Magnetism of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> manganite in structurally ordered and disordered states

The specific features of the crystal structure and the magnetic state of stoichiometric lithium manganite in the structurally ordered Li[Mn₂]O₄ and disordered Li_{1 − δ}Mn_δ[Mn_{2 − δ}Li_δ]O₄ (δ = 1/6) states have been investigated using neutron diffraction, X-ray diffraction, and magnetic methods. The structurally disordered state of the manganite was achieved under irradiation by fast neutrons (E _eff ≥ 1 MeV) with a fluence of 2 × 10²⁰ cm⁻² at a temperature of 340 K. It has been demonstrated that, in the initial sample, the charge ordering of manganese ions of different valences arises at room temperature, which is accompanied by orthorhombic distortions of the cubic spinel structure, and the long-range antiferromagnetic order with the wave vector k = 2π/c(0, 0, 0.44) is observed at low temperatures. It has been established that the structural disordering leads to radical changes in the structural and magnetic states of the LiMn₂O₄ manganite. The charge ordering is destroyed, and the structure retains the cubic symmetry even at a temperature of 5 K. The antiferromagnetic type of ordering transforms into ferrimagnetic ordering with local spin deviations in the octahedral sublattice due to the appearance of intersublattice exchange interactions.     

Destruction of manganite La0.825Ba0.175MnO3 ferromagnetism caused by structural disordering

The methods of neutron diffraction, X‐ray and magnetic measurements were used to study the structural and magnetic states of disordered samples of manganite La_0.825Ba_0.175MnO₃. A disordered state was attained by irradiation with fast neutrons. It was established that the ferromagnet → spin glass‐like magnetic transformation takes place at a substitution concentration of ～6%. A magnetic state diagram of structurally disordered manganite was constructed. The magnetic state transformations are explained by the effect of localization of e _g‐electrons responsible for kinetic ferromagnetic exchange. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Magnetic structure and transport properties of atomically disordered crystals of two-dimensional manganites La2−2x Sr1+2x Mn2O7

The magnetic structure and transport properties of partially disordered crystals of two-dimensional manganites La_2?2x Sr_1+2x Mn₂O₇ (x = 0.3, 0.4) are studied over a wide range of temperatures. The crystals are transformed into an atomically disordered state under irradiation with fast neutrons at a dose of 2 × 10¹⁹ cm^?2. The average concentration of substitutional defects in the crystal is ≈4%. It is found that substitutional defects are responsible for the transition of these manganites from the ferromagnetic metal state to the insulator state with a spin glass structure. The results obtained are discussed in terms of the ratio between the kinetic energy of charge carriers and the exchange energy of localized spins.     

(139La, 55Mn) NMR and magnetic susceptibility data on microscopic phase separation in La0.9MnO3 single crystal

Magnetic susceptibility of the La_0.9MnO₃ single crystal was measured and its (¹³⁹La, ⁵⁵Mn) NMR spectra were recorded. The data obtained indicate that the areas with an A-type antiferromagnetic order (T _N=140 K) and magnetic moments aligned with the b axis occupy a major part of the sample volume in manganite with a considerable concentration of cationic vacancies; simultaneously, the clusters with a canted magnetic sublattice and ferromagnetic interaction between magnetic moments are formed near the vacancies. Charge distribution in these clusters is materially different from that in the antiferromagnetic areas. Magnetic state and relative concentration of the clusters are discussed.     

Effects of structural disorder in lithium manganite and titanate oxides

The structures and magnetic states of stoichiometric lithium manganite LiMn₂O₄ and manganites and titanates Li_1.33Mn_1.67O₄ and Li_1.33Ti_1.67O₄ with excess lithium in both the initial (as-synthesized) state and after irradiation by fast (E _eff ≥ 1 MeV) neutrons with a fluence of 2 × 10²⁰ cm⁻² have been studied using neutron diffraction, X-ray diffraction, and magnetic methods. It has been established that the irradiation brings about a noticeable redistribution of manganese, titanium, and lithium cations over nonequivalent tetrahedral (8a) and octahedral (16d) positions of a spinel lattice. This structural disorder causes a radical change in the physical properties of the materials under study. The charge order existing in the initial LiMn₂O₄ sample is destroyed. There arises a strong intersublattice indirect exchange interaction Mn(8a)-O-Mn(16d). The disorder is accompanied by the antiferromagnet-ferrimagnet (LiMn₂O₄) and paramagnet-ferrimagnet (Li_1.33Mn_1.67O₄) magnetic transitions.     

