EPR and magnetic susceptibility studies of the interaction between Cu2+ and Mn2+ ions in x(CuO·MnO)(1−x)[2B2O3·K2O] glasses

EPR and magnetic susceptibility experiments have been performed on x(CuO·MnO)(1?x)[2B₂O₃·K₂O] glasses with x varying in the range 0?x?50 mol.%. For x?3 mol.% both Cu²⁺ and Mn²⁺ ions are present mostly as the isolated species. The increase of the g-tensor values and bonding parameters (α², β², δ²) for Cu²⁺ ions together with the increase of TM ions concentration in the 0.2–1 mol.% range was noticed. In the case of 5 ? x ? 30 mol.% the dipole-dipole and superexchange interactions occur between transition metal ions, the first type of interactions prevailing in this range of concentration. For x30 mol.% the superexchange interaction prevail. The strong interaction between Cu²⁺ and Mn²⁺ gives rise to the exchange coupled Cu²⁺Mn²⁺ pairs in the studied glasses with x 3 mol.%.     

EPR and magnetic susceptibility studies of xCuO·(1−x)[2B2O3·Li2O] glasses

The results of EPR and magnetic susceptibility studies on xCuO·(1?x)? [2B₂O₃·Li₂O] glasses with $\text{0?x?30 mol \%}$, are reported. The modification of EPR spectra with the increasing of CuO content are explained supposing that these are the result of the superposition of two EPR signals, one showing the hyperfine structure typical for isolated Cu²⁺ ions and other consisting from a broad line centered at g ～ 2 typical for the clustered Cu²⁺ ions. The values of the EPR parameters prove that the coordination of isolated Cu²⁺ -complexes remains approximately the same and show that Cu²⁺ ions are situated in axially distorted octahedral vicinities. EPR measurements have shown that the Cu²⁺ ions are present mostly as the isolated species when $\text{x?5 mol \%}$. Beside the dipole-dipole coupling between Cu²⁺ ions, the magnetic measurements suggest that for x>10 mol % superexchange interactions appear, too. From Curie constant is established that in this glass system the copper ions are in Cu²⁺ and Cu⁺ valence states. Also, the amounts of the copper ions in bivalent state are determined.     

Spectral studies on Mn ions doped in sodium-lead borophosphate glasses

Electron paramagnetic resonance (EPR), optical absorption, and luminescence spectral studies of Mn²⁺ ions doped in (30−x) (NaPO₃)₆+30PbO+40B₂O₃+xMnO₂ (x=1.0, 2.0, 3.0, 4.0, and 5.0 mol%) glasses have been studied. The EPR spectra exhibit resonance signals with effective g value at g_eff≈2.02 with six line hyperfine structure. A weak resonance signal with effective g value at g_eff≈4.3 is also observed for higher concentrations of Mn²⁺ ions. The EPR spectra of x =3.0 mol% of Mn²⁺ in sodium-lead borophosphate glass sample have been studied at various temperatures. It is observed that the resonance signal intensity decreases with increase in temperature. The optical absorption spectrum exhibits bands characteristic of Mn²⁺ ions in octahedral symmetry. From the analysis of the bands, the crystal-field parameter Dq and the Racah interelectronic repulsion parameters B and C have been evaluated. The emission spectrum exhibits single broad band in the green region.     

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.     

The migration of Mn2+ ions in Cd1−xMnxS nanocrystals: Thermal annealing control

This work reports evidence of the induced migration of Mn²⁺ ions in Cd_(1?x)Mn_xS nanocrystals (NCs) by selecting a specific thermal treatment for each sample. The growth and characterization of these magnetic dots were investigated by atomic force microscopy (AFM), optical absorption (OA), and electronic paramagnetic resonance (EPR) techniques. The comparison of experimental and simulated EPR spectra confirms the incorporation of Mn²⁺ ions both in the core and at the dot surface regions. The thermal treatment of a magnetic sample, via selected annealing temperature and/or time, affects the fine and hyperfine interaction constants which modify the shape and the intensity of the EPR transition spectrum. The identification of these changes has allowed tracing the magnetic ion migration from core to surface regions of a dot as well as inferring the local density of the magnetic impurity ions.     

