Long-Range Magnetic Interactions Induced by the Lattice Distortions and the Origin of the E-type Antiferromagnetic Phase in the Undoped Orthorhombic Manganites
With the increase of the lattice distortion, the orthorhombic manganites $R$MnO$_3$ ($R$$=$ La, Pr, Nd, Tb, and Ho) are known to undergo the phase transition from the layered A-type antiferromagnetic (AFM) state to the zigzag E-type AFM state. We consider the microscopic origin of this transition. Our approach consists of the two parts. First, we construct an effective lattice fermion model for the manganese 3d-bands and derive parameters of this model from the first-principles electronic structure calculations. Then, we solve this model in the Hartree-Fock approximation (HFA) and analyze the behavior of interatomic magnetic interactions. We argue that the nearest-neighbor interactions decrease with the distortion and at certain stage start to compete with the longer range (particularly, second- and third-neighbor) AFM interactions in the orthorhombic ab-plane, which lead to the formation of the E-phase. The origin of these interactions is closely related to the orbital ordering, which takes place in the distorted orthorhombic structure. The model is able to capture the experimental trend and explain why LaMnO$_3$ develops the A-type AFM order and why it tends to transform to the E-type AFM order in the more distorted compounds. Nevertheless, the quantitative agreement with the experimental data crucially depends on other factors, such as the magnetic polarization of the oxygen sites and the correlation interactions beyond HFA.
We study the existence of incommensurate phases in the phase diagram of the two orbital double exchange model coupled with Jahn-Teller phonons and with superexchange interactions. In agreement with experimental results, we find that undoped manganites $RMnO_3$ ($R$ being some rare earth element) show temperature induced commensurate-incommensurate phase transitions. In the incommensurate phase the magnetic wave vector varies with temperature. The incommensurate phase arises from the competition between the short range antiferromagnetic superexchange interaction and the long range ferromagnetic…
We study the ground state orbital ordering of $LaMnO_3$, at weak electron-phonon coupling, when the spin state is A-type antiferromagnet. We determine the orbital ordering by extending to our Jahn-Teller system a recently developed Peierls instability framework for the Holstein model [1]. By using two-dimensional dynamic response functions corresponding to a mixed Jahn-Teller mode, we establish that the $Q_2$ mode determines the orbital order.
We present a theoretical study on the relation between the size of the rare earth ions, often known as chemical pressure, and the stability of the coherent Jahn-Teller distortions in undoped perovskite manganites. Using a Keating model expressed in terms of atomic scale symmetry modes, we show that there exists a coupling between the uniform shear distortion and the staggered buckling distortion within the Jahn-Teller energy term. It is found that this coupling provides a mechanism by which the coherent Jahn-Teller distortion is more stabilized by smaller rare earth ions. We analyze the appear…
We argue that the homogeneous distribution of spins in the spin-spiral state of orthorhombic manganites is deformed by the relativistic spin-orbit interaction. The thus induced spin-spiral inhomogeneity gives rise to the ferroelectric response of the purely electronic origin in even-periodic magnetic structures. The mechanism is generic and explains the appearance of ferroelectricity in the twofold periodic structure of HoMnO3 as well as the fourfold periodic structure of TbMnO3. Nevertheless, odd-periodic magnetic structures preserve the inversion symmetry and thus are not ferroelectric. Our …
Novel ground-state spin structures in undoped and lightly-doped manganites are here investigated based on the orbital-degenerate double-exchange model, by using mean-field and numerical techniques. In undoped manganites, a new antiferromagnetic (AFM) state, called the E-type phase, is found adjacent in parameter space to the A-type AFM phase. Its structure is in agreement with recent experimental results. This insulating E-AFM state is also competing with a ferromagnetic metallic phase as well, suggesting that large magneto-resistant effects could exist even in undoped Mn oxides. For doped lay…
We present a linear spin and orbital wave theory to account for the spin and orbital orderings observed experimentally in undoped manganite. It is found that the anisotropy of the magnetic structure is closely related to the orbital ordering, and the Jahn-Teller effect stabilizes the orbital ordering. The phase diagram and the low energy excitation spectra for both spin and orbital orderings are obtained. The calculated critical temperatures can be quantitatively comparable to the experimental data.
