Long-range Ni/Mn structural order in epitaxial double perovskite La2NiMnO6 thin films

We report and compare the structural, magnetic, and optical properties of ordered La2NiMnO6 thin films and its disordered LaNi0.5Mn0.5O3 counterpart. An x-ray diffraction study reveals that the B-site Ni/Mn ordering induces additional XRD reflections as the crystal symmetry is transformed from a pseudocubic perovskite unit cell in the disordered phase to a monoclinic form with larger lattice parameters for the ordered phase. Polarized Raman spectroscopy studies reveal that the ordered samples are characterized by additional phonon excitations that are absent in the disordered phase. The appearance of these additional phonon excitations is interpreted as the clearest signature of Brillouin zone folding as a result of the long-range Ni/Mn ordering in La2NiMnO6. Both ordered and disordered materials display a single ferromagnetic-to-paramagnetic transition. The ordered films display also a saturation magnetization close to 4.8 mB/f.u. and a transition temperature (FM-TC) around 270 K, while the disordered ones have only a 3.7 mB/f.u. saturation magnetization and a FM-TC around 138 K. The differences in their magnetic behaviours are understood based on the distinct local electronic configurations of their Ni/Mn cations.Comment: 15 pages, 5 fig

Phase formation, phonon behavior, and magnetic properties of novel ferromagnetic La3BAlMnO9 (B = Co or Ni) triple perovskites

In the quest for novel magnetoelectric materials, we have grown, stabilized and explored the properties of La3BAlMnO9 (B = Co or Mn) thin films. In this paper, we report the influence of the growth parameters that promote B/Al/Mn ordering in the pseudo-cubic unit cell and their likely influence on the magnetic and multiferroic properties. The temperature dependence of the magnetization shows that La3CoAlMnO9 is ferromagnetic up to 190 K while La3NiAlMnO9 shows a TC of 130 K. The behavior of these films are compared and contrasted with related La2BMnO6 double perovskites. It is observed that the insertion of AlO6 octahedra between CoO6 and MnO6 suppresses significantly the strength of the superexchange interaction, spin-phonon and spin-polar coupling.Comment: 13 pages, 3 fig

Ferromagnetism and magneto-dielectric effect in insulating LaBiMn4/3Co2/3O6 thin films

High quality epitaxial thin films of LaBiMn4/3Co2/3O6 perovskite were fabricated on (001)-oriented SrTiO3 and LaAlO3 substrates by the pulsed laser deposition technique. Magnetization measurements reveal a strong magnetic anisotropy and a ferromagnetic behavior that is in agreement with a super-exchange interaction between Mn4+ and Co2+ ions, which are randomly distributed in the B-site. A distinct anomaly is observed in the dielectric measurements at 130K corresponding to the onset of the magnetic ordering, suggesting a coupling. Above this temperature, the extrinsic Maxwell-Wagner effect is dominating. Theses results are explained using the Raman spectroscopic studies indicating a weak spin-lattice interaction around this magnetic transition.Comment: Submitted to Appl. Phys. Lett. (2008

Probing the role of Nd3+ ions in the weak multiferroic character of NdMn2O5 by optical spectroscopies

Raman and infrared spectroscopies are used as local probes to study the dynamics of the Nd-O bonds in the weakly multiferroic NdMn2O5 system. The temperature dependence of selected Raman excitations reveals the splitting of the Nd-O bonds in NdMn2O5. The Nd3+ ion crystal field (CF) excitations in NdMn2O5 single crystals are studied by infrared transmission as a function of temperature, in the 1800-8000 cm-1 range, and under an applied magnetic field up to 11 T. The frequencies of all 4Ij crystal-field levels of Nd3+ are determined. We find that the degeneracy of the ground-state Kramers doublet is lifted ({\Delta}0 ~7.5 cm-1) due to the Nd3+-Mn3+ interaction in the ferroelectric phase, below TC ~ 28 K. The Nd3+ magnetic moment mNd(T) and its contribution to the magnetic susceptibility and the specific heat are evaluated from {\Delta}0(T) indicating that the Nd3+ ions are involved in the magnetic and the ferroelectric ordering observed below ~ 28 K. The Zeeman splitting of the excited crystal field levels of the Nd3+ ions at low temperature is also analyzed.Comment: This paper is accepted for publication as a Regular Article in Physical Review

Influence of Ni/Mn cation order on the spin-phonon coupling in multifunctional La2NiMnO6 epitaxial films by polarized Raman spectroscopy

We report the influence of Ni/Mn ordering on the spin-phonon coupling in multifunctional La2NiMnO6. Three types of films with different levels of structural order, including long-range Ni/Mn cation order, cation disorder, and an admixture of the ordered and disordered phases, are compared by polarized micro-Raman spectroscopy and magnetometry. Each film displays a strong dependence on the polarization configuration and a unique set of Raman active phonon excitations. Long-range cation ordering results in the splitting of Raman active phonon peaks because of Brillouin zone folding and lowering symmetry. Phonon mode softening begins clearly at a distinct temperature for each sample revealing a strong spin-lattice interaction. It follows closely the magnetization curve in ordered films. Unlike the admixture and the ordered films, softening behavior is strongly suppressed in the cation-disordered films. These differences may be understood based on the variation in amplitude of the spin-spin correlation functions due to the local Ni/Mn cation ordering.Comment: 17 pages, 7 fig

Investigation of phonon behavior in Pr2NiMnO6 by micro-Raman spectroscopy

The temperature dependence of phonon excitations and the presence of spin phonon coupling in polycrystalline Pr2NiMnO6 samples were studied using micro-Raman spectroscopy and magnetometry. Magnetic properties show a single ferromagnetic-to-paramagnetic transition at 228 K and a saturation magnetization close to 4.95 \muB/f.u.. Three distinct Raman modes at 657, 642, and 511 cm-1 are observed. The phonon excitations show a clear hardening due to anharmonicity from 300 K down to 10 K. Further, temperature dependence of the 657 cm-1 mode shows only a small softening. This reflects the presence of a relatively weak spin-phonon coupling in Pr2NiMnO6 contrary to other double perovskites previously studied.Comment: 10 pages, 4 fig

Infrared optical properties of Pr2CuO4

The ab-plane reflectance of a Pr2CuO4 single crystal has been measured over a wide frequency range at a variety of temperatures, and the optical properties determined from a Kramers-Kronig analysis. Above ~ 250 K, the low frequency conductivity increases quickly with temperature; the resistivity follows the form e^(E_a/k_BT), where E_a ~ 0.17 eV is much less than the inferred optical gap of ~ 1.2 eV. Transport measurements show that at low temperature the resistivity deviates from activated behavior and follows the form e^[(T_0/T)^1/4], indicating that the dc transport in this material is due to variable-range hopping between localized states in the gap. The four infrared-active Eu modes dominate the infrared optical properties. Below ~ 200 K, a striking new feature appears near the low-frequency Eu mode, and there is additional new fine structure at high frequency. A normal coordinate analysis has been performed and the detailed nature of the zone-center vibrations determined. Only the low-frequency Eu mode has a significant Pr-Cu interaction. Several possible mechanisms related to the antiferromagnetism in this material are proposed to explain the sudden appearance of this and other new spectral features at low temperature.Comment: 11 pages, 7 embedded EPS figures, REVTeX