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.     

Magnetic structure of a CaMnO2.75 crystal with ordered oxygen vacancies

The magnetic state of a CaMnO_{3 ? δ} crystal with ordered oxygen vacancies (for δ = 0.25, when the numbers of Mn⁴⁺ and Mn³⁺ ions in the manganite are equal to each other) is studied using neutron diffraction. Magnetic scattering in the CaMnO_2.75 crystal in the ground state is determined by the wave vector (1/2, 1/2, 1/2)2π/a _c (G-type antiferromagnetic order). In the crystal, long-range magnetic order disappears at the temperature T _N = 116 K, whereas short-range magnetic order is retained up to 240 K. It is shown that the instability of the G-type structure in the temperature range 60 K < T < T _N is associated, in many respects, with the formation of the C′ antiferromagnetic phase in the bulk of the crystal. The structure of the C′ antiferromagnetic phase involves chains with Mn³⁺-Mn⁴⁺ ferromagnetic interaction. A comparison of the results of the neutron diffraction investigations with the experimental data on the magnetic characteristics and electrical resistivity demonstrates that the specific features revealed in the spin system of the CaMnO_2.75 crystal are governed directly by the competition of the Mn³⁺-Mn⁴⁺ ferromagnetic double exchange with the antiferromagnetic superexchange between manganese ions.     

Effect of the chemical composition on amorphization of titanium-nickelide-based alloys with fast neutrons

The structural state of a Ti₅₀Ni₄₇Fe₃ single crystal irradiated with fast neutrons (F = 2.5 × 10²⁰ cm^?2) at a temperature of 340 K was studied using thermal neutron diffraction. The alloy of this chemical composition was chosen in searching for a radiation-resistant shape memory material. It is established that this alloy retains its crystalline state after irradiation, whereas the Ti₄₉Ni₅₁ crystal studied previously is completely amorphized after similar irradiation. A detailed analysis of the structural state of the irradiated ternary alloy allowed us to discover the main physical causes of its radiation resistance.     

NMR study of magnetic moments arising in superconducting cuprates under electron/neutron irradiation

The measurements of direct-current magnetic susceptibility and nuclear magnetic resonance (NMR) were performed in the superconducting cuprates YBa₂Cu₃O_6.9 (⁸⁹Y,⁶³Cu), Tl₂Ba₂CaCu₂O₈ (¹⁷O,²⁰⁵Tl), irradiated by fast neutrons (E _n = 1 MeV) and electrons (E _e = 5 MeV). The influence of the radiation-induced structural disorder on the spin susceptibility and magnetic state of atoms in the CuO₂ layer is considered. The possible effect onT _c of the spin-exchange scattering of carriers by localized moments arising under irradiation was estimated following the Abrikosov-Gorkov approach and its contribution was found to be too small in comparison with the real suppression ofT _c under irradiation.     

Magnetic hyperfine interactions of 119Sn probe atoms in the binary perovskite CaCu3Mn4O12

The manganite CaCu₃Mn₄O₁₂ doped by ¹¹⁹Sn atoms (about 1 at % with respect to Mn atoms) is studied by Mössbauer spectroscopy. The introduction of diamagnetic tin atoms is found not to affect the structure of the manganite. Tetravalent tin atoms are shown to substitute for the isovalent manganese atoms that are located in an octahedral oxygen surrounding. The cluster method of molecular orbitals is used to calculate the contributions of Mn⁴⁺ and Cu²⁺ cations that belong to different structural sublattices to the hyperfine magnetic field at ¹¹⁹Sn nuclei (H _Sn = 105 kOe at T = 77 K). These partial contributions are analyzed, and the intrasublattice Mn⁴⁺-O-Mn⁴⁺ exchange interactions are found to play a significant role in the formation of the magnetic structure of the manganite.     

