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.     

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.     

Investigation of the GdMn2O5 multiferroic by the μSR method

The GdMn₂O₅ multiferroic (a ceramic sample and a sample consisting of a large array of randomly oriented single crystals with linear dimensions 2–3 mm) has been studied by the μSR method within the temperature range 10–300 K. Three anomalies in the temperature behavior of the parameters of the muon polarization relaxation function, namely, close to the phase transition driven by the onset of long-range magnetic order in the manganese ion subsystem (T _N1 = 40–41 K), near the lock-in transition initiated by an abrupt change of the wave vector of magnetic order (T _L = 35 K), and close to the Gd³⁺ ion ordering temperature (T _N2 = 15 K), have been found. An analysis of the time spectra of muon spin precession in the internal magnetic field of the samples has revealed two positions of preferable muon localization sites in samples, which differ in precession frequencies and the character of their behavior with temperature. The lower-frequency precession driven by Mn⁴⁺ ions, ferromagnetic Mn4⁺-Mn⁴⁺ + muonium complexes, and Gd³⁺ions is observed throughout the temperature region T < T _N1 and is practically independent of temperature. At temperatures T < T _L = 35 K, a higher-frequency precession associated with Mn³⁺ ions appears also. It is characterized by a temperature dependence ～(T/T _N1)^β with the index β = 0.39, which is typical of Heisenberg-type 3D magnets. For T < T _N1, a deficiency of the rest total asymmetry is observed. This phenomenon can probably be assigned to formation of muonium, which suggests that charge transfer processes play an important role in formation of long-range magnetic order.     

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 paramagnetic resonance and optical absorption studies of manganese ions doped in polyvinyl(alcohol) complexed with polyethylene glycol polymer films

Electron paramagnetic resonance (EPR), optical absorption, and infrared spectral studies have been carried out on Mn²⁺ ions doped in poly(vinyl alcohol) (PVA) complexed with polyethylene glycol (PEG) films prepared by solution cast technique. The EPR spectra of 0.25?mol% Mn²⁺ ions doped polymer complex (PVA+PEG) at room temperature exhibit sextet hyperfine structure (hfs), centered at g????1.99. The spin?CHamiltonian parameter values indicate that the ground state of Mn²⁺ ion is d⁵ and the site symmetry around Mn²⁺ ions in tetragonally distorted octahedral site. The spin concentration participating in the resonance is measured as a function of temperature and it is observed that it obeys Boltzmann??s law. The paramagnetic susceptibility (??) is calculated from the EPR data at various temperatures (93?C333?K) and it obeys the Curie?CWeiss law. The optical absorption spectra exhibits two bands which are assigned to ⁶A_1g (S)??⁴A_1g (G) or ⁴E_g (G) and ⁶A_1g (S)??⁴T_2g (G) transitions. The infrared spectrum exhibits few bands due to the presence of O?CH, C?CH, and C=C groups.     

Superhyperfine Structure of the EPR Spectra of Nd<Superscript>3+</Superscript> Impurity Ions in Fluorite CaF<Subscript>2</Subscript>

EPR spectra of a CaF₂ single crystal that was grown from melt containing a small addition of NdF₃ were studied. Signals corresponding to tetragonal centers of Nd³⁺ ions and cubic centers of Er3+ and Yb3+ ions were found. Superhyperfine structure (SHFS) in the spectra of the Nd³⁺ ions was observed for the first time in this crystal; parameters of the superhyperfine interaction of the Nd³⁺ ions with the nearest nine fluorine ions were determined. The dependence of the resolution of the Nd³⁺ EPR spectrum SHFS on the incident microwave power at the temperature of T ≈ 6 K was studied. Obtained results are discussed and compared with the literature data.     

