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 study of exchange interactions of manganese ions in a CdGeAs<Subscript>2</Subscript> matrix

The results of an EPR study of the CdGeAs₂ compound doped with 6 at % Mn are reported. The experimental data are analyzed under the assumption that magnetic centers of the following two types are formed in the system: Mn_Cd, Mn ions that replace Cd²⁺ and have spin S = 5/2, and Mn_Ge, Mn ions that replace Ge⁴⁺ and form the Mn²⁺ + 2p complex with two “heavy” holes with spin S = 1/2. The absence of signals from isolated centers and the Lorentzian shape of an absorption curve suggest a strong exchange narrowing of the spectrum and the extension of an isotropic exchange interaction involving Mn_Ge to distances much longer than the lattice parameter. It is found that the exchange interaction between Mn²⁺ + 2p complexes is ferromagnetic, and it is stronger than the characteristic superexchange interaction involving Mn_Cd centers by three to four orders of magnitude. The form of the temperature dependence of susceptibility obtained by the double integration of spectra is indicative of the formation of nanoscale regions, which weakly interact with each other, with ferromagnetically ordered Mn²⁺ + 2p complexes at ～250 K.     

Electron spin resonance in Ge0.99Mn0.01 nanowires

Electron spin resonance (ESR) is measured in arrays of Ge_0.99Mn_0.01 nanowires (NWs). We show that the ESR spectrum comprises four lines corresponding to the different magnetic subsystems. Two lines are attributed to spin-wave excitations in the Mn⁺³ ion subsystem. The third component corresponds to the resonance in the Mn⁺² ions. The last component has an asymmetric Dyson form and characterizes the resonance in the mobile paramagnetic centers. We demonstrate that temperature dependences of ESR parameters are correlated in subsystems of the localized magnetic centers (Mn⁺³ and Mn⁺² ions) and delocalized band carriers. It implies the presence of exchange interactions between the localized Mn ions and spin-polarized carriers.     

Magnetic resonance in Ge0.99Mn0.01 nanowires

The contributions of several different subsystems to the magnetic properties of Ge_0.99Mn_0.01 nanowires are distinguished. The ferromagnetic resonance spectrum is found to have four components, two of which have the same temperature dependence and a Lorentzian shape. Presumably, these components correspond to the excitation of spin waves in the Mn³⁺ ion subsystem under the simultaneous influence of exchange and dipole-dipole interactions. There is also another Lorentzian-shaped component corresponding to resonance in the subsystem of localized Mn²⁺ centers. The fourth spectrum component has an asymmetric Dyson shape and is related to the resonance of mobile paramagnetic centers. A correlation is found between the temperature dependences of the spectral parameters of the magnetic resonances of the localized centers (Mn³⁺ and Mn²⁺ ions) and the charge carrier subsystem. This correlation indicates that the ferromagnetic exchange between the localized centers is due to carrier spin transport.     

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.     

Optical and EPR spectroscopy of manganese ions in Sr3Ga2Ge4O14 crystals

Results of investigations of the spectroscopic properties of manganese-activated single crystals of Sr₃Ga₂Ge₄O₁₄ by the methods of optical and EPR spectroscopy are reported. It is shown that magnagese activator ions form substitutional centers Mn³⁺ and Mn²⁺ in 1a-octahedral positions of the Sr₃Ga₂Ge₄O₁₄ lattice. Changes in the opticla properties of Sr₃Ga₂Ge₄O₁₄: Mn after vacuum thermal annealing are attributed to charge transfer of some of the manganese ions (Mn³⁺→Mn²⁺). The relationship between the spectroscopical properties of Mn²⁺ ions and the crystallochemical structure of the system are discussed. I. Franko L’vov State University, 50, Dragomanov St., L’vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 779–783, November–December, 1997.     

An EPR study of local fluctuations in the vicinity of the ferroelectric phase transition in Li2Ge7O15

EPR spectra of Mn²⁺ ions have been studied in the temperature interval containing the ferroelectric transition in crystalline lithium heptagermanate Li₂Ge₇O₁₅. The EPR linewidth and shape were measured as functions of temperature and orientation. It is shown that the critical resonance-line broadening observed to occur in the vicinity of the phase transition is due to fluctuations in the local order parameter with frequencies below 10⁷ Hz.     

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.     

Mössbauer effect study of Ni1−xCuxMnyFe2−yO4 system

The Mössbauer effect technique has been employed for the study of magnetic properties of spinel series Ni_1?xCu_xMn_yFe_2?yO₄ with 0.0≤x≤1.0, and y=0.6. The substitution of Mn³⁺ and Cu²⁺ ions results in a slight decrease of the hyperfine field at B‐ as well as A‐sites. The area ratio of Fe³⁺ ions at the A‐ and B‐site at 77 K indicates that Cu²⁺, Ni²⁺ and Mn³⁺ ions occupy the octahedral sites in an evidence for complete inverse spinel in this system. The temperature dependence of the hyperfine parameters has been studied for composition with x=0.5 where Nèel point T_N and Debye temperature θ_D are found to be 650 and 679 K, respectively. The temperature dependence of the sublattice magnetization σ(T) obeys a one‐third‐power law in the range 0.5N<0.99.     