Imperfection of the clustered perovskite structure, phase transitions, and magnetoresistive properties of ceramic La0.6Sr0.2Mn1.2 ? x Ni x O3 ± δ (x = 0–0.3)

Ceramic samples of lanthanum strontium manganite perovskites La_0.6Sr_0.2Mn_{1.2 ? x} Ni _x O_{3 ± ??} (0 ?? x ?? 0.3) have been investigated using the X-ray diffraction, magnetic (??_ac), ⁵⁵Mn NMR, resistive, and magnetoresistive methods. The specific features of the influence of the composition on the structure and properties of nonstoichiometric manganite perovskites have been established. It has been found that the rhombohedrally (R $\bar 3$ c) distorted perovskite structure contains cation and anion vacancies, as well as nanostructured clusters with Mn²⁺ ions in the A-positions. The substitution of Ni³⁺ ions (r = 0.74 ?) for Mn³⁺ ions (r = 0.785 ?) leads to a decrease in the lattice parameter a, the ferromagnetic-paramagnetic phase transition temperature T _C, and the metal-semiconductor phase transition temperature T _ms due to the disturbance of the superexchange interactions between heterovalent manganese ions Mn³⁺ and Mn⁴⁺. The observed anomalous magnetic hysteresis at 77 K has been explained by the antiferromagnetic effect of the unidirectional exchange anisotropy of the ferromagnetic matrix structure on the magnetic moments of the superstoichiometric manganese Mn²⁺ ions located in nanostructured planar clusters. An analysis of the asymmetrically broadened ⁵⁵Mn NMR spectra of the compounds has revealed a high-frequency electronic superexchange of the ions Mn³⁺ ? O^2? ? Mn⁴⁺; a local heterogeneity of their surrounding by other ions, vacancies, and clusters; and a partial localization of Mn⁴⁺ ions. The local hyperfine interaction fields on ⁵⁵Mn nuclei have been determined. The concentration dependences of the activation energy and charge hopping frequency have confirmed that the Ni ions decrease the electrical conductivity due to the weakening of the electronic superexchange Mn³⁺ ? O^2? ? Mn⁴⁺. Two types of magnetoresistive effects have been found: one effect, which is observed near the phase transition temperatures T _C and T _ms, is caused by scattering at intracrystalline nanostructured heterogeneities, and the other effect, which is observed in the low-temperature range, is induced by tunneling through intercrystalline mesostructured boundaries. The phase diagram has demonstrated that there is a strong correlation between magnetic and electrical properties in rare-earth manganites.     

Magnetic properties of La0.70Sr0.30MnO2.85 anion-deficient manganite under hydrostatic pressure

The magnetic properties of La_0.70Sr_0.30MnO_2.85 anion-deficient manganite are studied experimentally under hydrostatic pressure. The results show that, in the whole pressure range under investigation (0–1 GPa), the sample is a spin glass with a smeared phase transition to the paramagnetic state. It is found that the spin glass state arises from the frustration of the exchange coupling of the ferromagnetic clusters embedded in the antiferromagnetic matrix. The fraction of the sample volume occupied by the ferromagnetic phase is found to be V _fer ～ 13%. Under hydrostatic pressure, the freezing temperature T _f of the magnetic moments of the ferromagnetic clusters increases at a rate of 4.30 K/GPa and the magnetic ordering temperature T _MO increases at a rate of 12.90 K/GPa. In addition, the ferromagnetic part of the sample increases by ΔV _fer ～ 5%. The enhancement of the ferromagnetic properties of La_0.70Sr_0.30MnO_2.85 anion-deficient manganite under hydrostatic pressure is explained by the redistribution of oxygen vacancies and a decrease in the unit-cell parameters.     

