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 arran
gements are of canted type, A$_x$G$_y$ for TbCoO$_3$ and G$_x$A$_y$ for DyCoO$_3$ in Bertauts 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.
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 glas
s 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.
The electric, magnetic, and thermal properties of three perovskite cobaltites with the same 30% hole doping and ferromagnetic ground state were investigated down to very low temperatures. With decreasing size of large cations, the ferromagnetic Curie
temperature and spontaneous moments of cobalt are gradually suppressed - $T_C=130$ K, 55 K and 25 K and $m = 0.68 mu_B$, 0.34 $mu_B$ and 0.23 $mu_B$ for Nd$_{0.7}$Sr$_{0.3}$CoO$_3$, Pr$_{0.7}$Ca$_{0.3}$CoO$_3$ and Nd$_{0.7}$Ca$_{0.3}$CoO$_3$, respectively. The moment reduction with respect to moment of the conventional ferromagnet La$_{0.7}$Sr$_{0.3}$CoO$_3$ ($T_C=230$ K, $m = 1.71 mu_B$) in so-called IS/LS state for Co$^{3+}$/Co$^{4+}$, was originally interpreted using phase-separation scenario. Based on the present results, mainly the analysis of Schottky peak originating in Zeeman splitting of the ground state Kramers doublet of Nd$^{3+}$, we find, however, that ferromagnetic phase in Nd$_{0.7}$Ca$_{0.3}$CoO$_3$ and likely also Pr$_{0.7}$Ca$_{0.3}$CoO$_3$ is uniformly distributed over all sample volume, despite the severe drop of moments. The ground state of these compounds is identified with the LS/LS-related phase derived theoretically by Sboychakov textit{et al.} [Phys. Rev. B textbf{80}, 024423 (2009)]. The ground state of Nd$_{0.7}$Sr$_{0.3}$CoO$_3$ with an intermediate cobalt moment is inhomogeneous due to competing of LS/LS and IS/LS phases. In the theoretical part of the study, the crystal field split levels for $4f^3$ (Nd$^{3+}$), $4f^2$ (Pr$^{3+}$) and $4f^1$ (Ce$^{3+}$ or Pr$^{4+}$) are calculated and their magnetic characteristics are presented.
We present an extensive investigation (magnetic, electric and thermal measurements and X-ray absorption spectroscopy) of the Pr0.5Ca0.5CoO3 and (Pr1-yYy)0.7Ca0.3CoO3 (y=0.0625-0.15) perovskites, in which a peculiar metal-insulator (M-I) transition, a
ccompanied with pronounced structural and magnetic anomalies, occurs at 76 K and 40-132 K, respectively. The inspection of the M-I transition using the XANES data of Pr L3-edge and Co K-edge proofs the presence of Pr4+ ions at low temperatures and indicates simultaneously the intermediate spin to low spin crossover of Co species on lowering the temperature. The study thus definitively confirms the synchronicity of the electron transfer between Pr3+ ions and Co^(3+/4+)O3 subsystem and the transition to the low-spin, less electrically conducting phase. The large extent of the transfer is evidenced by the good quantitative agreement of the determined amount of the Pr4+ species, obtained either from the temperature dependence of the XANES spectra or via integration of the magnetic entropy change over the Pr4+ related Schottky peak in the low-temperature specific heat. These results show that the average valence of Pr3+/Pr4+ ions increases (in concomitance with the decrease of the formal Co valence) below TMI for (Pr0.925Y0.075)0.7Ca0.3CoO3 up to 3.16+ (the doping level of the CoO3 subsystem decreases from 3.30+ to 3.20+), for (Pr0.85Y0.15)0.7Ca0.3CoO3 up to 3.28+ (the decrease of doping level from 3.30+ to 3.13+) and for Pr0.5Ca0.5CoO3 up to 3.46+ (the decrease of doping level from 3.50+ to 3.27+).
Two extreme members of the cobaltite series, LaCoO3 and DyCoO3, were investigated by the electrical resistivity and thermopower measurements up to 800-1000 K. Special attention was given to effects of extra holes or electrons, introduced by light dop
ing of Co sites by Mg2+ or Ti4+ ions. The experiments on the La based compounds were complemented with magnetic measurements. The study shows that both kinds of charge carriers induce magnetic states on surrounding CoIII sites and form thus thermally stable polarons of large total spin. Their itinerancy is characterized by low temperature resistivity, which is of Arrhenius type r~exp(EA/kT) for the hole (CoIV) doped samples, while an unusual dependence r~1/Tn (n=8-10) is observed for the electron (CoII) doped samples. At higher temperatures, additional hole carriers are massively populated in the CoIII background, leading to a resistivity drop. This transition become evident at ~300 K and 450 K and culminates at TI-M=540 and 780 K for the La and Dy based samples, respectively. The electronic behaviours of the cobaltites are explained considering two excitation processes in parent compounds. The first one is related to a local excitation from the diamagnetic LS CoIII to close-lying paramagnetic HS CoIII state. Secondarily, a metallic phase of the IS CoIII character is formed through a charge transfer mechanism between LS/HS pairs. The magnetic polarons associated with doped carriers are interpreted as droplets of such IS phase.
The samples LaCoO3 with dilute substitutions on cobalt sites have been studied using the resistivity, thermopower and magnetic susceptibility measurements over the temperature range up to ~900 K. The Co-site substitution does not affect the magnetic
transition at ~100 K and the onset of massive population of hole carriers at ~500 K, characteristic for undoped LaCoO3. On the other hand, the low-temperature transport and magnetism is markedly distinct for samples with extra charge on cobalt ions introduced by the heterovalent dopants (Mg2+, Ti4+) compared to samples with minor non-stoichiometry (LaCoO3, Ga3+ doped sample). Magnetic properties suggest that these extra charges create thermally stable magnetic polarons of total S ~ 2-3. Common features of Co-site doped and La-site doped samples (La1-xSrxCoO3) are discussed
The diamagnetic-paramagnetic and insulator-metal transitions in LnCoO3 perovskites (Ln = La, Y, rare earths) are reinterpreted and modeled as a two-level excitation process. In distinction to previous models, the present approach can be characterized
as a LS-HS-IS (low-high-intermediate spin) scenario. The first level is the local excitation of HS Co3+ species in the LS ground state. The second excitation is based on the interatomic electron transfer between the LS/HS pairs, leading finally to a stabilization of the metallic phase based on IS Co3+. The model parameters have been quantified for Ln = La, Pr and Nd samples using the powder neutron diffraction on the thermal expansion of Co-O bonds, that is associated with the two successive spin transitions. The same model is applied to interpret the magnetic susceptibility of LaCoO3 and YCoO3.
