Phase separation with charge self-organization in the Tb0.95Bi0.05MnO3, Gd0.75Ce0.25Mn2O5, and Eu0.8Ce0.2Mn2O5 manganite multiferroics

New doped manganite multiferroics Tb_0.95Bi_0.05MnO₃, Gd_0.75Ce_0.25Mn₂O₅, and Eu_0.8Ce_0.2Mn₂O₅, which are semiconductors, have been grown and studied. The starting dielectric multiferroics TbMnO₃ and RMn₂O₅ (R = Gd and Eu) have close magnetic and ferroelectric ordering temperatures of 30–40 K. The crystals studied are multiferroics in which states with giant permittivity and ferromagnetism coexist at room temperature. An analysis of the dielectric properties suggests that, at temperatures T ≥ 180 K, these crystals undergo a phase separation involving dynamic periodic alternation of quasi-2D layers of mixed-valence manganese ions, a process accounting for the onset of charge-induced ferroelectricity. At low temperatures (T < 100 K), a small phase volume in the crystals is occupied by as-grown quasi-2D layers containing dopants and carriers. Most of the crystal volume is occupied by the carrier-free dielectric phase. Thermally activated hopping conduction involving carrier self-organization in the crystal matrix with ferroelectric frustrations drives a phase transition to the state of charge-induced ferroelectricity at T ∼ 180 K. Original Russian Text ? V.A. Sanina, E.I. Golovenchits, V.G. Zalesskiĭ, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 5, pp. 874–882.     

Magnetic-field-induced phase transition in Tb0.95Bi0.05MnO3+δ multiferroic

The effect of a magnetic field on the dielectric properties of Tb_0.95Bi_0.05MnO_3+δ single crystals has been analyzed. It has been shown that the state of the crystal for temperatures of 5–440 K is inhomogeneous and restricted domains of polar and spin correlations are exhibited in it. A phase transition in which the inhomogeneous state of the crystal changes substantially has been observed at a temperature of T ? 180 and 225 K (in the absence and presence of a magnetic field, respectively). The high-temperature phase contains large dielectric domains with a high dielectric constant (ε ～ 10⁵) and thin conducting layers at the boundaries of these domains. The magnetic field significantly affects the state of both low-and high-temperature phases of the crystal, shifting the temperature of the phase transition between them, and induces an additional phase transition at T ? 441 K.     

Magnetic properties and charge ordering in Pr0.75Na0.25MnO3 manganite

The structural and magnetic properties of Pr_0.75Na_0.25MnO₃ have been investigated experimentally. At room temperature, the compound shows paramagnetic characteristic. Along with decreasing temperature, a peak appears in the magnetization versus temperature curve around 220 K. To clarify whether this peak is associated with the ordering arrangement of Mn³⁺ and Mn⁴⁺ ions, electron diffraction experiments were carried out below and above 220 K respectively. Only basic Brag diffraction spots can be observed at high temperatures, however, superlattice diffraction appears below 220 K. This provides direct evidence for the existence of charge ordering in Pr_0.75Na_0.25MnO₃. We find the Mn³⁺ and Mn⁴⁺ cations form zigzag chains in a-c plane by analyzing the diffraction patterns. Combining with the magnetization measurements and the results of electron spin resonance, we confirm the antiferromagnetic phase and ferromagnetic component coexist in Pr_0.75Na_0.25MnO₃ below 120 K.     

Charge ordering and structural transitions in Pr0.5Sr0.41Ca0.09MnO3

The structural and magnetic transitions in Pr_0.5Sr_0.41Ca_0.09MnO₃ have been investigated by neutron diffraction and electron microscopy. Two structural transitions, Imma to I4/mcm and I4/mcm to Pmmn, are observed by decreasing the temperature. Two magnetic transitions, from a paramagnetic insulating to a ferromagnetic metallic and from a ferromagnetic metallic to an antiferromagnetic insulating states at T_C=250 K and T_N=180 K, respectively, are also observed. The structures of these three forms have been determined from neutron powder diffraction data. The first important result concerns the low temperature antiferromagnetic CE type and charge ordered structure, which has been refined in the Pmmn space group, without any constraint. This structure is completely long range ordered, with two Mn-sites, Mn³⁺ in tetragonally elongated octahedra, and Mn⁴⁺, off-centered in nearly regular octahedra. The second important point concerns the abrupt character of the structural transition from the I4/mcm to the Pmmn structure, without any appearance of incommensurability. The magnetic and transport properties of this compound are compared with those of Pr_0.5Sr_0.5MnO₃.     