We investigate the evolution of spin and orbital order in undoped LaMnO$_3$ under increasing temperature with a model including both superexchange and Jahn-Teller interactions. We used several cluster mean field calculation schemes and find coexisting $A$-type antiferromagnetic ($A$-AF) and $C$-type alternating orbital order at low temperature. The value of the Jahn-Teller coupling between strongly correlated $e_g$ orbitals is estimated from the orbital transition temperature at $T_{\rm OO}\simeq 780$ K. By a careful analysis of on-site and on-bond correlations we demonstrate that spin-orbital…
We investigate the electronic properties of multi-domain configurations in models for undoped manganites by means of variational and Monte Carlo techniques. These materials display simultaneous Jahn-Teller distortions and magnetic ordering. We find that a band of electronic states appears associated with Jahn-Teller domain walls, and this band is localized in the direction perpendicular to the walls. The energy and width of this band depends on the conformational properties of the domain walls. At finite temperatures, the conductance along the domain walls, induced by the localized domain wall…
Aiming at understanding the origin of the electronic contribution to ferroelectric polarization in undoped manganites, we evaluate the Berry phase of orbital-polarizable Bloch electrons as an orbital ordering (OO) establishes in the background of an antiferromagnetic E-type configuration. The onset of OO is tuned by the Jahn-Teller (JT) interaction in a tight-binding model for interacting electrons moving along zigzag chains. A finite polarization is found as soon as the JT coupling is strong enough to induce OO, supporting the large electronic contribution predicted from first principles.
The existence of a novel metal-insulator transition in the ferromagnetic state of models for undoped manganites is here discussed using numerical techniques applied to the $e_{\rm g}$-orbital degenerate Hubbard model tightly coupled with Jahn-Teller distortions. The ground-state phase diagram is presented in the plane defined by the electron-phonon coupling $λ$ and Coulomb interaction $u$. In contrast to the standard one-band Hubbard model for cuprates, the metallic phase is found to exist for finite values of both $λ$ and $u$ in the present $e_{\rm g}$-orbital Hubbard model even at half-filli…
The single layered manganite Pr$_{0.22}$Sr$_{1.78}$MnO$_4$ undergoes structural transition from high temperature tetragonal phase to low temperature orthorhombic phase below room temperature. The orthorhombic phase was reported to have two structural variants with slightly different lattice parameters and Mn-3$d$ levels show orbital ordering within both the variants, albeit having mutually perpendicular ordering axis. In addition to orbital ordering, the orthorhombic variants also order antiferromagnetically with different Néel temperatures. Our magnetic investigation on the polycrystalline sa…
The experimental observation of multiferroic behavior in perovskite manganites with a spiral spin structure demands to clarify the origin of these magnetic states and their relation to ferroelectricity. We show that spin-spiral phases with diagonal wavevector and also the E-type phase exist for intermediate values of the Hund's rule and the Jahn-Teller coupling in the orbitally ordered and insulating state of the standard two-band model Hamiltonian for manganites. Our results support the spin-current mechanism for ferroelectricity and present an alternative view to earlier conclusions where fr…
By directly measuring electrical hysteresis loops using the Positive-Up Negative-Down (PUND) method, we accurately determined the remanent ferroelectric polarization Pr of orthorhombic RMnO3 (R = Ho, Tm, Yb, and Lu) compounds below their E-type spin ordering temperatures. We found that LuMnO3 has the largest Pr of 0.17 uC/cm^2 at 6 K in the series, indicating that its single-crystal form can produce a Pr of at least 0.6 \muuC/cm^2 at 0 K. Furthermore, at a fixed temperature, Pr decreases systematically with increasing rare earth ion radius from R = Lu to Ho, exhibiting a strong correlation wit…
