EPR study of copper ions in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals

The EPR spectra of Cu²⁺ ions (² D _5/2) located at two structurally nonequivalent positions Cu1 and Cu2 in crystals of lithium heptagermanate Li₂Ge₇O₁₅ are recorded. The angular dependences of the EPR spectrum are measured in the paraelectric phase of the Li₂Ge₇O₁₅ compound (T = 300 K). The components of the g factor and the hyperfine interaction tensor A are determined, and the orientation of the magnetic axes with respect to the crystallographic basis is established. The EPR spectra are recorded in the temperature range in the vicinity of the temperature T _C = 283 K of the transition from the paraelectric phase to the ferroelectric phase. The position symmetry of the Cu1 and Cu2 centers is determined at temperatures above and below the phase transition temperature T _C . The localization of paramagnetic centers in the structure is discussed, An analysis of the results obtained demonstrates that the Cu1 and Cu2 centers in the Li₂Ge₇O₁₅ crystal lattice replace lithium ions located at two structurally nonequivalent positions with the symmetries described at temperatures above T _C by the triclinic C _i and monoclinic C ₂ point groups, respectively.     

Concentration quenching and migration of excitations in a bulk Cd<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>Te crystal

The curves of intracenter luminescence decay for Mn²⁺ ions in the Cd_0.5Mn_0.5Te semiconductor solid solution, obtained in a low-temperature experiment, have been simulated by the Monte Carlo method. The features of the kinetics of the 2-eV band in the time interval where significant nonexponentiality of relaxation at different points of the emission band profile manifests itself, as well the integral kinetics and energy relaxation, have been considered. Migration of ion excitations and concentration quenching (which was previously disregarded) are considered to be the main mechanisms determining the kinetic curve formation. It was established that excitation by 2.34-eV photons leads to both selective (intracenter) and band excitation of Mn²⁺ ions. Comparison of the results of numerical simulation and experiment showed that the characteristic values of the migration and quenching rates (W _m and W _q , respectively) are close in magnitude and W _{q, m} ≈ 0.1/τ, where τ is the lifetime at the long-wavelength band wing with the exponential kinetics. The estimated quantum yield (0.56) indicates significant influence of the concentration quenching on the 2-eV luminescence quantum yield in Cd_{1 ? x} Mn _x Te and Zn_{1 ? x} Mn _x S crystals with a high concentration of Mn²⁺ ions.     

Spin-wave resonance in Ge<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> films exhibiting percolation ferromagnetism

Magnetic properties of Ge_{1 ? x} Mn _x (x = 0.02, 0.04, 0.08) thin films obtained by ion-implanting Mn⁺ ions into single-crystal Ge plates are investigated. The contributions of the subsystem of dispersed Mn²⁺ ions, Ge³Mn⁵ ferromagnetic clusters, and Mn-enriched ferromagnetic domains of Ge to the magnetic moment of Ge_{1 ? x} Mn _x films are distinguished. In the subsystem of dispersed Mn²⁺ ions in Ge_{1 ? x} Mn _x films at temperatures below 10 K, a spin-wave resonance is observed in the magnetically ordered state due to percolation ferromagnetism. It is established that, in the films with percolation ferromagnetism, the exchange integrals determined from static measurements correspond to those determined by dynamic measurements.     

EPR-Determined Anisotropy of the <Emphasis Type="Italic">g</Emphasis>-Factor and Magnetostriction of a Cu<Subscript>2</Subscript>MnBO<Subscript>5</Subscript> Single Crystal with a Ludwigite Structure

Electron paramagnetic resonance (EPR) and magnetostriction of the Cu₂MnBO₅ single crystal have been studied. The EPR spectrum consists of a single Lorentzian line due to the exchange-coupled system of spins of Cu²⁺ and Mn³⁺ ions. It has been established experimentally that the g-factor in the paramagnetic region is strongly anisotropic and anomalously small, which is not typical of the exchange-coupled system of spins of Cu²⁺ and Mn³⁺ ions. At a temperature of 150 K, the g-factors along the crystallographic a, b, and c axes are 2.04, 1.96, and 1.87, respectively. Such small effective g-factor values can be due to the effect of the anisotropic Dzyaloshinskii–Moriya exchange interaction between the spins of Cu²⁺ and Mn³⁺ ions directed along the a axis. The presence of two Cu²⁺ and Mn³⁺ Jahn–Teller ions occupying four nonequivalent positions in the crystal is responsible for the absence of the inversion center. It is found that the behavior of the magnetostriction of Cu₂MnBO₅ is not typical of transition-metal crystals but is closer to the behavior of crystals containing rare-earth ions.     