EPR, luminescence and IR studies of Mn activated ZnGa2O4 phosphor

Electron paramagnetic resonance (EPR), luminescence and infrared spectra of Mn²⁺ ions doped in zinc gallate (ZnGa₂O₄) powder phosphor have been studied. The EPR spectra have been recorded for zinc gallate phosphor doped with different concentrations of Mn²⁺ ions. The EPR spectra exhibit characteristic spectrum of Mn²⁺ ions (S=I=5/2) with a sextet hyperfine pattern, centered at g_eff=2.00. At higher concentrations of Mn²⁺ ions, the intensity of the resonance signals decreases. The number of spins participating in the resonance has been measured as a function of temperature and the activation energy (E_a) is calculated. The EPR spectra of ZnGa₂O₄: Mn²⁺ have been recorded at various temperatures. From the EPR data, the paramagnetic susceptibility (χ) at various temperatures, the Curie constant (C) and the Curie temperature (θ) have been evaluated. The emission spectrum of ZnGa₂O₄: Mn²⁺ (0.08 mol%) exhibits two bands centered at 468 and 502 nm. The band observed at 502 nm is attributed to ⁴T₁→⁶A₁ transition of Mn²⁺ ions. The band observed at 468 nm is attributed to the trap-state transitions. The excitation spectrum exhibits two bands centered at 228 and 280 nm. The strong band at 228 nm is attributed to host-lattice absorption and the weak band at 280 nm is attributed to the charge-transfer absorption or d⁵→d⁴s transition band. The observed bands in the FT-IR spectrum are assigned to the stretching vibrations of M-O groups at octahedral and tetrahedral sites.     

Study of ESR spectra of Ce<Superscript>3+</Superscript> ions in polycrystalline Sr<Subscript>2</Subscript>B<Subscript>5</Subscript>O<Subscript>9</Subscript>Br

ESR spectra of Ce³⁺ ions in polycrystalline Sr₂B₅O₉Br were studied, and the two crystallographic positions of the Ce³⁺ ion in this compound were identified on the basis of the data obtained. The ESR spectrum of Ce³⁺ ions with local charge compensation contains a broad line indicating the existence of several types of charge compensation. ESR spectra of Ce³⁺ ions in samples activated additionally by K⁺ ions are similar to those of the regular Ce³⁺ centers, which indicates that the effect of the univalent cation on Ce³⁺ is negligible.     

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.     

Optical evidence of quantum rotor orbital excitations in orthorhombic manganites

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 recognized, is still elusive in the ground state properties. Here we discovered that, in these materials, there exist excitations whose energy spectrum is described in terms of the total angular momentum eigenstates and is quantized as in quantum rotors found in JT centers. We observed features originating from these excitations in the optical spectra of a model compound LaMnO₃ using ellipsometry technique. They appear clearly as narrow sidebands accompanying the electron transition between the JT split orbitals at neighboring Mn³⁺ ions, displaying anomalous temperature behavior around the Néel temperature T_N ≈ 140 K. We present these results together with new experimental data on photoluminescence found in LaMnO₃, which lend additional support to the ellipsometry implying the electronic-vibrational origin of the quantum rotor orbital excitations. We note that the discovered orbital excitations of quantum rotors may play an important role in many unusual properties observed in these materials upon doping, such as high-temperature superconductivity and colossal magnetoresistance.     

Influence of zeolite water on paramagnetic and ferromagnetic resonances in the Co2[Nb(CN)8] · 8H2O molecular magnet

The contributions of Co²⁺ and Nb⁴⁺ ions to the high-frequency dynamic magnetic susceptibility of the Co₂[Nb(CN)₈] · 8H₂O molecular magnet in the paramagnetic state at T > 12 K are separated. It is found that the ferromagnetic ordering, which leads to the reconstruction of the electron paramagnetic resonance spectrum into the ferromagnetic resonance spectrum, occurs at T < 12 K. The influence of zeolite water on the spectra of the paramagnetic and ferromagnetic resonances is found. Dehydration leads to a decrease in the time of the spin relaxation of the ferromagnetic system from 50 ps to 17 ps at T = 4 K and to the variation in the temperature dependences of the widths of the lines and g factors in the electron spin resonance spectra.     