We use ab initio electronic structure calculations within the generalized gradient approximation (GGA+U) to density functional theory (DFT) to determine the microscopic exchange interactions in the series of orthorhombic rare-earth manganites, o-$R$MnO$_3$. Our motivation is to construct a model Hamiltonian (excluding effects due to spin-orbit coupling), which can provide an accurate description of the magnetism in these materials. First, we consider TbMnO$_3$, which exhibits a spiral magnetic order at low temperatures. We map the exchange couplings in this compound onto a Heisenberg Hamiltoni…
We present a rationalization of the Raman spectra of orthorhombic and rhombohedral, stoichiometric and doped, manganese perovskites. In particular we study RMnO3 (R= La, Pr, Nd, Tb, Ho, Er, Y and Ca) and the different phases of Ca or Sr doped RMnO3 compounds as well as cation deficient RMnO3. The spectra of manganites can be understood as combinations of two kinds of spectra corresponding to two structural configurations of MnO6 octahedra and independently of the average structure obtained by diffraction techniques. The main peaks of compounds with regular MnO6 octahedra, as CaMnO3, highly Ca …
The microscopic origin of the magnetically-driven ferroelectricity in collinear AFM-E orthorhombic manganites is explained by means of first-principles Wannier functions. We show that the polarization is mainly determined by the "asymmetric electron hopping" of orbitally-polarized Mn eg states, implicit in the peculiar in-plane zig-zag spin arrangement in the AFM-E configuration. In ortho-HoMnO3, Wannier function centers are largely displaced with respect to corresponding ionic positions, implying that the final polarization is strongly affected by a purely electronic contribution, at variance…
To understand the orbital ordering of $LaMnO_3$ in the ground state, we study it in the A-type spin antiferromagnetic state. We calculate the two-dimensional response functions associated with the Jahn-Teller $Q_2$ and $Q_3$ distortions and find that they diverge at the wavevector $π$,$π$). Furthermore, the $Q_2$ response function diverges faster which indicates that perhaps the ordering of the orbitals at low temperatures is dominated by the $Q_2$ distortion. We calculate the ground state energy for the cases when only one of the $Q_2$ and $Q_3$ modes is excited cooperatively and find that th…
Recently we have reported the observation of colossal magnetostriction effect in HoMn2O5 single crystals. Besides we have made the supposition for possible correlation between the peculiarities, observed in the field depended polarization measurements, and the colossal magnetostriction effect at a 4.2 K temperature. In this article we present our results received by polarization and magnetostriction measurements on HoMn2O5 and TbMn2O5 single crystals and the strong correlation between magnetostriction and polarization phase transition for these two compounds. The origin of this correlation is …
We argue that many aspects of improper ferroelectric activity in orthorhombic manganites can be rationalized by considering the limit of infinite intra-atomic splitting between the majority- and minority-spin states (or the double exchange limit), which reduces the problem to the analysis of a spinless double exchange (DE) Hamiltonian. We apply this strategy to the low-energy model, derived from the first-principles calculations, and combine it with the Berry-phase theory of electric polarization. We start with the simplest two-orbital model, describing the behavior of the eg bands, and apply …
We show that the transition in AMnO3 from the orthorhombic perovskite phase to the hexagonal phase is promoted by inducing disorder on the A-site. The gap between the orthorhombic and the hexagonal phase is widened for disordered, mixed yttrium-gadolinium manganite samples. At the cost of the orthorhombic phase a two phase region emerges. The phase separation exhibits very unusual thermodynamical behaviour. We also show that high pressure synthesis favours the orthorhombic phase. YMnO3 is formed in the orthorhombic phase at 15 kbar.