Magnetic resonance of the M x Mn1 ? x S compounds (M = Cu, Cr)

Cation-substituted manganese monosulfide M _x Mn_{1 ? x} S (M = Cu, Cr) has been investigated using the electron paramagnetic resonance method. The temperature and concentration dependences of the width and shape of the magnetic resonance line have been considered using the Van Vleck method of moments. It has been shown that, if the Mn²⁺ ions are substituted by the copper and chromium ions, the change of the effective exchange interaction in the system that substantially affects the magnetic resonance spectra takes place.     

Evidence for the spin-dependent scattering of conduction electrons on Mn2+ ions in Hg1−xMnxTe and Cd1−xMnxSe mixed crystals

Changes in the resistivity of Hg_1?xMn_xTe and Cd_1?xMn_xSe mixed crystals associated with paramagnetic resonance of the Mn²⁺ ions have been observed at liquid helium temperature in a strong magnetic field. The effect was recorded by monitoring the submillimeter radiation induced photoconductivity in a swept magnetic field. An increase in the resistivity associated with EPR of the Mn²⁺ ions is interpreted in terms of the spin- dependent scattering of electrons on magnetic impurities, the spins of which are selectively depolarised by means of paramagnetic resonance. Some additional effects influencing the experiments are also discussed.     

The effect of the impurities on the magnetic,electronic and optical properties of Mn5Ge3

Earlier, we experimentally showed a significant effect of oxygen on the magnetic and structural properties of Mn₅Ge₃ due to the formation of a Nowotny phase of Mn₅Ge₃O_x. Here, in continuation of this study, we present a theoretical study of the magnetic and electronic properties of Mn₅Ge₃ and Mn₅Ge₃D_x (D = B, C, O). It was found that hexagonal Mn₅Ge₃ is a ferromagnetic metal with two nonequivalent manganese atoms in the structure. Our ab initio calculations also predict the existence of a spin-crossover in Mn₅Ge₃ under pressure. Impurities reduce saturation magnetization and electrical and thermal conductivity; however, the magnetic susceptibility and Curie temperature increase. Microscopic mechanisms of the effect of the impurities on the magnetic and electronic properties Mn₅Ge₃ are discussed.     

Structural, magnetic and electronic transport properties of MnxGe1−x/Ge(0 0 1) films grown by MBE at 350 °C

We report on the structural, magnetic and electronic transport properties of thin Mn_xGe_1−x films grown at 350 °C. Isolated Mn₅Ge₃ nanoclusters, about 100 nm in size, were formed at the top surface of the film, dominating the magnetic properties of the whole film. Electronic transport properties show Mn doping effect indicating the presence of substitutional Mn ions dispersed in the Ge host, contributing to the formation of a Mn_xGe_1−x diluted phase. Electrical behaviour indicates a saturation effect with the raise of the nominal Mn concentration in the film, above x ≅ 0.03.     

Magnetic and luminescent properties of manganese-doped ZnSe crystals

Magnetic and photoluminescent properties of manganese-doped ZnSe crystals with different impurity concentrations were investigated. The concentration of Mn²⁺ ions in ZnSe crystals has been varied from 0.01 to 0.3 at%. Magnetic and photoluminescent studies have confirmed the introduction of Mn in ZnSe crystals. It was established that Mn²⁺ ions are responsible for the emission bands with maximum at 616 nm and 633 nm, which correspond to ⁴T₂→⁶A₁ and ⁴T₁→⁶A₁ intracentre transitions of Mn²⁺ ions respectively. It was found that the concentration quenching of the photoluminescent bands is associated with Mn²⁺ ions, which are due to the formation of Mn–Mn clusters. Magnetic properties studies have shown that at high doping levels the manganese atoms form Mn–Mn clusters in ZnSe. From the temperature dependence of magnetic susceptibility of ZnSe:Mn crystals that follows the Curie–Weiss law, it was possible to estimate the Curie–Weiss temperature Θ(x) and the effective Mn–Mn antiferromagnetic exchange constant (J₁).     

Magnetic susceptibility of fluoride glasses with 3d and 4f elements

The low field ac magnetic susceptibility has been studied as a function of temperature and frequency in a series of fluoride glasses containing Mn²⁺, rare-earth ions, or an admixture of the two types. All glasses exhibit magnetic freezing in the ⁴He or ³He temperature ranges, but the nature of the freezing appears to depend on the local anisotropy. In the case of Mn²⁺ or Mn²⁺ -Gd³⁺ ions, a sharp freezing analogous to that in CuMn was observed. For Ln³⁺ or Mn²⁺ -Ln³⁺ ions (Ln=Dy, Ho), the observed progressive freezing could be of a dynamic nature.     

