Microscopic Model and Phase Diagrams of the Multiferroic Perovskite Manganites

Orthorhombically distorted perovskite manganites, RMnO3 with R being a trivalent rare-earth ion, exhibit a variety of magnetic and electric phases including multiferroic (i.e. concurrently magnetic and ferroelectric) phases and fascinating magnetoelectric phenomena. We theoretically study the phase diagram of RMnO3 by constructing a microscopic spin model, which includes not only the superexchange interaction but also the single-ion anisotropy (SIA) and the Dzyaloshinsky-Moriya interaction (DMI). Analysis of this model using the Monte-Carlo method reproduces the experimental phase diagrams as functions of the R-ion radius, which contain two different multiferroic states, i.e. the ab-plane spin cycloid with ferroelectric polarization P//a and the bc-plane spin cycloid with P//c. The orthorhombic lattice distortion or the second-neighbor spin exchanges enhanced by this distortion exquisitely controls the keen competition between these two phases through tuning the SIA and DMI energies. This leads to a lattice-distortion-induced reorientation of P from a to c in agreement with the experiments. We also discuss spin structures in the A-type antiferromagnetic state, those in the cycloidal spin states, origin and nature of the sinusoidal collinear spin state, and many other issues.Comment: 23 pages, 19 figures. Recalculated results after correcting errors in the assignment of Dzyaloshinsky-Moriya vector

Disproportionation and electronic phase separation in parent manganite LaMnO_3

Nominally pure undoped parent manganite LaMnO_3 exhibits a puzzling behavior inconsistent with a simple picture of an A-type antiferromagnetic insulator (A-AFI) with a cooperative Jahn-Teller ordering. We do assign its anomalous properties to charge transfer instabilities and competition between insulating A-AFI phase and metallic-like dynamically disproportionated phase formally separated by a first-order phase transition at T_{disp}=T_{JT}\approx 750 K. The unconventional high-temperature phase is addressed to be a specific electron-hole Bose liquid (EHBL) rather than a simple "chemically" disproportionated R(Mn^{2+}Mn^{4+})O_3 phase. New phase does nucleate as a result of the charge transfer (CT) instability and evolves from the self-trapped CT excitons, or specific EH-dimers, which seem to be a precursor of both insulating and metallic-like ferromagnetic phases observed in manganites. We arrive at highly frustrated system of triplet (e_g^2)^3A_{2g} bosons moving in a lattice formed by hole Mn^{4+} centers. Starting with different experimental data we have reproduced a typical temperature dependence of the volume fraction of high-temperature mixed-valent EHBL phase. We argue that a slight nonisovalent substitution, photo-irradiation, external pressure or magnetic field gives rise to an electronic phase separation with a nucleation or an overgrowth of EH-droplets. Such a scenario provides a comprehensive explanation of numerous puzzling properties observed in parent and nonisovalently doped manganite LaMnO_3 including an intriguing manifestation of superconducting fluctuations.Comment: 20 pages, 8 figure

Collinear-to-Spiral Spin Transformation without Changing Modulation Wavelength upon Ferroelectric Transition in Tb1-xDyxMnO3

Lattice modulation and magnetic structures in magnetoelectric compounds Tb1-xDyxMnO3 have been studied around the ferroelectric (FE) Curie temperature T_C by x-ray and neutron diffraction. Temperature-independent modulation vectors through T_C are observed for the compounds with 0.50< x < 0.68. This indicates that ferroelectricity with a polarization (P) along the c axis in the RMnO3 series cannot be ascribed to such an incommensurate-commensurate transition of an antiferromagnetic order as was previously anticipated. Neutron diffraction study of a single crystal with x=0.59 shows that the FE transition is accompanied by the transformation of the Mn-spin alignment from sinusoidal (collinear) antiferromagnetism into a transverse spiral structure. The observed spiral structure below T_C is expected to produce P along the c axis with the `inverse' Dzialoshinski-Moriya interaction, which is consistent with the observation.Comment: 9 pages, 4 figure