Doped and undoped manganites are modeled by the coupling between itinerant $e_g$ electrons and static $t_{2g}$ spins, the Jahn-Teller and breathing phonon modes, and the Coulomb interaction. We provide for a careful estimate of all parameters and solve the corresponding Hamiltonian by dynamical mean field theory. Our results for the one-electron spectrum, the optical conductivity, the dynamic and static lattice distortion, as well as the Curie temperature show the importance of all of the above ingredients for a realistic calculation as well as for describing the unusual dynamical properties o…
The phase diagram of quarter-hole-doped perovskite manganites is investigated using the doubleexchange model. An exotic striped type-II multiferroic phase, where 25% of the nearest-neighbor spin couplings are orthogonal to each other, is found in the narrow-bandwidth region. Comparing with the spiral-spin ordering phase of undoped manganites, the multiferroic Curie temperature of the new phase is estimated to be ~4 times higher, while the ferroelectric polarization is similar in magnitude. Our study provides a path for noncollinear spin multiferroics based on electronic self-organization, diff…
By using a realist microscopic model, we study the electric and magnetic properties of the interface between a half metallic manganite and an insulator. We find that the lack of carriers at the interface debilitates the double exchange mechanism, weakening the ferromagnetic coupling between the Mn ions. In this situation the ferromagnetic order of the Mn spins near the interface is unstable against antiferromagnetic CE correlations, and a separation between ferromagnetic/metallic and antiferromagnetic/insulator phases at the interfaces can occur. We obtain that the insertion of extra layers of…
The phase diagram and low temperature properties of the doped manganites A1-xBxMnO3 are discussed for the concentrations x < 0.4. The transition from insulating antiferromagnetic to metallic ferromagnetic state at x_cr = 0.16 is treated by means of percolation theory. The unifying description of insulating and metallic states is presented. The undoped manganite is a band insulator consisting of ferromagnetic layers, which are coupled antiferromagnetically along the c direction with a low Neel temperature. The metallic phase can be described by the two-band Fermi liquid picture. The behavior of…
We show that the symmetry of the spin zigzag chain E phase of the orthorhombic perovskite manganites and nickelates allows for the existence of a finite ferroelectric polarization. The proposed microscopic mechanism is independent of spin-orbit coupling. We predict that the polarization induced by the E-type magnetic order can potentially be enhanced by up to two orders of magnitude with respect to that in the spiral magnetic phases of TbMnO3 and similar multiferroic compounds.
Using LDA+GTB multi-band approach, we studied the compression dependence of the electronic structure and in-plane superexchange interaction J(P) in the antiferromagnetic La214 at the 0% and 3% - hydrostatic and unaxial (along c axial) compression. We obtained the superexchange interaction J(P=0)~0.15eV is enhanced by ~20% under the 3% - hydrostatic compression and vice versa the J(P) is decreased slightly by ~5,7% under the 3% - uniaxial compression. In both cases the J(P) correlates with the in-plane hopping parameters and dd-excitation energy δ_s=e(^3B_{1})-e(A_{1})$ involving the the two-ho…
This work reports an experimental investigation of the magneto-elastic coupling and polarization character of magnetic phases of the orthorhombic Eu1-xYxMnO3 system at low temperatures. The temperature dependence of the polarization reversal curves clearly reveals the existence of a reentrant improper ferroelectric phase for x = 0.2 and 0.3. Although a ferroelectric phase is also stable for x = 0.4, we have no experimental evidence that it vanishing at finite temperatures. From these results and those obtained from other experimental techniques, the corresponding (x,T) phase diagram was traced…
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 …
The formation of a long-range Jahn-Teller distortion in undoped manganites is studied within the dynamical mean-field theory taking both electron-phonon and electron-electron interactions into account. We find that the observed insulating behavior at temperatures above the Jahn-Teller transition and the bond-length changes below it can most naturally by explained by assuming a strong electronic repulsion and a rather weak electron-phonon coupling.