Synthesis and dielectric characteristics of La0.5Bi0.5MnO3 ceramics

La_0.5Bi_0.5MnO₃ ceramics with a single phase were prepared by a solid-state reaction method, and their dielectric properties were characterized. Two dielectric relaxations with a giant dielectric constant were identified in the temperature range from 125 to 350 K. The electron hopping between Mn³⁺ and Mn⁴⁺ was found to be the origin of the dielectric relaxation at low temperatures (125–200 K) with an activation energy of 0.18 eV. The high temperature (200–350 K) dielectric relaxation can be attributed to the conduction.     

Nature of unusual spontaneous and field-induced phase transitions in multiferroics RMn2O5

Complex magnetic, magnetoelectric and magnetoelastic studies of spontaneous and field-induced phase transitions in TmMn₂O₅ were carried out. In the vicinity of spontaneous phase transition temperatures (35 and 25 K) the magnetoelectric and magnetoelastic dependences demonstrated the jumps of polarization and magnetostriction induced by the field ∼150 kOe. These anomalies can be attributed to the influence of magnetic field on the conditions of incommensurate-commensurate phase transition at 35 K and the reverse one at 25 K. In b-axis dependences the magnetic field-induced spin-reorientation phase transition was also observed below 20 K. Finally the magnetoelectric anomaly associated with metamagnetic transition is observed below the temperature of rare-earth subsystem ordering at relatively small critical fields of 5 kOe. This variety of spontaneous and induced phase transitions in RMn₂O₅ stems from the interplay of three magnetic subsystems: Mn³⁺, Mn⁴⁺, R³⁺. The comparison with YMn₂O₅ highlights the role of rare earth in low-temperature region (metamagnetic and spin-reorientation phase transitions), while the phase transition at higher temperatures between incommensurate and commensurate phases should be ascribed to the different temperature dependences of Mn³⁺ and Mn⁴⁺ ions. The strong correlation of magnetoelastic and magnetoelectric properties observed in the whole class of RMn₂O₅ highlights their multiferroic nature.     

Magnetic phase coexistence in Tb- and Sr-doped La0.7Ca0.3MnO3 manganite:A temperature-dependent neutron diffraction study

We report the results of the temperature-dependent neutron diffraction measurements on the nearly half-doped (La_0.325Tb_0.125)(Ca_0.3Sr_0.25)MnO₃ manganite sample. The simultaneous doping of magnetic Tb³⁺ and divalent Sr²⁺ in the La_0.7Ca_0.3MnO₃ system results into a large A-site size disorder. Rietveld refinement of neutron diffraction data reveal that the single phase sample crystallizes in a distorted orthorhombic structure. Increased 〈r_A〉 value affects the transport behavior that results into an insulating-like behavior of the sample. Under application of 1 T field sample exhibit insulating-like behavior while insulator-metal transition (T_IM) is exhibited under 5 and 8 T fields. Variable range hoping (VRH) mechanism of charge carriers is exhibited in the insulating region. Field cooled and zero field cooled magnetization measurement shows the Curie temperature (T_C)~47 K. The refinement of the ND data collected at various temperatures below 300 K shows that there is no structural phase transition in the compound. Around 100 K, a magnetic peak appears at lower angle that can be ascribed to the presence of the A-type antiferromagnetic (AFM) phase. Two more peaks are observed around 50 K at lower angles that can be fitted in CE-type antiferromagnetic phase. Splitting of the peaks at lower temperatures is the signature of orbital ordering in the presently studied nearly half-doped manganite system. Results of the detailed structural analysis of the temperature-dependent ND measurements on (LaTb)_0.45(CaSr)_0.55MnO₃ sample has been discussed in the light of coexisting A-type and CE-type antiferromagnetic phases present in the sample at low temperature.     

Phase transition in electronic manganite Ca0.85Sm0.15MnO3

The resistivity, the magnetic susceptibility, the magnetization, and the specific heat of electronic manganite Ca_0.85Sm_0.15MnO₃ were studied. The data obtained suggest that this compound undergoes phase transition into the insulator antiferromagnetic state at T _c ～115 K and displays negative magnetoresistance at T<T _c . A minor ferromagnetic component of 0.025µ_B in the magnetization of Ca_0.85Sm_0.15MnO₃ may be caused by the deviation of this composition from the exact stoichiometry Mn³⁺: Mn⁴⁺=1: 8. The Debye temperature Θ_D=575 K and the entropy of phase transition ΔS=5.1 J/(mol K) were derived from the temperature dependence of specific heat.     