Theory of magnetic field-induced metaelectric critical end point in BiMn2_2O5_5

A recent experiment on the multiferroic BiMn$_2$O$_5$ compound under a strong applied magnetic field revealed a rich phase diagram driven by the coupling of magnetic and charge (dipolar) degrees of freedom. Based on the exchange-striction mechanism, we propose here a theoretical model with the intent to capture the interplay of the spin and dipolar moments in the presence of a magnetic field in BiMn$_2$O$_5$. Experimentally observed behavior of the dielectric constants, magnetic susceptibility, and the polarization is, for the most part, reproduced by our model. The critical behavior observed near the polarization reversal $(P=0)$ point in the phase diagram is interpreted as arising from the proximity to the critical end point.Comment: Theory; relevant experiment uploaded as arXiv:0810.190

Magnetoelectric coupling in polycrystalline FeVO4

We report coupling between magnetic and electric orders for antiferromagnetic polycrystalline FeVO4 in which magnetism-induced polarization has been recently found in noncollinear antiferromagnetic state below the second antiferromagnetic phase transition at TN2=15.7K. In this low symmetry phase space group P-1, the magnetic field dependence of electric polarization evidences a clear magnetoelectric coupling in the noncollinear spin-configured antiferromagnetic phase. The discontinuity of magnetodielectric effect observed at the vicinity of the polar to nonpolar transition evidences competition between different magnetodielectric couplings in the two different antiferromagnetic states. The existence of thermal expansion anomaly near TN2 and magnetostriction effect support magnetoelastically mediated scenario of the observed magnetoelectric effect.Comment: 4 pages, 6 figures, Phys. Rev. B 80, 172103 (2009

Anomalous thermal expansion and strong damping of the thermal conductivity of NdMnO3_3 and TbMnO3_3 due to 4f crystal-field excitations

We present measurements of the thermal conductivity $\kappa$ and the thermal expansion $\alpha$ of NdMnO$_3$ and TbMnO$_3$. In both compounds a splitting of the $4f$ multiplet of the $R^{3+}$ ion causes Schottky contributions to $\alpha$. In TbMnO$_3$ this contribution arises from a crystal-field splitting, while in NdMnO$_3$ it is due to the Nd-Mn exchange coupling. Another consequence of this coupling is a strongly enhanced canting of the Mn moments. The thermal conductivity is greatly suppressed in both compounds. The main scattering process at low temperatures is resonant scattering of phonons between different energy levels of the $4f$ multiplets, whereas the complex 3d magnetism of the Mn ions is of minor importance.Comment: 9 pages including 6 figure

Magnetoelectric Effect and Spontaneous Polarization in HoFe3_3(BO3_3)4_4 and Ho0.5_{0.5}Nd0.5_{0.5}Fe3_3(BO3_3)4_4

The thermodynamic, magnetic, dielectric, and magnetoelectric properties of HoFe$_3$(BO$_3$)$_4$ and Ho$_{0.5}$Nd$_{0.5}$Fe$_3$(BO$_3$)$_4$ are investigated. Both compounds show a second order Ne\'{e}l transition above 30 K and a first order spin reorientation transition below 10 K. HoFe$_3$(BO$_3$)$_4$ develops a spontaneous electrical polarization below the Ne\'{e}l temperature (T$_N$) which is diminished in external magnetic fields. No magnetoelectric effect could be observed in HoFe$_3$(BO$_3$)$_4$. In contrast, the solid solution Ho$_{0.5}$Nd$_{0.5}$Fe$_3$(BO$_3$)$_4$ exhibits both, a spontaneous polarization below T$_N$ and a magnetoelectric effect at higher fields that extends to high temperatures. The superposition of spontaneous polarization, induced by the internal magnetic field in the ordered state, and the magnetoelectric polarizations due to the external field results in a complex behavior of the total polarization measured as a function of temperature and field.Comment: 12 pages, 15 figure