Exchange Bias in Layered GdBaCo<Subscript>2</Subscript>O<Subscript>5.5</Subscript> Cobaltite

It is established that excess oxygen content δ influences the exchange bias (EB) in layered GdBa-Co₂O_{5 + δ} cobaltite. The EB effect arises in p-type (δ > 0.5) cobaltite and disappears in n-type (δ < 0.5) cobaltite. The main parameters of EB in GdBaCo₂O_5.52(2) polycrystals are determined, including the field and temperature dependences of EB field H _EB , blocking temperature T _B , exchange coupling energy J _i of antiferromagnet–ferromagnet (AFM–FM) interface, and dimensions of FM clusters. The training effect inherent in systems with EB has been studied. The results are explained in terms of exchange interaction between the FM and AFM phases. It is assumed that the EB originates from the coexistence of Co³⁺ and Co⁴⁺ ions that leads to the formation of monodomain FM clusters in the AFM matrix of cobaltite.     

Critical behavior of La<Subscript>0.825</Subscript>Sr<Subscript>0.175</Subscript>MnO<Subscript>2.912</Subscript> anion-deficient manganite in the magnetic phase transition region

For La _0.825 ³⁺ Sr _0.175 ² +Mn³⁺O _2.912 ^2? anion-deficient manganite, the specific magnetization, the dynamic magnetic susceptibility, and the heat capacity are investigated. This material is found to be an inhomogeneous ferromagnet below the Curie point T _C ≈ 122 K, which is much lower than the Curie point determined for the stoichiometric composition (T _C ≈ 268 K). An increase in magnetic field by two orders of magnitude leads to an increase in the Curie temperature by ΔT ≈ 12 K. The presence of oxygen vacancies leads to the frustration of a part, namely, V _fr ≈ 22%, of the indirect Mn³⁺-O-Mn³⁺ exchange interactions, but the spin glass state is not realized. The ferromagnetic matrix of the material under study is characterized by a scatter in the exchange interaction intensities. The heat capacity is found to exhibit an anomalous behavior. Based on the Banerjee magnetic criterion, it is established that the ferromagnet-paramagnet transition observed for La _0.825 ³⁺ Sr _0.175 ²⁺ Mn³⁺O _2.912 ^2? anion-deficient manganite is a second-order thermodynamic phase transition. The mechanism and origin of the critical behavior of the system under investigation are discussed.     

Substitution effects on the bulk and surface properties of (Li,Ni)Mn<Subscript>2</Subscript>O<Subscript>4</Subscript>

Manganese oxides of spinel structure, LiMn₂O₄, Li_1-x Ni _x Mn₂O₄ (0.25 ≤ x≤ 0.75), and NiMn₂O₄, were studied by EDS, XRD, SEM, magnetic (M-H, M-T), and XPS measurements. The samples were synthesized by an ultrasound-assisted sol-gel method. EDS analysis showed good agreement with the formulations of the oxides. XRD and Rietveld refinement of X-ray data indicate that all samples crystallize in the Fd3m space group characteristic of the cubic spinel structure. The a-cell parameter ranges from a = 8.2276 Å (x = 0) to a = 8.3980 Å (x = 1). SEM results showed particle agglomerates ranging in size from 2.3 μm (x = 0) down to 0.8 μm (x = 1). Hysteresis magnetization vs. applied field curves in the 5–300K range was recorded. ZFC-FC measurements indicate the presence of two magnetic paramagnetic-ferrimagnetic transitions. The experimental Curie constant was found to vary from 5 to 7.1 cm³ K mol^?1 for the range of compositions studied (0 ≤ x ≤ 1). XPS studies of these oxides revealed the presence of Ni²⁺, Mn³⁺, and Mn⁴⁺. The experimental Ni/Mn atomic ratios obtained by XPS were in good agreement with the nominal values. A linear relationship of the average oxidation state of Mn with Ni content was observed. The oxide’s cation distributions as a function of Ni content from x = 0 ?Li⁺[Mn³⁺Mn⁴⁺]O₄ to x = 1 \( {\mathrm{Ni}}_{0.35}^{2+}{\mathrm{Mn}}_{0.65}^{3+}\left[{\mathrm{Ni}}_{0.65}^{2+}\right.\left.{\mathrm{Mn}}_{1.35}^{3+}\right]{\mathrm{O}}_4 \) were proposed.     