Structure and magnetism of the manganite LaMnO3 with defects

The structural and magnetic states of LaMnO₃ samples containing various concentrations of antisite defects created by fast-neutron irradiation were studied by neutron diffraction, x-ray diffraction, and magnetic measurements. It is found that the static uncorrelated displacements of oxygen ions induced by the formation of antisite defects break the Jahn-Teller Q ₂ mode and the initial orthorhombic O′-type structure transforms into the pseudocubic O ^* modification. As a result, the indirect ferromagnetic exchange caused by the overlap of the e _g orbitals of manganese ions and the p _σ orbitals of oxygen ions becomes three-dimensional and the initial A-type antiferromagnetic phase transforms into a canted ferromagnetic phase. The magnetic phase diagram of LaMnO₃ is plotted for various defect concentrations.     

Magnetic,electrical transport and electron spin resonance studies of Fe-doped manganite LaMn0.7Fe0.3O3+δ

We have investigated the magnetic, electrical transport and electron spin resonance (ESR) properties of polycrystalline Fe-doped manganite LaMn_0.7Fe_0.3O_3+δ prepared by sol–gel method. A typical cluster-glass feature is presented by DC magnetization and AC susceptibility measurements and a sharp but shallow memory effect was observed. Symmetrical Lorentzian lines of the Mn/Fe spectra were detected above 120 K, where the sample is a paramagnetic (PM) insulator. When the temperature decreases from 120 K, magnetic clusters contributed from ferromagnetic (FM) interaction between Mn³⁺ and Mn³⁺/Fe³⁺ ions develop and coexist with PM phase. At lower temperature, these FM clusters compete with antiferromagnetic (AFM) ones between Fe³⁺ ions, which are associated with a distinct field-cooled (FC) effect in characteristic of cluster-glass state.     

Small-angle neutron scattering study of radiation defects in synthetic quartz

The superatomic structure of synthetic quartz single crystals with dislocation densities ρ = 54 and 570 cm^?2 was studied in the initial state and after irradiation with fast neutrons with energies E _n > 0.1 MeV in a WWRM reactor (St. Petersburg Nuclear Physics Institute) in the fluence range F = 0.2 × 10¹⁷?5.0 × 10¹⁸ neutrons/cm². Weak irradiation with F = 0.2 × 10¹⁷ neutrons/cm² causes only slight structural changes, whereas appreciable generation of defects with radii of gyration r _g ～ 1–2 nm and R _G ～ 40–50 nm occurs at F = 7.7 × 10¹⁷?5.0 × 10¹⁸ neutrons/cm². As the fluence increases further, the number and volume fraction of point defects, as well as extended (channels ～2 nm in radius) and globular (amorphous phase nuclei) defects, increase.     

Mictomagnetic State in an EuBaCo<Subscript>2–<Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>5.5–δ</Subscript> Single Crystal

The magnetic properties of an EuBaCo_1.9O_5.36 single crystal are studied in the temperature range T = 2–300 K and the magnetic field range H ≤ 90 kOe. This binary layered cobaltite single crystal has vacancies in the cobalt and oxygen sublattices, in contrast to the stoichiometric EuBaCo₂O_5.5 composition. All cobalt ions in EuBaCo1.9O5.36 are in a trivalent state. The single crystal has an orthorhombic structure with space group Pmmm, and its unit cell parameters are a = 3.883 Å, b = 7.833 Å, and c = 7.551 Å. The field and temperature dependences of the magnetization of the single crystal demonstrate that it is ferrimagnet below T_C = 242 K. At T < 300 K, all three spin states of the Co³⁺ ions are present. The nearest-neighbor interactions give antiferromagnetic (AFM) and ferromagnetic (FM) contributions to the exchange energy. The ratio of the AFM to the FM contributions changes when temperature decreases because of a change in the spin state of the Co³⁺ ions. The single crystal exhibits signs of mictomagnetism at low temperatures in high magnetic fields. At T = 2 K and H = 90 kOe, the zero-field and nonzero-field magnetizations are strongly different because of a uniaxial magnetic anisotropy, which tends to set magnetization along the magnetic field applied in cooling throughout the crystal volume. As a result, a complex ferrimagnetic structure with a noncollinear direction of Co³⁺ spins appears. The following phenomena characteristic of mictomagnets are also observed in the EuBaCo_1.9O_5.36 single crystal: a shift in a magnetization hysteresis loop when temperature decreases, retained hysteretic phenomena and no magnetization saturation in high magnetic fields, and an orientation transition. The mictomagnetic state in EuBaCo_1.9O_5.36 is shown to be caused by the structural distortions induced by vacancies in the cobalt and oxygen sublattices and by the frustration of AFM and FM exchange interactions.     