The double exchange (DE) model is systematically applied for studying the coupling between ferroelectric (FE) and magnetic orders in several prototypical types of multiferroic manganites. The model was constructed for the magnetically active Mn $3d$ bands in the basis of Wannier functions and include the effect of screened on-site Coulomb interactions. The essence of our approach for the FE polarization is to use the Berry phase theory, formulated in terms of occupied Wannier functions, and to evaluate the asymmetric spin-dependent change of these functions in the framework of the DE model. Th…
In magnetic compounds with Jahn-Teller (JT) ions (such as Mn3+ or Cu2+), the ordering of the electron or hole orbitals is associated with cooperative lattice distortions. There the role of JT effect, although widely recognised, is still elusive in the ground state properties. We suggest that, in these materials, there exist elementary excitations whose energy spectrum is described in terms of the total angular momentum eigenstates and is quantised as in quantum rotors found in JT centers. We observed features originating from these excitations in the optical spectra of a model compound LaMnO3 …
Neutron scattering measurements on a magnetoresistive manganite La$_{0.75}$(Ca$_{0.45}$Sr$_{0.55}$)$_{0.25}$MnO$_3$ show that uncorrelated dynamic polaronic lattice distortions are present in both the orthorhombic (O) and rhombohedral (R) paramagnetic phases. The uncorrelated distortions do not exhibit any significant anomaly at the O-to-R transition. Thus, both the paramagnetic phases are inhomogeneous on the nanometer scale, as confirmed further by strong damping of the acoustic phonons and by the anomalous Debye-Waller factors in these phases. In contrast, recent x-ray measurements and our …
We analyze the symmetry changes of the paramagnetic to the A-type antiferromagnetic and to the ferromagnetic phase transitions in undoped and moderately doped LaMnO$_3$, respectively. We show that in the orthorhombic-distorted perovskite manganites the phase separation at low doping is associated with the noncollinear nature of the magnetic orders permitted by symmetry. A simple model for the competition between the two phase transitions is put forward within the framework of Landau theory of phase transitions.
First-principles calculations have been performed for different collinear magnetic orderings in orthorhombic manganites, such as HoMnO3, TbMnO3 and YMnO3, showing large GdFeO3-like distortions. Our results suggest that the AFM-E type ordering, experimentally observed in HoMnO3 and recently proposed from model hamiltonian studies as a potentially novel phase, is indeed the magnetic ground state. Its stability is strongly connected with octahedral distortions and points to the relevance of structural more than chemical effects. The calculated exchange constants, extracted from a Heisenberg model…
The Kondo lattice Hamiltonian with ferromagnetic Hund's coupling as a model for manganites is investigated. The classical limit for the spin of the (localized) $t_{2g}$ electrons is analyzed on lattices of dimension 1,2,3 and $\infty$ using several numerical methods. The phase diagram at low temperature is presented. A regime is identified where phase separation occurs between hole undoped antiferromagnetic and hole-rich ferromagnetic regions. Experimental consequences of this novel regime are discussed. Regions of incommensurate spin correlations have also been found. Estimations of the criti…
Complete magnetoelectric (ME) phase diagrams of orthorhombic $R$MnO$_{3}$ with and without magnetic moments on the $R$ ions have been established. Three kinds of multiferroic ground states, the $ab$-cycloidal, the $bc$-cycloidal, and the collinear $E$-type phases, have been identified by the distinct ME responses. The electric polarization of the $E$-type phase dominated by the symmetric spin exchange ($bm{S}_{i} cdot bm{S}_{j}$) is more than 10 times as large as that of the $bc$-cycloidal phase dominated by the antisymmetric one ($bm{S}_{i} times bm{S}_{j}$), and the ME response is enhanced n…