Magnetic Structures and Magnetic Phase Transitions in Rare-Earth <Emphasis Type="Italic">R</Emphasis>Mn<Subscript>2</Subscript>Si<Subscript>2</Subscript> Intermetallic Compounds (<Emphasis Type="Italic">R</Emphasis> = Sm,Tb)

The magnetic structures that form in La_1–xR_xMn₂Si₂ (R = Sm, Tb) layered compounds with various concentrations x have been determined by magnetic neutron diffraction and magnetic measurements, and the magnetic phase diagrams have been built. It is shown that the formation of the magnetic structures is dependent not only on exchange interactions, but also on the type of the magnetic anisotropy of a rare-earth atom. It is found that, in La_1–xTb_xMn₂Si₂ compounds with 0.2 < x < 0.5, the competition of the Tb–Mn and Mn–Mn interlayer exchange interactions and the existence of a strong uniaxial magnetic anisotropy in the Mn and Tb sublattices leads to the frustrated magnetic state and prevents the formation of the long-range magnetic order in the Tb sublattice.     

Electron paramagnetic resonance of Cr<Superscript>3+</Superscript>-Li<Superscript>+</Superscript> centers in (Cr,Li): Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> synthetic forsterite

Synthetic single crystals of chromium-and lithium-doped forsterite, namely, (Cr,Li): Mg₂SiO₄, are studied using electron paramagnetic resonance spectroscopy. It is revealed that, apart from the known centers Cr³⁺(M1) and Cr³⁺(M2) (with local symmetries C_i and C_s, respectively), these crystals involve two new types of centers with C₁ symmetry, namely, Cr³⁺(M1)′ and Cr³⁺(M2)′ centers. The standard parameters D and E in a zero magnetic field [zero-field splitting (ZFS) parameters expressed in GHz] and principal components of the g tensor are determined as follows: D=31.35, E=8.28, and g=(1.9797, 1.9801, 1.9759) for Cr³⁺(M1)′ centers and D=15.171, E=2.283, and g=(1.9747, 1.9769, 1.9710) for Cr³⁺(M2)′ centers. It is found that the lowsymmetric effect of misalignment of the principal axes of the ZFS and g tensors most clearly manifests itself (i.e., its magnitude reaches 19°) in the case of Cr³⁺(M2)′ centers. The structural models Cr³⁺(M1)-Li⁺(M2) and Cr³⁺(M2)-Li⁺(M1) are proposed for the Cr³⁺(M1)′ and Cr³⁺(M2)′ centers, respectively. The concentrations of both centers are determined. It is demonstrated that, upon the formation of Cr³⁺-Li⁺ ion pairs, the M1 position for chromium appears to be two times more preferable than the M2 position. Reasoning from the results obtained, the R₁ line (the ²E → ⁴A₂ transition) observed in the luminescence spectra of (Cr,Li): Mg₂SiO₄ crystals in the vicinity of 699.6 nm is assigned to the Cr³⁺(M1)′ center.     

Dilute ferrimagnetism of ilmenites Mn<Subscript>3</Subscript>FeTiSbO<Subscript>9</Subscript> and Mn<Subscript>4</Subscript>FeTi<Subscript>2</Subscript>SbO<Subscript>12</Subscript>

Metastable solid solutions (SS) Mn₃FeTiSbO₉ and Mn₄FeTi₂SbO₁₂ with the ilmenite structure (space group R\(\bar 3\)) have been prepared by quenching at normal conditions. The compositions of the compounds have been justified using EDX spectroscopy and X-ray diffraction. The magnetic properties of SSs have been analyzed by comparison with ferrimagnetic ilmenite Mn₂FeSbO₆ (T_N = 269 K) as a natural mineral and ceramics obtained at high pressure and high temperature. The solid solutions have been characterized as dilute magnetic systems formed as a result of substitution of nonmagnetic cations Ti⁴⁺ for a part of Fe³⁺ and Sb⁵⁺ cations. Mn₃FeTiSbO₉ is considered as a ferromagnetic with T_N = 171 K and Mn₄FeTi₂SbO₁₂ as a magnetic with the concentration of magnetic clusters below the percolation threshold.     

Photoluminescence of the nanosized xerogel Zn<Subscript>2</Subscript>SiO<Subscript>4</Subscript>:Mn<Superscript>2+</Superscript> in pores of anodic alumina

The photoluminescence properties of a composite material prepared by the introduction of the nanosized phosphor Zn₂SiO₄:Mn²⁺ into porous anodic alumina have been investigated. Scanning electron microscopy studies have revealed that Zn₂SiO₄:Mn²⁺ particles are uniformly distributed in 70% of the volume of the pore channels. The samples exhibit an intense luminescence in the range of 2.3–3.0 eV, which corresponds to the emission of different types of F centers in alumina. After the formation of Zn₂SiO₄:Mn²⁺ nanoparticles in the pores, an intense photoluminescence band is observed at 2.4 eV due to the ⁴T₁–⁶A₁ electronic transition within the 3d shell of the Mn²⁺ activator ion. It has been found that the maximum of the photoluminescence of Zn₂SiO₄:Mn²⁺ xerogel nanoparticles located in the porous matrix is shifted to higher energies, and the luminescence decay time decreases significantly.     