Calculation of the electronic structure,lattice dynamics,and optical and magnetic properties of europium tetraborate EuB<Subscript>4</Subscript>O<Subscript>7</Subscript>

The electronic band structure, lattice vibration frequencies, and optical and magnetic properties of EuB₄O₇ crystal with α-SrB₄O₇-type structure are calculated within the density functional method. It is found that this compound is a dielectric with a band gap of the order of 4 eV. It is found that the ground state of this crystal is the state with ferromagnetic ordering of Eu²⁺ spins. Exchange interaction constants are calculated; the ferromagnetic ordering temperature is estimated within the molecular field approximation (T_c ≈ 1 K). The EuB₄O₇ compound is a magnetic pyroelectric and, hence, can exhibit magnetoelectric properties. The calculated polarization change during ferromagnetic ordering of this crystal is 3973 μC/m².     

Role of the Cluster Structure of Amorphous Fe<Subscript>67</Subscript>Cr<Subscript>18</Subscript>B<Subscript>15</Subscript> Alloy in Magnetism and in the Changing of Electron Scattering Mechanisms under the Influence of Ion (Ar<Superscript>+</Superscript>) Irradiation

The contribution of clusters of different sizes to magnetism and the switching of electron scattering mechanisms in amorphous Fe₆₇Cr₁₈B₁₅ alloy during ion Ar⁺ irradiation is studied. The cluster magnetism is found to be related to the presence of clusters of the following two types: large α-(Fe, Cr) clusters of size D = 150–250 Å and small (D = 40–80 Å) clusters in a random intercluster medium. The generation of small ferromagnetic and antiferromagnetic clusters during ion irradiation leads to the formation of cluster glass, which affects the electrical properties of the alloy and causes a magnetic frustration. The temperature dependence of the barrier height is shown to characterize the magnetic state of the alloy in low fields. On the whole, the temperature dependence of the order parameter is a universal characteristic of the system. The temperature dependence of resistivity of initial alloys in the temperature range 98–300 K (ρ(T) ∝ T²) is determined by electron scattering by quantum defects, and the transition into a ferromagnetic state is revealed when the derivative ?ρ/?T ∝ T is analyzed. The increase in resistivity and the relation ρ ∝ T^1/2 in strongly inhomogeneous samples after irradiation at a dose Φ = 1.5 × 10¹⁸ ions/cm² are caused by weak localization effects, and the transition to a ferromagnetic state becomes obvious when the derivative ?ρ/?T ∝ T^–1/2 is considered. Irradiation by fluence Φ = 3 × 10¹⁸ ions/cm2 induces a giant (twofold) increase in the alloy density, restores the ferromagnetism of large clusters, decreases the resistivity by 37%, and restores the relation ρ(T) ∝ T², which results from the overlapping of the irradiation-induced small clusters when their concentration increases and from an increase in the alloy density. The overlapping of clusters lowers the barrier height and decreases the sensitivity of the alloy to an applied field. The relation ρ(T) ∝ T² is valid for the entire temperature range T = 2–300 K because of the partial screening of the magnetic moments of large clusters by a medium having the properties of cluster glass.     