Growth and properties of magnetron cosputtering grown MnxGe1−x on Si (001)

We have grown Mn_xGe_1−x films (x=0, 0.06, 0.1) on Si (001) substrates by magnetron cosputtering, and have explored the resulting structural, morphological, electrical and magnetic properties. X-ray diffraction results show there is no secondary phase except Ge in the Mn_0.06Ge_0.94 film while new phase appears in the Mn_0.1Ge_0.9 film. Nanocrystals are formed in the Mn_0.06Ge_0.94 film, determined by field-emission scanning electron microscopy. Hall measurement indicates that the Mn_0.06Ge_0.94 film is p-type semiconductor and hole carrier concentration is 6.07×10¹⁹ cm⁻³ while the Mn_xGe_1−x films with x=0 has n-type carriers. The field dependence of magnetization was measured using alternating gradient magnetometer, and it has been indicated that the Mn_0.06Ge_0.94 film is ferromagnetic at room temperature.     

Manganese location and magnetic structure determination of SrMn2—W hexagonal ferrite by means of neutron diffraction

The Mn cation distribution in the seven sublattices of theW-type structure has been determined from high temperature neutron diffraction data of a SrMn₂Fe₁₆O₂₇ powder sample. The Mn²⁺ ions enter the tetrahedral sites of blockS with a preference for site 4e. Mn³⁺ ions in small amounts are found in the octahedral sites, substituting for Fe³⁺, while 0.3 Fe²⁺ has been found in site 6g. The sample has the formula SrMn_2.4Fe_15.6O₂₇. The crystal structure has been described in the non-centrosymmetric Pˉ62c space group, instead of the usual P6₃/mmc one. The magnetic structure, obtained from low temperature (4.2 K) data, is collinear, with the spins parallel to thec axis, according to the Gorter model. The magnetic moments of the sites give an experimental magnetization valueM _s=28.4(1.5) μ_B/f.u., in good agreement with magnetic measurements and the theoretical value.     

EPR study of the impurity paramagnetic centres in (CaO−Ga2O3−GeO2) glasses

The X-band EPR spectra of Cr³⁺, Mn²⁺, and Fe³⁺ impurity ions in glasses of (CaO?Ga₂O₃?GeO₂) system are investigated in the 77÷300 K temperature range. The experimental data analysis yields the following results: (i) Impurity chromium ions are incorporated into the (CaO?Ga₂O₃?GeO₂) glasses network in Cr³⁺ (3d³,⁴F_3/2) paramagnetic valence state only and occupy the strong distorted oxygen coordinated octahedral sites. (ii) For all activated and non-activated (CaO?Ga₂O₃?GeO₂) glasses the iron impurity is present at concentration roughly 0.01 wt.%. Isotropic EPR signals atg _eff=4.29 andg _eff=2.00 are assigned to Fe³⁺ (3d⁵,⁶S_5/2) ions in the sites with strong rhombic distortion and in the sites with nearly cubic symmetry respectively. (iii) The manganese EPR spectrum in (CaO?Ga₂O₃?GeO₂) glasses is weakly dependent on temperature, doping procedure as well as manganese concentration. EPR spectra of impurity manganese ions in glasses with Ca₃Ga₂Ge₃O₁₂ and Ca₃Ga₂Ge₄O₁₄ compositions are virtually identical and belong to Mn²⁺ (3d⁵,⁶S_5/2) ions. Impurity manganese ions are incorporated into the (CaO?Ga₂O₃?GeO₂) glass network as isolated Mn²⁺ centres and clusters of Mn²⁺ ions.     

Substantial Ca doping site effect on structure of La0.5Ca0.5MnO3 at low temperature

Six possible structures of La_0.5Ca_0.5MnO₃ corresponding to different Ca doping sites are studied at low temperature using atomistic simulation techniques. It is found that Ca doping site has substantial effect on structure of La_0.5Ca_0.5MnO₃ and this effect may explain the existence of four similar phases with slightly different lattice parameters in La_0.5Ca_0.5MnO₃ at low temperature. Structures I and II are found to be favorable La_0.5Ca_0.5MnO₃ structures. They have an ordering arrangement of La³⁺ and Ca²⁺ ions and different arrangements of Mn³⁺ and Mn⁴⁺ ions, which may affect the charge, orbital and magnetic ordering in La_0.5Ca_0.5MnO₃ at low temperature.     

Analysis of the exchange magnetic structure in Pb<Subscript>3</Subscript>Mn<Subscript>7</Subscript>O<Subscript>15</Subscript>

The indirect-coupling model is used to analyze the exchange magnetic structure of Pb₃Mn₇O₁₅ in the hexagonal setting. The ratios of manganese ions Mn⁴⁺/Mn³⁺ in each nonequivalent position are determined. Pb₃(Mn_0.95Ge_0.05)₇O₁₅ and Pb₃(Mn_0.95Ga_0.05)₇O₁₅ single crystals are grown by the solution–melt method in order to test the validity of the proposed model. The structural and magnetic properties of the single crystals are studied. The magnetic properties of the grown single crystals are compared with those of nominally pure Pb₃Mn₇O₁₅.