Optical spectroscopy of Mn2+ ions in CaCl2 single crystals

Abstract

In the present investigation the excitation and fluorescence spectra and lifetimes of Mn²⁺ ions in calcium chloride, for various manganese concentrations and sample temperatures have been studied for the first time. The fluorescence spectrum consists of an asymmetric broad band, which upon lowering the sample temperature, shifts its maximum from 580 nm at 300 K to 596 nm at 11 K. This luminescence band was associated with the ⁴T_lg(⁴G)→⁶A_lg(⁶S) spin-forbidden transition in the manganese ions occupying Ca-sites in the lattice of CaCl₂. The excitation spectrum of the Mn²⁺ fluorescence revealed the features of manganese ions in octahedral coordination and consisted of nine excitation peaks which were associated with Mn²⁺-crystal-field-sensitive transitions. A crystal field analysis of the wavelength positions of these transitions by means of the model developed by Curie et al. allowed us to determine the magnitude of the cubic field splitting 10Dq, the reduced Racah parameter B', the Koide-Pryce covalency parameter ε and the spin transfer coefficients f _[sgrave] and f _σ. From the measurement of the temperature dependence of the Mn²⁺ fluorescence lifetime, we have also obtained information about the different mechanisms which are involved in the relaxation of excited Mn²⁺ ions in this host crystal in the temperature range (11–300 K).     

Thermal dependence of impurity induced fluorescence in the system RbMgxMn1-xF3

The absorption spectrum of RbMnF₃ and the excitation spectra of the system RbMg_xMn_1-xF₃ at 10 K as well as the fluorescence spectra and lifetimes of Mn²⁺ in the systems RbMg_xMn_1-xF₃ and KMg_xMn_1-xF₃ in the region 10–300 K were measured. The lifetime and fluorescence temperature dependence suggest that the origin of the fluorescence occurs at Mn²⁺ sites slightly perturbed by impurity ions and that a non-radiative energy transfer mechanism is responsible for the observed thermal quenching. By using different Mn²⁺ concentrations in the above systems the dependence of the energy transfer on the Mn²⁺ concentration is shown. Finally, a preliminary observation on laser stimulated Mn²⁺ luminescence in the system RbMg_xMn_1-xF₃ is reported.     

EPR and photoluminescence properties of green light emitting LaAl11O18:Mn phosphors

The LaAl₁₁O₁₈:Mn²⁺ powder phosphor has been prepared using a self-propagating synthesis. Formation and homogeneity of the LaAl₁₁O₁₈:Mn²⁺ phosphor has been verified by X-ray diffraction and energy dispersive X-ray analysis respectively. The EPR spectra of Mn²⁺ ions exhibit resonance signals with effective g values at g≈4.8 and g≈1.978. The signal at g≈1.978 exhibits six-line hyperfine structure and is due to Mn²⁺ ions in an environment close to tetrahedral symmetry, whereas the resonance at g≈4.8 is attributed to the rhombic surroundings of the Mn²⁺ ions. It is observed that the number of spins participating in resonance for g≈1.978 increases with decreasing temperature obeying the Boltzmann law. Upon 451 nm excitation, the photoluminescence spectrum exhibits a green emission peak at 514 nm due to ⁴T₁ (G)→⁶A₁ (S) transition of Mn²⁺ ions. The crystal field parameter Dq and Racah inter-electronic repulsion parameters B and C have been evaluated from the excitation spectrum.     

Electron paramagnetic resonance and optical spectroscopy of K3Na(CrO4)2 ferroelastics activated by MnO 4 2− molecular impurity ions

Crystals of a proper ferroelastic K₃Na(CrO₄)₂ containing molecular impurity ions MnO ₄ ^2? are studied using electron paramagnetic resonance (EPR) and optical spectroscopy. The EPR spectrum of the Mn⁶⁺ ion contained in the molecular impurity ion MnO ₄ ^2? is identified at low temperatures (T ≤ 20 K). The intensity of this spectrum decreases unusually fast as the temperature increases. A broad IR luminescence band with a vibronic structure well resolved at a temperature of 8 K is revealed. Theoretical treatment of the Mn⁶⁺ ion involved in the molecular impurity ions MnO ₄ ^2? of the K₃Na(CrO₄)₂ ferroelastic crystal suggests that an important role in this case is played by the pseudo-Jahn-Teller. The pseudo-Jahn-Teller effect offers an explanation for the appearance of a fine structure in the vibronic replicas in the luminescence spectrum, on the one hand, and accounts for the fast decrease in the intensity of the EPR spectrum of K₃Na(CrO₄)₂: MnO ₄ ^2? with increasing temperature, on the other.     

