No Arabic abstract
We have investigated the effect of Ti doping on the transport properties coupled with the magnetic ones in Sm$_{0.55}$Sr$_{0.45}$Mn$_{1-eta}$Ti$_{eta}$O$_3$ ($0 leq eta leq 0.04$). The parent compound, Sm$_{0.55}$Sr$_{0.45}$MnO$_3$, exhibits a first-order paramagnetic-insulator to ferromagnetic-metal transition just below $T_{rm c}$ = 128 K. With substitution of Ti at Mn sites ($B$-site), $T_{rm c}$ decreases approximately linearly at the rate of 22 K$%^{-1}$ while the width of thermal hysteresis in magnetization and resistivity increases almost in an exponential fashion. The most spectacular effect has been observed for the composition $eta$=0.03, where a magnetic field of only 1 T yields a huge magnetoresistance, $1.2 times 10^7$ $%$ at $T_capprox$ 63 K. With increasing magnetic field, the transition shifts towards higher temperature, and the first-order nature of the transition gets weakened and eventually becomes crossover above a critical field ($H_{cr}$) which increases with Ti doping. For Ti doping above 0.03, the system remains insulting without any ferromagnetic ordering down to 2 K. The Monte-Carlo calculations based on a two-band double exchange model show that the decrease of $T_{rm c}$ with Ti doping is associated with the increase of the lattice distortions around the doped Ti ions.
The defect chemistry of perovskite compounds is directly related to the stoichiometry and to the valence states of the transition metal ions. Such relations are of high interest as they offer the possibility to influence the catalytic activity of perovskites for the application in solid-oxide fuel- and electrolyser cells. Combining theoretical and experimental approaches, we explore the feasibility of actively manipulating the valence state of Fe and the concentration of point defects by synthesizing non-stoichiometric LaFeO$_3$ (LFO). In the theoretical part, formation energies and concentrations of point defects were determined as a function of processing conditions by first-principles DFT+U calculations. Based on the DFT+U results, significant compositional deviations from stoichiometric LFO cannot be expected by providing rich or poor conditions of the oxidic precursor compounds (Fe$_2$O$_3$ and La$_2$O$_3$) in a solid-state processing route. In the experimental part, LFO was synthesized with a targeted La-site deficiency. We analyze the resulting phases in detail by X-ray diffraction and dedicated microscopy methods, namely scanning electron microscopy (SEM) and (scanning) transmission electron Microscopy ((S)TEM) in combination with energy dispersive X-ray spectroscopy (EDS) and electron energy-loss spectrometry (EELS). Instead of a variation of the La/Fe ratio, a mixture of two phases, Fe$_2$O$_3$/LaFeO$_3$, was observed resulting in an invariant charge state of Fe, which is in line with the theoretical results. We discuss our findings with respect to partly differing assumptions made in previously published studies on this material system.
Charge transfer induced interfacial ferromagnetism and its impact on the exchange bias effect in La$_{0.7}$Sr$_{0.3}$MnO$_3$/NdNiO$_3$ correlated oxide heterostructures were investigated by soft x-ray absorption and x-ray magnetic circular dichroism spectra in a temperature range from 10 to 300 K. Besides the antiferromagnetic Ni$_3^+$ cations which are naturally part of the NdNiO$_3$ layer, Ni$_2^+$ ions are formed at the interface due to a charge transfer mechanism involving the Mn element of the adjacent layer. They exhibit a ferromagnetic behavior due to the exchange coupling to the Mn$_4^+$ ions in the La$_{0.7}$Sr$_{0.3}$MnO$_3$ layer. This can be seen as detrimental to the strength of the unidirectional anisotropy since a significant part of the interface does not contribute to the pinning of the ferromagnetic layer. By analyzing the line shape changes of the x-ray absorption at the Ni L$_{2,3}$ edges, the metal-insulator transition of the NdNiO$_3$ layer is resolved in an element specific manner. This phase transition is initiated at about 120 K, way above the paramagnetic to antiferromagnetic transition of NdNiO$_3$ layer which measured to be 50 K. Exchange bias and enhanced coercive fields were observed after field cooling the sample through the Neel temperature of the NdNiO$_3$ layer. Different from La$_{0.7}$Sr$_{0.3}$MnO$_3$/LaNiO$_3$, the exchange bias observed in La$_{0.7}$Sr$_{0.3}$MnO$_3$/NdNiO$_3$ is due to the antiferromagnetism of NdNiO$_3$ and the frustration at the interface. These results suggest that reducing the interfacial orbital hybridization may be used as a tunable parameter for the strength of the exchange bias effect in all-oxide heterostructures which exhibit a charge transfer mechanism.
