Photostimulated electron transfer and its action on paramagnetism of Sp<Subscript>3</Subscript>Cr(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript> single crystals

The effect of irradiation by ultraviolet light on the effective magnetic moment of a paramagnetic single crystal based on photochrome spiropyran (Sp) and chromium oxalates Sp₃Cr(C₂O₄)₃ molecules is detected. It is shown that the deviation of the temperature dependence of the magnetic moment from the Curie law is caused not by the exchange interaction, but by electron redistribution between Cr³⁺ and Cr⁴⁺ ions and spiropyran molecules Sp⁰ and Sp⁺. Analysis of the angular dependence of EPR spectra makes it possible to determine the contribution of Cr³⁺ ions to the magnetic properties of the crystals and to determine the crystal field parameters D = 0.619 cm⁻¹ and E = 0.024 cm⁻¹. Irradiation of hydrated samples by ultraviolet light leads to intensity redistribution of EPR lines attributed to Cr³⁺ and Sp⁰. Thermally stimulated paramagnetism of triplet states of spiropyran ions Sp⁺ and the SpI salt is observed.     

Jahn-teller chromium ions in CdF<Subscript>2</Subscript> and CaF<Subscript>2</Subscript> crystals: An EPR spectroscopic study in the frequency range 9.3–300 GHz

The bivalent chromium impurity centers in CdF₂ and CaF₂ crystals are investigated using electron paramagnetic resonance (EPR) in the frequency range 9.3–300 GHz. It is found that Cr²⁺ ions in the lattices of these crystals occupy cation positions and form [CrF₄F₄]^6? clusters whose magnetic properties at low temperatures are characterized by orthorhombic symmetry. The parameters of the electron Zeeman and ligand interactions of the Cr²⁺ ion with four fluorine ions in the nearest environment are determined. The initial splittings in the system of spin energy levels of the cluster are measured.     

Structural and magnetic phase transformations in the BiFeO<Subscript>3</Subscript>-CaFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> system

The crystal structure and magnetic properties of the Bi_{1 ? x} Ca _x Fe_{1 ? x/2}Nb _x/2O₃ system were studied. It is shown that, at x ≤ 0.15, the unit-cell symmetry of solid solutions is rhombohedral (space group R3c). Solid solutions with x ≥ 0.3 have an orthorhombic unit cell (space group Pbnm). The rhombohedral compositions are antiferromagnetic, while the orthorhombic compositions exhibit a small spontaneous magnetization due to Dzyaloshinski?-Moriya interaction. In CaFe_0.5Nb_0.5O₃, the Fe³⁺ and Nb⁵⁺ ions are partially ordered and the unit cell is monoclinic (space group P2₁/n). In the concentration range 0.15 < x < 0.30, a two-phase state (R3c + Pbnm) is revealed.     

Electron paramagnetic resonance of Ce<Superscript>3+</Superscript> and Nd<Superscript>3+</Superscript> impurity ions in YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6.13</Subscript>

The electron paramagnetic resonance (EPR) spectra of Ce³⁺ and Nd³⁺ impurity ions in unoriented powders of the YBa₂Cu₃O_6.13 compound are observed and interpreted for the first time. It is demonstrated that, upon long-term storage of the samples at room temperature, the EPR signals of these ions are masked by the spectral line (with the g factor of approximately 2) associated with the intrinsic magnetic centers due to the significant increase in its intensity.     

Spin-spin interaction and the EPR spectrum of KDy(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The EPR spectrum of a KDy(WO₄)₂ monoclinic crystal is investigated. It is found that the EPR spectrum of magnetically concentrated materials at a low frequency (9.2 GHz) undergoes a substantial transformation in addition to the well-known broadening of the EPR lines. At low Dy³⁺ concentrations (x<10^?2), the EPR spectrum of an isomorphic crystal, namely, KY_(1?x)Dy_x(WO₄)₂, is characterized by the parameters g_x=0, g_y=1.54, and g_z=14.6. For a magnetically concentrated crystal KDy(WO₄)₂, the g values are as follows: g_x=0, g_y=0.82, and g_z=2.52. It is demonstrated that the difference in the parameters is associated with the specific spin-spin interaction between Dy³⁺ ions, including the Dzyaloshinski interaction, which is not observed at high frequencies.     

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.     