EPR and IR spectral studies on Mn ions in nickel maleate tetrahydrate single crystals

Electron paramagnetic resonance (EPR) studies have been carried out on Mn²⁺ ions doped in nickel maleate tetrahydrate single crystals in the temperature range 103-413 K on X-band frequency. The EPR spectrum at room temperature exhibits a group of five fine structure transitions each splits into six hyperfine components. Angular variation studies reveal the presence of a single site and it is found that Mn²⁺ ions enter the lattice substitutionally. From the observed EPR spectrum, the spin-Hamiltonian parameters have been evaluated. The variation of zero-field splitting parameter (D) with temperature is measured. The observed EPR spectra exhibit a large anisotropy in the widths of Mn²⁺ resonance lines. The widths of Mn²⁺ resonance lines increase with the Zeeman field intensity and these observations have been discussed in detail. The infrared spectrum exhibits bands characteristic of the carboxylic acid salts.     

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.     

Low temperature ESR spectra of nickel — doped NaCl crystals

Paramagnetic resonance of Bridgman-grown NaCl crystals nominally doped with divalent nickel was studied over the temperature range from 4 K to 300 K. The broad isotropic EPR line with g = 2.12 ÷ 2.23 and ΔH _pp = 280 ÷ 780 G was detected at temperatures higher than 130 K for samples of various thermal history. The origin of these spectra was attributed to aggregated and precipitated Ni²⁺ ions. At temperatures lower than 40 K another ESR signal was registered. It was an anisotropic one, the intensity of which strongly depends upon the temperature. This spectrum results from substitutional Ni⁺ ions with tetragonally distorted surrounding along a S100T direction. The angular dependence of the ESR line positions was fitted to an appropriate spin-Hamiltonian with the g-factor components g _∥ and g _⊥ equal to 2.86 and 2.10, respectively. The temperature-dependence of the signal intensity at temperatures between 4 and 110 K has been interpreted in terms of a transition from the static to dynamic Jahn-Teller effect.     

Paramagnetic resonance study of the structural phase transition in sodium azide

The electron paramagnetic resonance (EPR) of Mn²⁺ impurities in sodium azide (NaN₃) single crystals has been measured between 178 K and 300 K in order to study the transition between the monoclinic low temperature α phase and the trigonal high temperature β phase of NaN₃. The analysis of the EPR spectra yields the parameters of the zero-field splitting (zfs) in the spin Hamilton operatorD(S _ξ ² ?1/3S(S+1))+E(S _ξ ² ?S _η ² ) associated with any of four different pair states of a Mn²⁺ ion and a cation vacancy. The obtained zfs, which is temperature dependent in α-NaN₃ and constant in β-NaN₃, is consistent with a continuous phase transition atT _c =292 K. Using a point charge model for the crystal potential the zfs parameters are related to the lattice structure in the vicinity of the Mn²⁺ ion. The zfs is not consistent with the temperature dependent atomic displacements in α-NaN₃ obtained previously from an X-ray diffraction study. The critical exponents of the zfs parameters, derived in the temperature range 1 K<T _c ?T<114 K, differ from the critical exponents of atomic displacements in α-NaN₃.     

ESR experiments with egg shells of chickens

The electron spin resonance spectra fromGallus domesticus egg shells exhibit a strong free radical singlet, a spectrum due to Mn²⁺ ions in a calcite site, a low field line line atg≈30/7 due to Mn²⁺ in a rhombic site, and spectral lines arising from Fe³⁺ ions. Details of the ESR spectral lines did not correlate with fertile, non-fertile or color type egg-shell characteristics.