ABSTRACT
We present an abinitio study of the quasi-2D layered perovskite Sr3Hf2O7 compound, performed within the framework of the density functional theory and lattice dynamics analysis. At high temperatures, this compound takes a I4/mmm centrosymmetric structure (S.G. n. 139); as the temperature is lowered, the symmetry is broken into other intermediate polymorphs before reaching the ground-state structure, which is the Cmc21 ferroelectric phase (S.G. n. 36). One of these intermediate polymorphs is the Ccce structural phase (S.G. n. 68). Additionally, we have probed the C2/c system (S.G n. 15), which was obtained by following the atomic displacements corresponding to the eigenvectors of the imaginary frequency mode localized at the Γ-point of the Ccce phase. By observing the enthalpies at low pressures, we found that the Cmc21 phase is thermodynamically the most stable. Our results show that the I4/mmm and C2/c phases never stabilize in the 0-20 GPa range of pressure values. On the other hand, the Ccce phase becomes energetically more stable at around 17 GPa, surpassing the Cmc21 structure. By considering the effect of entropy and the constant-volume free energies, we observe that the Cmc21 polymorph is energetically the most stable phase at low temperature; however, at 350 K, the Ccce system becomes the most stable. By probing the volume-dependent free energies at 19 GPa, we see that Ccce is always the most stable phase between the two structures and also throughout the studied temperature range. When analyzing the phonon dispersion frequencies, we conclude that the Ccce system becomes dynamically stable only around 19-20 GPa and that the Cmc21 phase is metastable up to 30 GPa.
ABSTRACT
Rare-earth orthochromites with distorted perovskite structure (e.g. RCrO3, R = Sm, Gd) have been under strong debate with respect to the origin of their ferroelectric order. Of particular interest is the question of whether such orthochromites are, in fact, magnetically driven improper ferroelectrics, as many rare-earth manganites or orthoferrites. Here we show, by studying at the atomic scale the rare-earth SmCrO3 system that a distortion of the Sm local environment emerges within the paramagnetic phase, near room temperature. Our Electric Field Gradient measurements combined with first-principles calculations show that the emergent phase cannot be simply ascribed to the Pna21 structure as reported for GdCrO3 or SmCrO3. Instead a local inhomogeneous state, where regular non-polar and polar distorted environments coexist, develops at low temperatures.
ABSTRACT
Highly ordered nanohole arrays of [Formula: see text] manganite have been synthesized using pulsed laser deposition on nanoporous alumina template. Their structure and phase formation were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive x-ray spectroscopy (EDX) and x-ray diffraction (XRD). The magnetic measurements were performed with respect to temperature and field and exhibit a ferromagnetic to paramagnetic transition at 284 K. In addition, the temperature dependence of electrical resistance was measured at different magnetic fields and an insulating phase throughout all the temperatures was observed. The low temperature ferromagnetic insulating state is discussed by the presence of a canted ferromagnetic state induced by the nanoholes. The present work shows the feasibility of combining both the nanoporous alumina template and pulsed laser ablation for the fabrication of perovskite manganite nanohole arrays which can also be extended to fabricate other multicomponent oxide nanohole materials.
ABSTRACT
We report perturbed angular correlation measurements with (111m)Cd/(111)Cd and (111)In/(111)Cd probes, at the ISOLDE-CERN facility, in the manganite compounds BaMnO3, with the 6H and 15R polymorphs, and SrMnO3, with the 4H polymorph. The electric field gradient (EFG) is measured, and found approximately constant in a large temperature range for all the compounds. The EFG is also calculated from first principles with density functional theory, and compared with experimental results by considering diluted substitutional Cd impurities. Based on the results, we assign as sites for the probes the Ba (for BaMnO3-6H, 15R) and Sr (for SrMnO3-4H) sites, apart from fractions of undetermined origin in the case of BaMnO3-6H. We predict the hyperfine parameters in the recently synthesized multiferroic manganite Sr(0.5)Ba(0.5)MnO3, and its variation with the structure and electric polarization, which is found to be very small.
Subject(s)
Barium Compounds/chemistry , Cadmium Radioisotopes/chemistry , Indium Radioisotopes/chemistry , Manganese Compounds/chemistry , Strontium/chemistry , Electricity , Molecular Structure , Quantum Theory , TemperatureABSTRACT
The evolution of the local Jahn-Teller distortion across the LaMnO3+Δ phase diagram was obtained using the perturbed angular correlation local probe technique. We found that upon doping, the local distortion decreases continuously with increasing doping and that no fully Jahn-Teller distorted Mn(3+)O6 octahedra are observed within the orthorhombic insulating phase. A local single-phase scenario is established for the orbital disordered orthorhombic crystallographic structure. We also show that the continuous weakening of the Jahn-Teller distortions is not limited to a single-phase environment and occurs in a similar manner within an undistorted rhombohedric matrix upon lowering the temperature.
ABSTRACT
Highly ordered La2/3Ca1/3MnO3 nanotube arrays were successfully synthesized by a simple and rapid process, combining nanoporous alumina template-assisted synthesis with microwave irradiation. The method offers a quick hands-on route to produce manganite bulk sample and nanotube arrays at relative low-temperatures. We obtain thin wall nanotubes of uniform diameter of 80 nm. The growth mechanism of nanotubes is briefly discussed. Magnetic measurements indicate that the ferromagnetic transition temperature T(c) of the nanotubes is depleted with respect to its bulk counterpart possibly due to the geometric confinement imposed by the thin wall of the nanotubes.
ABSTRACT
In this Letter a detailed study of the electric field gradient (EFG) across the Pr(1-x)Ca(x)MnO(3) phase diagram and its temperature dependence is given. Clearly, distinct EFG behavior for samples outside or inside the charge order (CO) region are observed. The EFG temperature dependence evidences a new phase transition occurring over the broad CO region of the phase diagram. This transition is discontinuous and occurs at temperatures between the charge ordering and the Néel temperatures. The prominent features observed in the EFG are associated with polar atomic vibrations which eventually lead to a spontaneous local electric polarization below CO transition.