The electron doping of undoped high-$T_c$ cuprates via the transfer of charge from manganites (or other oxides) using heterostructure geometries is here theoretically discussed. This possibility is mainly addressed via a detailed analysis of photoemission and diffusion voltage experiments, which locate the Fermi level of manganites above the bottom of the upper Hubbard band of some cuprate parent compounds. A diagram with the relative location of Fermi levels and gaps for several oxides is presented. The procedure discussed here is generic, allowing for the qualitative prediction of the charge…
Structural, magnetic and electric properties of a metal-ordered perovskite YBaMn2O6 have been studied by means of powder X-ray diffraction, DSC, magnetic susceptibility, and electric resistivity. It is found that this material undergoes a 1st order structural phase transition at Tc1=520 K, from a pseudo orthorhombic (monoclinic) phase to a pseudo tetragonal (monoclinic) one. Accompanied by this transition, the susceptibility exhibits a sharp drop, where ferromagnetic exchange interaction becomes antiferromagnetic. Furthermore, two more transitions, a metal-insulator transition at Tc2=480 K and…
The ABO3 type charge-ordered antiferromagnetic Nd0.50Ca0.50MnO3 (NCMO) manganite is doped at A-site by 3 % of Ba2+ for Ca2+. The resulting system, Nd0.50Ca0.47Ba0.03MnO3 (NCBMO), is studied for the effects of Ba doping on the magnetic and electronic properties. On application of magnetic field to NCBMO, strongly correlated successive sharp metamagnetic and electronic transitions are observed from antiferromagnetic-insulating to ferromagnetic-metallic state at 2.5 K. The critical magnetic field (Hc) required for metamagnetism is found to reduce drastically from 15 T for undoped NCMO to 3 T for …
We investigate spin-charge-orbital ordering in a Mn$^{3+}$/Mn$^{4+}$ mixed valence state on a hollandite-type lattice using unrestricted Hartree-Fock calculation on a multi-band Mn 3$d$-O 2$p$ lattice model. The calculations show that the Mn$^{3+}$-Mn$^{4+}$ double exchange interaction, the Mn$^{3+}$-Mn$^{3+}$ and Mn$^{4+}$-Mn$^{4+}$ superexchange interactions are ferromagnetic and play important roles to stabilize the charge and orbital ordering pattern. The most stable charge and orbital ordering pattern is consistent with the $1\times1\times1$ orthorhombic or monoclinic structure of K$_{1.6…
We introduce an effective model for $e_g$ electrons to describe three-dimensional perovskite (La$_{1-x}$Sr$_{x}$MnO$_3$ and La$_{1-x}$Ca$_{x}$MnO$_3$) manganites and study the magnetic and orbital order on $4\times 4\times 4$ cluster using correlated wave functions. The model includes the kinetic energy, and on-site Coulomb interactions for $e_g$ electrons, antiferromagnetic superexchange interaction between $S=3/2$ core spins, and the coupling between $e_g$ electrons and Jahn-Teller modes. The model reproduces the experimentally observed magnetic order: ($i$) $A$-type antiferromagnetic phase …
A spin-tunnel-junction based on manganites, with La$_{1-x}$Sr$_x$MnO$_3$ (LSMO) as ferromagnetic metallic electrodes and the undoped parent compound LaMnO$_3$ (LMO) as insulating barrier, is here theoretically discussed using double exchange model Hamiltonians and numerical techniques. For an even number of LMO layers, the ground state is shown to have anti-parallel LSMO magnetic moments. This highly resistive, but fragile, state is easily destabilized by small magnetic fields, which orient the LSMO moments in the direction of the field. The magnetoresistance associated with this transition is…
The orbital order-disorder transition temperature (T_OO) versus tolerance factor (t) plot switches from monotonic to non-monotonic beyond a doping level (x) ~ 10 atom% in a family of R(1-x)A(x)MnO3 systems(R = La, Pr, Nd; A = Ca, Sr; x = 0.0-0.2). T_OO reaches maximum at a 'doping-dependent' critical tolerance factor t_C(x) (for 0.1<x<0.2)at which the orthorhombic distortion (D) also maximizes. Such an observation reflects influence of charge carriers on both 'intrinsic' octahedral-site distortion and its bias on the orbital order in doped perovskite manganites and, thus, deviation from what h…
We report a pervasive phenomenon of gradual emergence of negative magnetization in typical $R_{1-x}D_x$MnO$_3$ orthorhombic perovskite manganites in nano form (with $R^{3+}$ being a trivalent high-magnetic-moment ion from the heavier rare-earth elements Gd, Tb, Dy and $D^{2+}$ refers to divalent alkaline elements Sr, Ca, etc.), while the bulk form manifests no negative magnetization. Extensive magnetization studies have been carried out in Gd$_{1-x}$Ca$_x$MnO$_3$ manganites around half doping. We demonstrate experimentally that particle size reduction in nano-form manganites enhances the prope…