EPR and magnetic susceptibility studies of iron ions in ZnO-Fe2O3-SiO2-CaO-P2O5-Na2O glasses

Room temperature electron paramagnetic resonance (EPR) spectra and temperature dependent magnetic susceptibility data have been obtained on bulk x(ZnO,Fe₂O₃)(65−x)SiO₂20(CaO, P₂O₅)15Na₂O (6≤x≤21 mole%) glasses prepared by melt quenching method. EPR spectra of the glasses revealed absorptions centered at g≈2.1 and 4.3. The variations of the intensity and line width of these absorption lines with composition have been interpreted in terms of the variation in the concentration of the Fe²⁺ and Fe³⁺ ions in the glass and the interaction between the iron ions. EPR and magnetic susceptibility data of the glasses reveal that both Fe²⁺ and Fe³⁺ ions are present in the glasses, with their relative concentration being dependent on the glass composition. The studies reveal superexchange type interactions in these glasses, which are strongly dependent on their iron content.     

Mixed alkali effect in borate glasses—EPR and optical absorption studies in xNa2O–(30−x)K2O–70B2O3 glasses doped with Mn2+

The mixed alkali borate xNa₂O–(30−x)K₂O–70B₂O₃ (5≤x≤25) glasses doped with 1 mol% of manganese ions were investigated using EPR and optical absorption techniques as a function of alkali content to look for ‘mixed alkali effect’ (MAE) on the spectral properties of the glasses. The EPR spectra of all the investigated samples exhibit resonance signals which are characteristic of the Mn²⁺ ions. The resonance signal at g≅2.02 exhibits a six line hyperfine structure. In addition to this, a prominent peak with g≅4.64, with a shoulder around g≅4.05 and 2.98, was also observed. From the observed EPR spectrum, the spin-Hamiltonian parameters g and A have been evaluated. It is interesting to note that some of the EPR parameters do show MAE. It is found that the ionic character increases with x and reaches a maximum around x=20 and thereafter it decreases showing the MAE. The number of spins participating in resonance (N) at g≅2.02 decreases with x and reaches a minimum around x=20 and thereafter it increases showing the MAE. It is also observed that the zero-field splitting parameter (D) increases with x, reaches a maximum around x=15 and thereafter decreases showing the MAE. The optical absorption spectrum exhibits a broad band around ∼20,000 cm⁻¹ which has been assigned to the transition ⁶A_1g(S)→⁴T_1g(G). From ultraviolet absorption edges, the optical bandgap energies and Urbach energies were evaluated. It is interesting to note that the Urbach energies for these glasses decrease with x and reach a minimum around x=15. The optical band gaps obtained in the present work lie in the range 3.28–3.40 eV for both the direct and indirect transitions. The physical parameters of all the glasses were also evaluated with respect to the composition.     

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.     

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.     

EPR of Er3+, Nd3+, and Ce3+ ions in YAlO3 single crystals

EPR spectra of the Er³⁺, Nd³⁺, and Ce³⁺ ions substituting for the Y³⁺ ion in the YAlO₃ yttrium orthoaluminate lattice are studied. The EPR spectra of these rare-earth ions are described by a spin Hamiltonian of rhombic symmetry with an effective spin S=1/2. The principal values of the g tensors were determined from an analysis of the angular dependences of the EPR spectra. The orientation of the local magnetic axes of paramagnetic centers relative to the YAlO₃ crystallographic directions are shown to depend on the actual rare-earth species. The EPR spectra exhibit a hyperfine structure due to the ¹⁶⁷Er, ¹⁴³Nd, and ¹⁴⁵Nd odd isotopes, which permitted unambiguous identification of these spectra. The hyperfine coupling constants for the odd erbium and neodymium isotopes are determined.     

Magnetic properties of xCuO · (1 - x) [2B2O3 · PbO] glasses

The results of magnetic studies on xCuO · (1 ? x) [2B₂O₃ · PbO] glasses with 0 ? x ? 50 mol.%, are reported. These results evidenced that the copper ions, in this glass system, are in Cu²⁺ and Cu⁺ valence states. From Curie constant is determined the amount of the copper ions in bivalent state. For glasses with x > 5 mol.% CuO, an antiferromagnetic behaviour is evidenced.     