Frustrated antiferromagnetism in the Sr<Subscript>2</Subscript>YRuO<Subscript>6</Subscript> double perovskite

The spins of Ru⁵⁺ ions in Sr₂YRuO₆ form a face-centered cubic lattice with antiferromagnetic nearest neighbor interaction J≈25 meV. The antiferromagnetic structure of the first type experimentally observed below the Néel temperature T _N =26 K corresponds to four frustrated spins of 12 nearest neighbors. In the Heisenberg model in the spin-wave approximation, the frustrations already cause instability of the antiferromagnetic state at T=0 K. This state is stabilized by weak anisotropy D or exchange interaction I with the next-nearest neighbors. Low D/J～I/J～10^?3 values correspond to the experimental T _N and sublattice magnetic moment values.     

The influence of chromium impurity centers on the critical properties of a weakly polar ferroelectric Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript>

The Cr³⁺ EPR spectra of Li₂Ge₇O₁₅ (LGO) crystals are analyzed in the temperature range of the ferroelectric phase transition. The temperature dependence of the local order parameter is determined from the measured splittings of the EPR lines in the polar phase. The experimental critical exponent of the order parameter β=0.31 in the range from the phase transition temperature T _C to (T _C -T) ～ 40 K corresponds to the critical exponent of the three-dimensional Ising model. Analysis of the available data demonstrates that, away from the phase transition temperature T _C , the macroscopic and local properties of LGO crystals are characterized by a crossover from the fluctuation behavior to the classical behavior described in terms of the mean-field theory. The temperature dependence of the local order parameter for LGO: Cr crystals does not exhibit a crossover from the Ising behavior (β=0.31) to the classical behavior (β=0.5). This is explained by the defect nature of Cr³⁺ impurity centers, which weaken the spatial correlations in the LGO host crystal. The specific features of the critical properties of LGO: Cr³⁺ crystals are discussed within a microscopic model of structural phase transitions.     

Research of the Spin-Hamiltonian Parameters and Defect Structure for the Trigonal Mn<Superscript>4+</Superscript> Centers in Y<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript>:Mn<Superscript>4+</Superscript> Crystal

The high-order perturbation formulas founded on the two-mechanism model are applied in this paper to compute the spin-Hamiltonian parameters (g factors g _//, g _⊥ and zero-field splitting D) of the trigonal Mn⁴⁺ centers in Y₂Ti₂O₇:Mn⁴⁺ crystal. In this model, besides the contributions from the traditional crystal-field (CF) mechanism (in the CF theory) related to CF excited states, those from the charge-transfer (CT) mechanism connected with CT excited states are contained. The calculated results are reasonably coincident with the observed values. The calculations show that the contributions of CT mechanism to spin-Hamiltonian parameters (in particular, the g factors) for (MnO₆)^8? clusters are large and cannot be neglected. The defect structure of trigonal (MnO₆)^8? clusters in Y₂Ti₂O₇:Mn⁴⁺ crystals is also evaluated. The results are discussed.     

Simulation of the magnetic properties of manganese oxide Pb<Subscript>3</Subscript>Mn<Subscript>7</Subscript>O<Subscript>15</Subscript>

The magnetic susceptibility, heat capacity, and spin-spin correlation functions of manganese oxide Pb₃Mn₇O₁₅ are calculated by the Monte Carlo method. Two critical temperatures are determined: T ₁ ≈ 20 K, above which a modulated structure along the hexagonal axis is formed, and T ₂ ≈ 70 K, at which the long-range magnetic order disappears. The antiferromagnetic exchange interaction constant in a hexagonal plane is estimated to be J ₁ ～ 7 K, and the antiferromagnetic and ferromagnetic exchange interaction constants between hexagonal planes are calculated to be J ₂ ～ 3 K and K ～ 50 K, respectively.     