In this work, we report an atomic scale study on the ferromagnetic insulator manganite LaMnO$_{3.12}$ using $γ-γ$ PAC spectroscopy. Data analysis reveals a nanoscopic transition from an undistorted to a Jahn-Teller-distorted local environment upon cooling. The percolation thresholds of the two local environments enclose a macroscopic structural transition (Rhombohedric-Orthorhombic). Two distinct regimes of JT-distortions were found: a high temperature regime where uncorrelated polaron clusters with severe distortions of the Mn$^{3+}$O$_{6}$ octahedra survive up to $T \approx 800 K$ and a low …
We studied the correlation between magnetic, electrical, structural, and magnetostriction properties of the electron doped manganites Ca$_x$Sm$_{1-x}$MnO$_3$ (x = 0.85, 0.8). The paramagnetic to antiferromagnetic transition in both the compounds while cooling is accompanied by an abrupt increase of the spontaneous volume thermal expansion ($Δ$V/V = 0.07 % for x = 0.85 and 0.25 % for x = 0.2). The x = 0.15 exhibits multiple phase separation at 5 K: G-type, and C-type antiferromagnetic phases in orthorhombic (\QTR{it}{Pnma}) and monoclinic (\QTR{it}{P2}$_1$\QTR{it}{/m}) structures respectively. …
The effect of Pr-doping on structural, magnetic and transport properties in electron-doped manganites La0.9-xPrxTe0.1MnO3 with fixed carrier concentration are investigated. The room temperature structural transition from rhombohedral (R3C) to orthorhombic (Pbnm) symmetry is found in the samples with by the Rietveld refinement of x-ray powder diffraction patterns. The Curie temperature of samples decreases and the transition becomes broader with increasing Pr-doping level. For the samples with, there exist insulator-metal (I-M) transition. And the low-temperature I-M transition is observed at a…
We present a systematic study of the structure and lattice dynamics at room temperature, and the phonon behavior at low temperatures in orthorhombic Gd$_{1-x}$Y$_{x}$MnO$_{3}$ manganites, with 0 $\leq$ x $\leq$ 0.4, using powder x-ray diffraction and Raman scattering. A thorough analysis towards the correlation between both structural and Raman modes parameters was undertaken. The data obtained at room temperature reveal structural distortions arising from the Jahn-Teller distortion and octahedra tilting. The Jahn-Teller distortion is apparently x-independent, while an increase of Mn-O1-Mn bon…
The influence of the A-site ionic radii (<rA>) on the magnetic structure has been investigated in La0.5Ca0.5-xSrxMnO3 compounds (0 .GE. x .LE. 0.5) using neutron diffraction, magnetization, and resistivity techniques. All compounds in the composition range x .LE. 0.3 crystallize in the orthorhombic structure (Space Group Pnma). No further structural transition is observed as temperature is lowered below 300K. The compound x = 0.4, is a mixture of two orthorhombic phases crystallizing in Pnma and Fmmm space group. The x = 0.5 compound has a tetragonal structure in the space group, I4/mcm. The c…
The origin of the spiral spin-order in perovskite multiferroic manganites $R$MnO$_{3}$ ($RE=$ Tb or Dy) is here investigated using a two $e_{\rm g}$-orbitals double-exchange model. Our main result is that the experimentally observed spiral phase can be stabilized by introducing a relatively weak next-nearest-neighbor superexchange coupling ($\sim10%$ of the nearest-neighbor superexchange). Moreover, the Jahn-Teller lattice distortion is also shown to be essential to obtain a realistic spiral period. Supporting our conclusions, the generic phase diagram of undoped perovskite manganites is obtai…
In the orthorhombic manganites o-RMnO3, where R is a heavy rare earth (R = Gd-Yb), the Mn3+ sublattice is known to undergo two magnetic transitions. The low temperature phase has an antiferromagnetic structure (collinear or elliptical), which has been well characterized by neutron diffraction in most of these compounds. The intermediate phase, occurring in a narrow temperature range (a few K), is documented for R = Gd-Ho as a collinear modulated structure, incommensurate with the lattice spacings. We report here on a 57Fe Mössbauer study of 2% 57Fe doped o-YbMnO3, where the spin only Fe3+ ion …