Microscopic origin of the ferromagnetic (FM) exchange coupling in CrCl$_3$ and CrI$_3$, their common aspects and differences, are investigated on the basis of density functional theory combined with realistic modeling approach for the analysis of interatomic exchange interactions. We perform a comparative study based on the pseudopotential and linear muffin-tin orbital methods by treating the effects of electron exchange and correlation in GGA and LSDA, respectively. The results of ordinary band structure calculations are used in order to construct the minimal tight-binding type models describing the behavior of the magnetic Cr $3d$ and ligand $p$ bands in the basis of localized Wannier functions, and evaluate the effective exchange coupling ($J_{rm eff}$) between two Cr sublattices employing four different technique: (i) Second-order Greens function perturbation theory for infinitesimal spin rotations of the LSDA (GGA) potential at the Cr sites; (ii) Enforcement of the magnetic force theorem in order to treat both Cr and ligand spins on a localized footing; (iii) Constrained total-energy calculations with an external field, treated in the framework of self-consistent linear response theory. We argue that the ligand states play crucial role in the ferromagnetism of Cr trihalides, though their contribution to $J_{rm eff}$ strongly depends on additional assumptions, which are traced back to fundamentals of adiabatic spin dynamics. Particularly, by neglecting ligand spins in the Greens function method, $J_{rm eff}$ can easily become antiferromagnetic, while by treating them as localized, one can severely overestimate the FM coupling. The best considered approach is based on the constraint method, where the ligand states are allowed to relax in response to each instantaneous reorientation of the Cr spins, controlled by the external field.
The effects of rhenium doping in the range 0 to 10 atomic percent on the static and dynamic magnetic properties of Fe65Co35 thin films have been studied experimentally as well as with first principles electronic structure calculations focusing on the change of the saturation magnetization and the Gilbert damping parameter. Both experimental and theoretical results show that the saturation magnetization decreases with increasing Re doping level, while at the same time Gilbert damping parameter increases. The experimental low temperature saturation magnetic induction exhibits a 29 percent decrease, from 2.31 T to 1.64 T, in the investigated doping concentration range, which is more than predicted by the theoretical calculations. The room temperature value of the damping parameter obtained from ferromagnetic resonance measurements, correcting for extrinsic contributions to the damping, is for the undoped sample 0.0027, which is close to the theoretically calculated Gilbert damping parameter. With 10 atomic percent Re doping, the damping parameter increases to 0.0090, which is in good agreement with the theoretical value of 0.0073. The increase in damping parameter with Re doping is explained by the increase in density of states at Fermi level, mostly contributed by the spin-up channel of Re. Moreover, both experimental and theoretical values for the damping parameter are observed to be weakly decreasing with decreasing temperature.
The incorporation of Eu into the diamond lattice is investigated in a combined theoretical-experimental study. The large size of the Eu ion induces a strain on the host lattice, which is minimal for the Eu-vacancy complex. The oxidation state of Eu is calculated to be 3+ for all defect models considered. In contrast, the total charge of the defect-complexes is shown to be negative -1.5 to -2.3 electron. Hybrid-functional electronic-band-structures show the luminescence of the Eu defect to be strongly dependent on the local defect geometry. The 4-coordinated Eu substitutional dopant is the most promising candidate to present the typical Eu3+ luminescence, while the 6-coordinated Eu-vacancy complex is expected not to present any luminescent behaviour. Preliminary experimental results on the treatment of diamond films with Eu-containing precursor indicate the possible incorporation of Eu into diamond films treated by drop-casting. Changes in the PL spectrum, with the main luminescent peak shifting from approximately 614 nm to 611 nm after the growth plasma exposure, and the appearance of a shoulder peak at 625 nm indicate the potential incorporation. Drop-casting treatment with an electronegative polymer material was shown not to be necessary to observe the Eu signature following the plasma exposure, and increased the background luminescence.