rh$_{x}$O$_3$ perovskite series ($x=0.02-0.5$) has been studied by X-ray diffraction, electric transport and magnetization measurements, complemented by electronic structure GGA+U calculations in supercell for different concentration regimes. No charge transfer between Co$^{3+}$ and Rh$^{3+}$ is evidenced. The diamagnetic ground state of LaCoO$_3$, based on Co$^{3+}$ in low-spin (LS) state, is disturbed even by a small doping of Rh. The driving force is the elastic energy connected with incorporation of a large Rh$^{3+}$ cation into the matrix of small LS Co$^{3+}$ cations, which is relaxed by formation of large Co$^{3+}$ in high-spin (HS) state in the next-nearest sites to the inserted Rh atom. With increasing temperature, the population of Co$^{3+}$ in HS state increases through thermal excitation, and a saturated phase is obtained close to room temperature, consisting of a nearest-neighbor correlation of small (LS Co$^{3+}$) and large (HS Co$^{3+}$ and LS Rh$^{3+}$) cations in a kind of double perovskite structure. The stabilizing role of elastic and electronic energy contributions is demonstrated in supercell calculations for dilute Rh concentration compared to other dopants with various trivalent ionic radius.

cond-mat.mtrl-sci↗