EPR studies of Cu2+ and V4+ ions in phosphate glasses

Two lead-phosphate glass systems doped with both copper and vanadium ions in different ratios were studied by EPR (electron paramagnetic resonance) method. EPR spectra and parameters (g_‖ = 2.44, g_⊥ = 2.08 andA _‖ = 117.6 · 10⁻⁴ cm⁻¹) obtained for x(CuO · V₂O₅)(l−x)[2P₂O₅ · PbO] glasses withx ≤ 10 mol% suggest a tetrahedral (Td) coordination of Cu²⁺ ions and not a tetragonally elongated octahedron as has been assumed in previous works. The ground state of the paramagnetic electron is thed _xy copper orbital with a 4p_z contribution of 6%. For 20 ≤x ≤ 40 mol% a broad line (ΔB = 307 G) characteristic for clustered ions appears atg = 2.18. The V⁴⁺ ions are evidenced only in the spectra of x(CuO · 2V₂O₅)(1 −x)[2P₂O₅ · PbO] glasses and the resonance parameters suggest a pentacoordinated C_4v local symmetry for these ions. The hyperfine structures characteristic for Cu²⁺ and V⁴⁺ ions disappear for 10 ≤x ≤ 40 mol% due to the mixed exchange Cu²⁺−V⁴⁺ pair formation in these glasses.     

EPR investigation of two types of Syrian's natural zeolites

Two different samples of natural zeolite have been investigated by X-band electron paramagnetic resonance (EPR) spectroscopy. The observed EPR spectra are typical to those observed for Fe³⁺ and Mn²⁺ ions. The lines, related to the iron, are observed, respectively at g≈4.3 and g≈2. The observed six lines, at g≈2, are the hyperfine structure due to the Mn²⁺ ions. The simulation of the experimental EPR spectra suggests that both of the manganese and the iron are present in more one site. The temperature dependence of the EPR spectra has been also investigated. The nature of the different sites involved in the EPR absorption is discussed.     

Spectroscopic studies on Fe and Mn doped SrB4O7 glasses

EPR and optical absorption studies on Fe³⁺ and Mn²⁺ doped strontium tetraborate (SrB₄O₇) glasses are carried out at room temperature. The EPR spectrum of the Fe³⁺ doped glass consists of signals with g-values 9.04, 4.22 and 2.04, whereas the EPR spectrum of Mn²⁺ doped glass exhibits a characteristic hyperfine sextet around g=2.0. The spectroscopic analyses of the obtained results confirmed distorted octahedral site symmetry for the Fe³⁺ and Mn²⁺ impurity ions. Crystal field and Racah parameters evaluated from optical absorption spectra are: Dq=790, B=700 and C=3000 cm⁻¹ for Fe³⁺doped glass and Dq=880, B=700 and C=2975 cm⁻¹ for Mn²⁺ doped glass.     

EPR and magnetic properties of MgO-CaO-SiO2-P2O5-CaF2-Fe2O3 glass-ceramics

Glass-ceramics have been derived from 4.5MgO(45−x)CaO34SiO₂16P₂O₅0.5CaF₂xFe₂O₃ (x=5, 10, 15, 20 wt%) glasses by heat treatment. Room temperature electron paramagnetic resonance (EPR) spectra and temperature-dependent magnetic susceptibility (χ) of the glass-ceramics have been obtained. The EPR absorption line centered at g≈4.3 disappeared at higher concentrations of iron oxide. The intensity and line width of the EPR absorption line centered at g≈2.1 increased as the iron oxide concentration was increased. Temperature-dependent magnetization of samples with low iron oxide content revealed ferrimagnetic as well as paramagnetic contributions. Information about the structural changes involving iron ions, their valence state and the type of magnetic interactions between the Fe ions as a function of composition was obtained using EPR and χ studies.     

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.     

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.     

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.     

Mn activated MgSrAl10O17 green-emitting phosphor—A luminescence and EPR study

This paper reports on the luminescence and electron paramagnetic resonance (EPR) investigations on MgSrAl₁₀O₁₇:Mn²⁺ green-emitting phosphor. Single-phase MgSrAl₁₀O₁₇ was successfully synthesized by the one-step solution combustion route without the need for post-annealing at a higher temperature. Crystallization of the powder was confirmed by X-ray diffraction. The luminescence of Mn²⁺- activated MgSrAl₁₀O₁₇ shows a strong green-emission peak around 515 nm due to the ⁴T₁→⁶A₁ transition of Mn²⁺ ions under the excitation (453 nm). The EPR spectra of Mn²⁺ ions exhibit a sextet hyperfine structure centered at g ≈1.995. The Mn²⁺ ion occupies Mg sites which are in tetrahedral symmetry. The magnitude of the hyperfine splitting (A) indicates that Mn²⁺ is in a moderately ionic environment. The number of spins participating in resonance (N), the paramagnetic susceptibility (χ) and the zero-field splitting parameter (D) have been evaluated and discussed.