Effect of Ca doping on the magnetic properties of Nd0.5Sr0.5MnO3 studied by electron spin resonance

The magnetic properties of Ca-doped Nd_0.5Sr_0.5MnO₃ have been studied by electron spin resonance (ESR) and dc magnetization measurements. The antiferromagnetic order and charge order are found to occur separately at T_N=200 K and T_co=150 K, respectively. Compared to the undoped Nd_0.5Sr_0.5MnO₃, the ferromagnetic correlations are suppressed by doping of the small Ca²⁺ ion. In addition, the antiferromagnetic transition temperature is enhanced to 200 K, which can be explained by an increase of superexchange interaction between Mn³⁺ and Mn⁴⁺ ions as their distance decreases.     

Manifestation of a series of phase transitions in IR spectra of a multiferroic TbMnO3

We have studied IR transmittance spectra of a multiferroic TbMnO₃. Three phase transitions (T _N = 43 K, T _FE = 28 K, and T _Tb = 7 K), which manifest themselves in a shift of the absorption band edge of manganese and in changes in the spectral parameters of lines of f-f transitions of terbium, have been detected. An incommensurate character of the magnetic structure leads to nonequivalence of terbium positions and to an additional inhomogeneous broadening. The spontaneous electric polarization, which arises at T < T _FE, significantly affects the crystal field that acts on terbium and noticeably shifts its energy levels. The phase transition with ordering of terbium (7 K) is accompanied by a lowering of the energy of the ground state of the Tb³⁺ ion.     

Phase separation in a manganite La<Subscript>0.95</Subscript>Ba<Subscript>0.05</Subscript>MnO<Subscript>3</Subscript> crystal

The structure and magnetic states of a crystal of lightly doped manganite La_0.95Ba_0.05MnO₃ were studied using thermal-neutron diffraction, magnetic measurements, and electrical resistance data in a wide temperature range. It is shown that, in terms of its magnetic properties, the orthorhombic crystal is characterized by two order parameters, namely, antiferromagnetic (T _N = 123.6 K) and ferromagnetic (T _C = 136.7 K). The results obtained differ in detail from known information on the manganites La_0.95Ca_0.05MnO₃ and La_0.94Sr_0.06MnO₃. Two models of the magnetic state of the La_0.95Ba_0.05MnO₃ crystal are discussed, one of which is a model of a canted antiferromagnetic spin system and another is associated with the phase separation of the manganite. Arguments are advanced in favor of the coexistence in this crystal of the antiferromagnetic phase (about 87%) with a Mn⁴⁺ ion concentration of 0.048 and the 1/16-type charge-ordered ferromagnetic phase (about 13%) with a Mn⁴⁺ ion concentration of 0.0625. The specific features of the manganite studied are due to self-organization of the La_0.95Ba_0.05MnO₃ crystal lattice caused by the relatively large barium ion size.     

Influence of Tb substitution for La on the structure,magnetic and magneto-transport properties of La1.2Sr1.8Mn2O7

The physical properties of Tb³⁺ ions substitution at A-site are investigated in the layered manganite La_1.2Sr_1.8Mn₂O₇. A series of La_1.2−xTb_xSr_1.8Mn₂O₇ (x=0, 0.05, 0.15, and 0.20) shows that doping with a Tb ion of smaller radius in La_1.2Sr_1.8Mn₂O₇ caused diffraction peaks to shift to high angle. Some samples have an impure diffraction at about 30°, but all samples form single-phase. Samples can be well indexed on a Sr₃Ti₂O7-type tetragonal structure with the space group I4/mmm. According to the M-T curves, when x≤0.05, the series of samples shows ferromagnetism at low temperatures. With increasing temperature, they have two magnetic transitions at different temperatures. When x≥0.15, the magnetizations dramatically decrease. The ρ–T curves of samples show the metal–insulator transition for x=0, 0.05, and the maximum MR values in magnetic field 5 T are 74% at about 73 K and 94% at about 86 K. When x≥0.15, the samples remain in the insulator state in the whole observed temperature range, and the maximum MR values of 86% and 69% appeared at 74 K and 42 K.     