Structural and magnetic inhomogeneities,phase transitions, 55Mn nuclear magnetic resonance,and magnetoresistive properties of La0.6 − x Nd x Sr0.3Mn1.1O3-δ ceramics

The structure, lattice imperfection, and properties of ceramic samples La_{0.6 ? x} Nd _x Sr_0.3Mn_1.1O_3-δ (x = 0–0.4) have been investigated using the X-ray diffraction, resistive, magnetic (χ_ac, ⁵⁵Mn NMR), magnetoresistive and microscopic methods. It has been shown that there is a satisfactory agreement between the concentration decrease in the lattice parameters a of the rhombohedral (x = 0, 0.1, 0.2) and cubic (x = 0.3, 0.4) perovskite structures and the average ionic radii $\bar R$ for the lattice containing anion vacancies, cation vacancies, and nanostructured clusters with Mn²⁺ ions in A-positions. With an increase in the neodymium concentration x, the vacancy-type imperfection increases, the cluster-type imperfection decreases, the temperatures of metal-semiconductor phase transition T _ms and ferromagnetic-paramagnetic phase transition T _C decrease, and the content of the ferromagnetic phase decreases. The anomalous hysteresis is associated with the appearance of unidirectional exchange anisotropy induced in a clustered perovskite structure consisting of a ferromagnetic matrix and a planar antiferromagnetic cluster coherently coupled with it. An analysis of the asymmetrically broadened ⁵⁵Mn NMR spectra has revealed a high-frequency electronic double exchange (Mn³⁺-O^2?-Mn⁴⁺) ? (Mn⁴⁺-O^2?-Mn³⁺) and an inhomogeneity of the magnetic and charge states of manganese due to the heterogeneous environment of the manganese ions by other ions and defects. The observed changes in the resonant frequency and width of the resonance curve are caused by changes in the ratio Mn³⁺/Mn⁴⁺ and magnetic inhomogeneity. An increase in the neodymium concentration x leads to a decrease in the ferromagnetic phase content determined from the dependences 4πNχ_ac(T) and the ⁵⁵Mn NMR curves. The phase diagram characterizes an interrelation between the composition, the imperfection of the structure, and the transport, magnetic, and magnetoresistive properties of lanthanum neodymium manganite perovskites. It has been found that there is a correlation between the imperfection, magnetic inhomogeneity, coercive force, and magnetoresistance effect exhibited by the perovskite structure.     

Probing the magnetic state by linear and non-linear ac magnetic susceptibility measurements in under-doped manganite Nd0.8Sr0.2MnO3

We have thoroughly investigated the entire magnetic states of under-doped ferromagnetic-insulating manganite Nd_0.8Sr_0.2MnO₃ through temperature-dependent linear and non-linear complex ac magnetic susceptibility measurements. This ferromagnetic-insulating manganite is found to have frequency-independent ferromagnetic to paramagnetic transition temperature at around 140 K. At around 90 K (≈T_?) the sample shows a second frequency-dependent re-entrant magnetic transition as explored through complex ac susceptibility measurements. Non-linear ac susceptibility measurements (higher harmonics of ac susceptibility) have also been performed (with and without the superposition of a dc magnetic field) to further investigate the origin of this frequency dependence (dynamic behavior at this re-entrant magnetic transition). Divergence of 3rd harmonic of ac susceptibility in the limit of zero exciting field indicates a spin-glass-like freezing phenomena. However, large value of spin-relaxation time (τ₀=10⁻⁸ s) and small value of coercivity (∼22 Oe) obtained at low temperature (below T_?) from critical slowing down model and dc magnetic measurements, respectively, are in contrast with what generally observed in a canonical spin glass (τ₀=10⁻¹²-10⁻¹⁴ s and very large value of coercivity below freezing temperature). We have attributed our observation to the formation of finite size ferromagnetic clusters which are formed as consequence of intrinsic phase separation and undergo cluster glass-like freezing below certain temperature in this under-doped manganite. The results are supported by the electronic- and magneto-transport data.