Cr<Superscript>3+</Superscript> spectroscopy study in ZnO-codoped and Zn-in-diffused congruent LiNbO<Subscript>3</Subscript>:Cr crystals

This paper reports on the spectroscopy properties, absorption and luminescence, of Cr³⁺ ions in singly doped, ZnO-codoped, and Zn in-diffused LiNbO₃:Cr crystals. In addition to the broad absorption, inter-ionic transitions ascribed to Cr³⁺ ions located in Li⁺ and Nb⁵⁺ sites; [Cr]_Li and [Cr]_Nb centres two absorption bands at higher energy are reported and ascribed to the charge transfer transitions of the Cr³⁺ ions of the two defect centres. The charge transfer transitions are used as optical probe to study the role of the Zn ions in the Zn in-diffused LiNbO₃:Cr samples. It has been observed that the Zn-in-diffused processes created [Cr]_Nb centres in the diffusion zone. The location of the diffused Zn²⁺ ions is considered to be in Li⁺ site, displacing the Cr³⁺ ions from the Li⁺ sites, [Cr]_Li, to the Nb⁵⁺ positions, [Cr]_Nb.     

Three types of photomagnetic effects in Sp<Subscript>3</Subscript>Cr(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript> crystals

Three different photomagnetic effects caused by ultraviolet light in paramagnetic crystals based on molecules of spiropyrans (Sp) Sp₃Cr(C₂O₄)₃ and SpI have been revealed and separated: (1) in the high-temperature range (30–300 K), the photomagnetic effect in Sp₃Cr(C₂O₄)₃ is determined by the charge transfer between chromium ions and spiropyran molecules; (2) in the low-temperature range (2 K), the photomagnetic effect in Sp₃Cr(C₂O₄)₃ is due to the photoisomerization of spiropyran molecules, the change in the crystal field, and the splitting of the levels of Cr³⁺ ions in zero field; and (3) in the temperature range 2–20 K, the generation of radiation-induced paramagnetic defects contributes to the magnetic moment of the organic sublattice Sp⁺.     

The Formation of Dimeric Centers of Copper,Iron and Gadolinium in Modified Pb<Subscript>5</Subscript>Ge<Subscript>3</Subscript>O<Subscript>11</Subscript>

It is discovered that the electron paramagnetic resonance (EPR) spectrum of the doubly charged copper centers occurs in single crystals of Pb₅Ge₃O₁₁ doped with gadolinium or iron after annealing in an atmosphere containing chlorine and bromine. Similar annealing of the crystals doped with copper in a chlorine and fluorine atmosphere leads to redistribution of the intensities of the EPR spectra of two types of Cu²⁺ centers. The influence of annealing on the ongoing intensity of spectra of the dimeric triclinic centers Fe³⁺–A, Gd³⁺–A (where A represent Cl^?, Br^?, O^2?, F^?) was the subject of this research. Consideration is given to the mechanisms for changing the charge state and association of copper center with defects.     

CaCuMn<Subscript>6</Subscript>O<Subscript>12</Subscript> vs. CaCu<Subscript>2</Subscript>Mn<Subscript>5</Subscript>O<Subscript>12</Subscript>: A comparative study

The ferrimagnetic compounds Ca(Cu_xMn_3?x)Mn₄O₁₂ of the double distorted perovskites AC₃B₄O₁₂ family exhibit a rapid increase of the ferromagnetic component in magnetization at partial substitution of square coordinated (Mn³⁺)_C for (Cu²⁺)_C. In the transport properties, this is seen as a change of the semiconducting type of resistivity for the metallic one. The evolution of magnetic properties of Ca(Cu_xMn_3?x)Mn₄O₁₂ is driven by strong antiferromagnetic exchange interaction of (Cu²⁺)_C with (Mn³⁺/Mn⁴⁺)_B coordinated octahedra. The competing interactions of (Mn³⁺)_C with (Mn³⁺/Mn⁴⁺)_B lead to the formation of noncollinear magnetic structures that can be aligned by magnetic fields.     

Antisite defects and valence state of vanadium in Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

Electron paramagnetic resonance (EPR) studies have been performed with the aim of determining the valence state and local crystal structure of the nearest environment of vanadium ions in the initial, charged, and discharged samples of the cathode material Na_xV₂(PO₄)₃ (1 ≤ x ≤ 3). It has been found that the charged sample (x = 1) is characterized by an intense signal corresponding to V⁴⁺ ions located in a highly distorted octahedral crystal field. An EPR signal with the g-factor close to the g-factor of the V⁴⁺ ion has also been observed in the initial sample (x = 3), where the intensity of the resonance signal is one order of magnitude lower than that in the charged sample. It has been revealed that the resonance signal under consideration is associated with the formation of antisite defects when a part of vanadium ions are located in sites of sodium ions. It has also been found that the intensity of this signal increases after a complete charge–discharge cycle (x = 3).     