Extensive experimental results are presented on the multi-scale phase modulation phenomena observed in colossal magnetoresistance manganites. Two key types of phase inhomogeneities directly relevant to the colossal magnetoresistance (CMR) are discussed. The first type involves micrometer-scale coexistence of structurally and electronically different phases. We present extensive experimental data for a prototypical system exhibiting such a phase coexistence, (La,Pr)$_{5/8}$Ca$_{3/8}$MnO$_{3}$. These data reveal that percolative transport phenomena play the key role in the metal-insulator transi…
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" d…
Epitaxial La3/4Ca1/4MnO3/MgO(100) (LCMO) thin films show unusual rhombohedral (R-3c) structure with a new perovskite superstructure due to unique ordering of La and Ca at the A-site positions. Very sharp insulator-metal and para-ferromagnetic phase transitions at temperatures up to TMI ~ TC=295 K were observed. The ordered films were electronically homogeneous down to 1 nm scale as revealed by scanning tunnelling microscopy/spectroscopy. In contrast, orthorhombic and A-site disordered LCMO demonstrate broadened phase transitions as well as mesoscopic phase separation for T<<TC. The unique La/C…
There has been tremendous research activity in the field of magneto-electric (ME) multiferroics after Kimura et al. [1] showed that antiferromagnetic and ferroelectric order coexist in orthorhom- bically distorted perovskite TbMnO3 and are strongly coupled. It is now generally accepted that ferroelectricity in TbMnO3 is induced by magnetic long range order that breaks the symmetry of the crystal and creates a polar axis [2]. One remaining key question is whether magnetic order can induce ferroelectric polarization that is as large as that of technologically useful materials. We show that ferro…
We have investigated dielectric properties in a series of crystals of $R$MnO$_{3}$ ($R$ is a rare earth ion) under magnetic fields and quasihydrostatic pressure. We have found that ferroelectric phase appeared in GdMnO$_3$ crystal below 13K. We have confirmed that a small spontaneous polarization exists along a axis ($P_a$) in the orthorhombic $Pbnm$ setting and that $P_a$ can be reversed by the dc electric field. The dielectric anomaly due to the ferroelectric transition accompanied thermal hysteresis and lattice striction. The ferroelectric transition temperature decreased with quasihydrosta…
We investigate the interplay between spin and orbital correlations in monolayer and bilayer manganites using an effective spin-orbital t-J model which treats explicitly the e_g orbital degrees of freedom coupled to classical t_{2g} spins. Using finite clusters with periodic boundary conditions, the orbital many-body problem is solved by exact diagonalization, either by optimizing spin configuration at zero temperature, or by using classical Monte-Carlo for the spin subsystem at finite temperature. In undoped two-dimensional clusters, a complementary behavior of orbital and spin correlations is…
The main properties of realistic models for manganites are studied using analytic mean-field approximations and computational numerical methods, focusing on the two-orbital model with electrons interacting through Jahn-Teller (JT) phonons and/or Coulombic repulsions. Analyzing the model including both interactions by the combination of the mean-field approximation and the exact diagonalization method, it is argued that the spin-charge-orbital structure in the insulating phase of the purely JT-phononic model is not qualitatively changed by the inclusion of the Coulomb interactions. As an import…
We present a study of the effect of very high pressure on the orthorhombic perovskite GdMnO3 by Raman spectroscopy and synchrotron x-ray diffraction up to 53.2 GPa. The experimental results yield a structural and insulator-to-metal phase transition close to 50 GPa, from an orthorhombic to a metrically cubic structure. The phase transition is of first order with a pressure hysteresis of about 6 GPa. The observed behavior under very high pressure might well be a general feature in rare-earth manganites.