Magnetic and ferroelectric properties of exchange-frustrated multiferroics (Ni1 ? xTx)3V2O8 (T = Co, Mn, Zn)

The effect of the substitution of Co²⁺, Mn²⁺, and Zn²⁺ ions for Ni²⁺ ions on the magnetic, dielectric, and ferroelectric properties of vanadate single crystals (Ni_{1 − x} T _x )₃V₂O₈ has been analyzed. It has been found that the low-level (x ≤ 0.1) substitution of both magnetic and nonmagnetic ions stabilizes the ferroelectric state with a cycloidal magnetic structure. The existence region of this state is expanded to low temperatures down to 3 K for Zn²⁺ and below 1.8 K for Co²⁺ and Mn²⁺ owing to the suppression of a low-temperature weak ferromagnetic phase. At the same time, the ferroelectric phase disappears completely at large concentrations of Co and Mn. The effect of magnetic fields on the magnetic and ferroelectric states has been analyzed. It has been shown that the magnetic field along the c axis suppresses the ferroelectric state, whereas the magnetization along the antiferromagnetism axis (a axis) induces the reentrant phase transition from a paraelectric weak ferromagnetic structure to a ferroelectric structure. The corresponding H-T phase diagrams have been drawn.     

Dielectric and magnetic properties of the multiferroic Tb<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Bi<Subscript>x</Subscript>MnO<Subscript>3</Subscript>: Electric dipole glass and self-organization of charge carriers

Single crystals of the new multiferroic Tb_(1?x)Bi_xMnO₃ have been grown and studied. A semiconductor compound with x = 0.05 is investigated in most detail. At temperatures T ≥ 165 K, the electric dipole glass state is realized in the crystal. Localized charge carriers form conducting drops of electrons and holes, which are located predominantly in thin layers at the boundaries of polar domains. When drops escape as the temperature increases, jumps in conductance and capacitance are observed. The state of drops is controlled by low bias voltage. The long-range magnetic order arises at temperatures T ≤ 90 K. Negative magnetoresistance is observed at temperatures of the existence of localized charge carriers.     

Structural,magnetic, and physical properties of La(1–x)MnO3±δ nano-manganite

A detailed structural, magnetic and physics properties of La_1?xMnO_3±δ (LMO) nanomanganites were investigated to find out the role of cationic vacancies (La vacancy with Mn³⁺/Mn⁴⁺) in grain size modulation. Crystal structure and phase analysis of all samples were carried out by Rietveld refinement of high-resolution XRD and neutron diffraction data. We report here, the oxygen content in studied LMO compound decreases with increase in La vacancies in parent site and a parasitic Mn₃O₄ phase has been evolved in the range of 0.9 ≥ La/Mn ≥ 0.7. Para to ferro magnetic transition temperature (T_C) of all nanometric samples (La/Mn < 0.9) was found at high temperature side (≥260 K) whereas, the same for bulk one (La/Mn ≥ 0.9) was around 160 K. The enhancement of T_C (~70 K) with size reduction is attributed to broadening of bandwidth due to compaction of MnO₆ octahedra in system unit cell. In bulk sample, a secondary cluster/spin glassy phase is found below 50 K, whereas the glassy phase has been suppressed in nanoscale. Field-dependent magneto-resistance measurements are also carried out for all samples at different temperatures to get a profound insight of magneto-transport dynamics of the present system.     

Modulated quasi-two-dimensional antiferromagnetic structures in La1 − y Nd y MnO3 + δ manganites

