No Arabic abstract
The d.c. magnetization and magnetic relaxation studies of the calcium doped samples, Y0.95Ca0.05BaCo2O5.5 and YBa0.95Ca0.05Co2O5.5, show the existence of a magnetic glass like behaviour in the family of cobaltites for the first time. Our investigations reveal glass-like arrest of kinetics at low temperature which prevents the system from reaching its magnetic ground state. We show that the low temperature state of these calcium doped phases, which consists of coexisting antiferromagnetic and ferro (or ferri) magnetic phase fractions, can be tuned in a number of ways. Our observations establish that the low temperature state of this oxide is not in thermal equilibrium. The glassy state is formed with the assistance of an external magnetic field, which makes it distinctly different from the more well known metastable state, the spin glass state. The cooling field can tune the fractions of the coexisting phases, and the glass-like state formed at low temperature can also be devitrified by warming the sample. The role of Ca doping in the appearance of these phenomena is discussed in terms of phase separation, involving Co3+ disproportionation into Co4+ ferromagnetic clusters and Co2+ antiferromagnetic clusters.
Doped perovskite cobaltites (e.g., La$_{1-x}$Sr$_x$CoO$_3$) have been extensively studied for their spin-state physics, electronic inhomogeneity, and insulator-metal transitions. Ferromagnetically-interacting spin-state polarons emerge at low $x$ in the phase diagram of these compounds, eventually yielding long-range ferromagnetism. The onset of long-range ferromagnetism ($x approx 0.18$) is substantially delayed relative to polaron percolation ($x approx 0.05$), however, generating a troubling inconsistency. Here, Monte-Carlo simulations of a disordered classical spin model are used to establish that previously ignored magnetic frustration is responsible for this effect, enabling faithful reproduction of the magnetic phase diagram.
The triple magnetic-transport-structural transition versus temperature in three series of 114 cobaltites - Y1-xYbxBaCo4O7, Y1-xCaxBaCo4O7 and Yb1-xCaxBaCo4O7 - has been studied using magnetic, transport and differential scanning calorimetric measurements. The effect of the size mismatch {sigma}2, due to cationic disordering at the Ln sites upon such a transition is shown for the first time in a triangular lattice. We show that increasing <rLn> has an effect of increasing TS dramatically, while the size mismatch {sigma}2 at the Ln sites decreases TS substantially. Moreover, the cationic mismatch at the Ln sites modifies the nature of the hysteretic transition by turning the sharp first order transition seen in the undoped samples into an intermix of first and second order transitions. These results are discussed on the basis of the particular nature of the high temperature form which exhibits a hexagonal close packed structure (space group: P63mc) with respect to the low temperature orthorhombic form (space group: Pbn21), the latter corresponding to a distortion of the former due to a puckering of the kagome layers.
We report data on the luminescence spectra associated with photochromic centers in X-ray irradiated calcium fluoride crystals doped with Lu ions. Irradiation in low energy photochromic centers absorption band excites emission, which can be identify with transitions into photochromic centers. Ab initio calculation of absorption spectrum of photochromic center agrees rather well with experimental data.
Ce3+ doped oxide materials are promising for optical emission in the green spectral range. The growth of CaSc2O4:Ce3+ single crystals is reported here for the first time. Laser heated pedestal growth (LHPG) proved to be suitable for this refractive material, if performed in nitrogen of 99.999% purity. If the oxygen content of the growth atmosphere is substantially larger, Ce4+ is formed, which shows no useful optical emission. If the oxygen content is substantially lower, severe evaporation of calcium impedes stable crystal growth. Thermodynamic equilibrium calculations allowed to describe evaporation of species and cerium dopant charging under different growth conditions. The evaporation could be investigated by quadrupole mass spectrometry of emanating gases and by chemical analysis of fibers with ICP-OES. The congruent melting point was confirmed by DTA at 2110 degrees centigrade. Photoluminescence spectrometry of fibers revealed the dependence of optical emission in the green spectral range on growth conditions.
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 other applications depending upon their particular properties. The A-site ordereddisordered cobaltites exhibit ferromagnetism and metal-insulator transitions as well as other properties depending on the composition, size of A-site cations and various external factors such as pressure, temperature, magnetic field etc. Ordered cobaltites, having a 112-type layered structure, are also reported to have an effectively stronger electron coupling due to layered A-site cationic ordering. Most importantly for the present article we focus on La-Ba-Co-O based ordered-disordered perovskite phases, which exhibit interesting magnetic and electron transport properties with ferromagnetic transition, TC ~ 177K, and it being the first member of lanthanide series. Zener double exchange mechanism considered to be crucial for understanding basic physics of the ferromagneticmetallic phase, yet does not explain clearly the insulating-type phase. In terms of electron transport the ferromagnetic-metallic or insulating/semiconducting states have been discussed in the present article with different types of hopping model.