High-pressure induced magnetoresistance in <Emphasis Type="Italic">p</Emphasis>-InAs:Mn and <Emphasis Type="Italic">p</Emphasis>-CdGeAs<Subscript>2</Subscript>:Mn

The baric (P ≤ 5GPa) and magnetic-field (H ≤ 5 kOe) dependences of the transverse magnetore-sistance Δρ _xx /ρ₀ have been measured for p-InAs (R _H = 22.5 cm³/C, ρ = 0.15 Ω cm) and the new ferromag-netic semiconductor p-CdGeAs₂ (R _H = 5 cm³/C, ρ = 0.62 Ω cm), doped with a magnetic impurity (Mn), near the temperature T = 297 K. The dependences Δρ _xx /ρ₀ (P, H) for p-InAs:Mn and p-CdGeAs₂:Mn exhibit a magnetoresistive effect with an increase in pressure, and a pressure-induced magnetoresistance hysteresis is observed in p-CdGeAs₂:Mn with a pressure drop.     

Role of structure imperfection in the formation of the magnetotransport properties of rare-earth manganites with a perovskite structure

The structure, the structure imperfection, and the magnetoresistance, magnetotransport, and microstructure properties of rare-earth perovskite La_0.3Ln_0.3Sr_0.3Mn_1.1O_3–δ manganites are studied by X-ray diffraction, thermogravimetry, electrical resistivity measurement, magnetic, ⁵⁵Mn NMR, magnetoresistance measurement, and scanning electron microscopy. It is found that the structure imperfection increases, and the symmetry of a rhombohedrally distorted R3?c perovskite structure changes into its pseudocubic type during isovalent substitution for Ln = La³⁺, Pr³⁺, Nd³⁺, Sm³⁺, or Eu³⁺ when the ionic radius of an A cation decreases. Defect molar formulas are determined for a real perovskite structure, which contains anion and cation vacancies. The decrease in the temperatures of the metal–semiconductor (T _ms) and ferromagnet–paramagnet (T _C) phase transitions and the increase in electrical resistivity ρ and activation energy E _a with increasing serial number of Ln are caused by an increase in the concentration of vacancy point defects, which weaken the double exchange 3d ⁴(Mn³⁺)–2p ⁶(O^2–)–3d ³(Mn⁴⁺)–V ^(a)–3d ⁴(Mn³⁺). The crystal structure of the compositions with Ln = La contains nanostructured planar clusters, which induce an anomalous magnetic hysteresis at T = 77 K. Broad and asymmetric ⁵⁵Mn NMR spectra support the high-frequency electronic double exchange Mn³⁺(3d ⁴) ? O^2–(2p ⁶) ? Mn⁴⁺(3d ³) and indicate a heterogeneous surrounding of manganese by other ions and vacancies. A correlation is revealed between the tunneling magnetoresistance effect and the crystallite size. A composition–structure imperfection–property experimental phase diagram is plotted. This diagram supports the conclusion about a strong influence of structure imperfection on the formation of the magnetic, magnetotransport, and magnetoresistance properties of rare-earth perovskite manganites.     

The origin of frustration of magnetic coupling in the NiFeCrO<Subscript>4</Subscript> ferrite

The magnetostriction of the NiFeCrO₄ ferrite is investigated for the first time. It is found that the frustration of magnetic coupling occurs only in the B sublattice of the NiFeCrO₄ ferrite, whereas the A sublattice has a usual magnetic structure. The inference is made that the frustration of magnetic coupling in the B sublattice is caused not only by the negative direct BB exchange interaction Cr _B ³⁺ -Cr _B ³⁺ but also by the positive indirect AB exchange interaction Fe _A ³⁺ -O^2?-Cr _B ³⁺ . Reasoning from the experimental data and an analysis of the exchange interactions in the NiFeCrO₄ ferrite sample, it is demonstrated for the first time that the magnetic moments of Fe _A ³⁺ ions in this ferrite deviate from collinearity. It is established that, at low temperatures, the B sublattice of the NiFeCrO₄ ferrite is responsible for the total magnetic moment n_0exp.     

EPR study of impurity iron ion clusters in BaF<Subscript>2</Subscript> crystals

Tetragonal paramagnetic centers with spin S = 7/2 were detected in x-ray-irradiated BaF₂: Fe (c_Fe ≈ 0.002 at. %) crystals using the EPR method. Electronic transitions between the |±1/2〉 states of a Kramers doublet were observed in the X and Q ranges. In the EPR spectra of the tetragonal centers, a ligand hyperfine structure (LHFS) was observed corresponding to the interaction of the electron magnetic moment of the tetragonal center with eight equivalent ligands. The large spin moment, significant anisotropy of the magnetic properties, and the characteristic LHFS indicate that the tetragonal center is a Fe^1.5+?Fe^1.5+ dimer in which the two iron ions are bound via superexchange interaction. It is assumed that, before crystal irradiation, this dimer was in the Fe³⁺(3d⁵)?Fe⁺(3d⁷) state.