The structural, electronic, and magnetic phase transitions induced by the isovalent substitution of the rare-earth Nd³⁺ ion for the La³⁺ ion with a larger radius have been investigated in the system of self-doped manganites La_{1 ? y} Nd _y MnO_{3 + δ} (0 ≤ y ≤ 1; δ ～ 0.1). For the average radius of the ions in A-sites of the lattice 〈r _A 〉 〈 1.19 Å (y 〉 0.5), the phenomena revealed in the manganites are as follows: the ordering of Mn e _g orbitals, the transition from the pseudocubic O* phase to the orthorhombic O’ phase, the opening of the dielectric Jahn-Teller gap, the frustration of the collinear ferromagnetic (FM) state, and the transition from the lowtemperature canted FM to canted antiferromagnetic (AFM) state of Mn spins. It is assumed that, in samples with neodymium concentrations y = 0.9 and 1.0 (〈r _A 〉 ≈ 1.16 Å) at temperatures T < 12 K, there coexist A- and E-type modulated AFM states similar to the sinusoidal and helical structures of Mn spins, which were previously studied in RMnO₃ multiferroics. The magnetic T-H phase diagrams of these samples are characteristic of quasi-two-dimensional antiferromagnets with a very low (zero) magnetic anisotropy in the ab planes. Under these conditions, the phase transition from the A-type AFM phase to the spin-flop state occurs in a relatively weak magnetic field. The AFM ordering of the Nd magnetic moments with a critical phase transition temperature T _Nd ≌ 6 K is induced in magnetic fields with a strength H ≥ 3.5 kOe. For the NdMnO_{3 + δ} manganite in a magnetic field H = 10.7 kOe, the curves M(T) are characterized by additional very narrow peaks near temperatures T ₁ ≌ 4.5 K and T ₂ ≌ 5 K. The additional features revealed for the first time in the magnetization near T = 0 are assumed to be caused by the quantization of the spectrum of free holes in the ab planes by a strong magnetic field.     

Magnetic ordering in the T* phase La1.2Tb0.8CuO4

We report a muon spin relaxation study of the magnetic properties of the La_1.2Tb_0.8CuO₄ phase with the T^* structure. Random magnetic order is revealed between 280 and 170 K by the zero field data. A spontaneous muon precession then appears below 170 K, arising from antiferromagnetic long range order of the Cu²⁺ spins. Evidence exists below 20 K for ordering of the Tb³⁺ ions. We find that the T^* phase adopts the same magnetic structure as the (T/O) phase La₂CuO₄.     

Dielectric relaxation and magnetic characteristics of the Bi0.5La0.5MnO3 ceramics

The complex permittivity ?* of ceramics of bismuth-lanthanum manganite Bi_0.5La_0.5MnO₃ has been measured in ranges of temperatures T = 10–200 K and frequencies f = 10²–10⁶ Hz. Clearly pronounced regions of the non-Debye dielectric relaxation have been revealed at low temperatures (T < 90 K). To describe them, the possible mechanisms have been proposed and discussed. The temperature dependences of magnetization, the anomalous behavior of which can be associated with the phase transition from the paramagnetic phase into the ferromagnetic phase occurring at T ～ 40–80 K, have been measured in the temperature range T = 10–120 K.     

Interaction between the magnetic moments of the 3d and the 4f electrons in manganite, probed by Ga substitution

The substitution of Ga for Mn in manganite Nd_0.6Dy_0.1Sr_0.3MnO₃ with a ferromagnetic (FM) ground state has been performed to study the influence of the Mn-sublattice magnetic ordering on the magnetic rare-earth sublattice. It is found that the substitution of Mn³⁺ with Ga³⁺ ions results in a sharp decrease of T_C, reflecting the reduction of the double-exchange interactions strength J_Mn-Mn. At the same time, a depinning effect of the rare-earth magnetic moment has been observed. This behavior unambiguously proves that the exchange interaction between Mn and rare-earth ions J_Mn-R strongly influences the rare-earth magnetic ordering at temperatures below T_C and stabilizes the rare-earth magnetic ground state.     

Causes of the Metamagnetism in a Disordered EuMn<Subscript>0.5</Subscript>Co<Subscript>0.5</Subscript>O<Subscript>3</Subscript> Perovskite

The magnetic properties of the EuMn_0.5Co_0.5O₃ perovskite synthesized under various conditions are studied in fields up to 140 kOe. The sample synthesized at T = 1500°C is shown to exhibit a metamagnetic phase transition, which is irreversible below T = 40 K, and the sample synthesized at T = 1200°C demonstrates the field dependence of magnetization that is typical of a ferromagnet. Both samples have T_C = 123 K and approximately the same magnetization in high magnetic fields. The metamagnetism is assumed to be related to a transition from a noncollinear ferromagnetic phase to a collinear phase, and the presence of clusters with ordered Co²⁺ and Mn⁴⁺ ions leads to ferromagnetism. The noncollinear phase is formed due to the competition between positive Co²⁺–Mn⁴⁺ and negative Mn⁴⁺–Mn⁴⁺ and Co²⁺–Co²⁺ interactions, which make almost the same contributions, and to the existence of a high magnetic anisotropy.