Relations between physical properties of the biferroic Pb(Fe<Subscript>1-x</Subscript>Nb<Subscript>x</Subscript>)O<Subscript>3</Subscript>ceramics and their composition change

The work shows basic features of ferromagnetic ceramics Pb(Fe_{1 - x}Nb_x)O₃ with various contents of Fe/Nb (x=1/3, 1/2, 2/3). The synthesis were carried out by powders sintering and calcination whereas densification by hot uniaxial pressing and conventional sintering methods. Optimum conditions of PFN obtention with various contents were based on X-ray, microstructural, dielectrical and conductivity tests together with increase of iron contents in Pb(Fe_{1 - x}Nb_x)O₃ usage parameters of those ceramics worsen. Optimum parameters are shown by the ceramics with contents Pb(Fe_{1 / 2}Nb_{1 / 2})O₃ synthetized using calcination method and densified by hot uniaxial pressing method.     

Phase transition and electrical properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)(Nb<Subscript>1-x</Subscript>Ta<Subscript>x</Subscript>)O<Subscript>3</Subscript> lead-free piezoelectric ceramics

(K_0.5Na_0.5)(Nb_1-xTa_x)O₃ lead-free piezoelectric ceramics have been prepared by an ordinary sintering technique. The results of X-ray diffraction reveal that Ta⁵⁺ diffuses into the K_0.5Na_0.5NbO₃ lattices to form a solid solution with an orthorhombic perovskite structure. Because of the high melting temperature of KTaO₃, the (K_0.5Na_0.5)(Nb_1-xTa_x)O₃ ceramics can be sintered at higher temperatures. The partial substitution of Ta⁵⁺ for the B-site ion Nb⁵⁺ decreases both paraelectric/cubic–ferroelectric/tetragonal and ferroelectric/tetragonal–ferroelectric/orthorhombic phase transition temperatures, T_C and T_O-T. It also induces a relaxor phase transition and weakens the ferroelectricity of the ceramics. The ceramics become ‘softened’, leading to improvements in d₃₃, k_p, k_t and ε_r and a decease in E_c, Q_m and N_p. The ceramics with x=0.075–0.15 become optimum, having d₃₃=127–151 pC/N, k_p=0.43–0.44, k_t=0.43–0.44, ε_r=541–712, tanδ=1.75–2.48% and T_C=378–329 °C. PACS 77.65.-j; 77.84.Dy; 77.84.-s     

Luminescence of Cr<Superscript>3+</Superscript> impurity ions in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> nanocrystals and clusters embedded in lithium germanate glasses

The properties of Cr³⁺-doped Li₂Ge₇O₁₅ (LGO) lithium germanate nanocrystals produced in lithium germanate glasses under isothermal heating were studied. The samples were characterized by x-ray diffraction and small-angle scattering, as well as by transmission electron microscopy. The luminescence spectra of the impurity chromium measured in lithium germanate glasses containing LGO crystals revealed transitions in Cr³⁺ ions residing in the glass phase and in LGO crystallites starting from extremely small clusters. This provided the possibility of following the process of crystallization of the lithium germanate glass from Cr³⁺ luminescence spectra. The effects observed in the Cr³⁺ luminescence spectrum revealed a ferroelectric phase transition in LGO nanocrystals embedded in the glass.     

High-frequency EPR of Tb<Superscript>3+</Superscript>-doped KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> crystal

High-frequency electron paramagnetic resonance (EPR) spectra of the KPb₂Cl₅:Tb³⁺ crystal have been investigated. Three types of spectra were observed in the frequency range of 74–200 GHz. The most intensive spectrum with the resolved hyperfine structure corresponded to transitions between sublevels of the¹⁵⁹Tb³⁺ ground quasi-doublet with the zero-field splitting (ZFS) close to 48 GHz. Experimental results were analyzed by the exchange charge model of the crystal field affecting terbium ions in low-symmetry Pb²⁺ positions with the chlorine sevenfold coordination and the charge compensating vacancy in the nearest potassium site. The calculated values ofg-factors and ZFS were in agreement with the experimental data. The nature of a broad EPR line with ZFS of about 180 GHz and of additional weak EPR lines observed as satellites of the main Tb³⁺ lines was discussed.     

Ferroelectric phase transition of Nb-doped Bi<Subscript>3.25</Subscript>La<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ceramics

Bi_3.25La_0.75Ti_3-yNb_yO₁₂ (y=0.0, 0.03, 0.09, 0.15, 0.21) were synthesized using the solid-state reaction method. The effects of Nb doping on ferroelectric properties were studied through dielectric and P-E measurements. The value of P_r increases with increasing Nb content. Bi_3.25La_0.75Ti_3-yNb_yO₁₂ ceramics exhibit a maximum remanent polarization of P_r=27 μC/cm² at an Nb content of y=0.09. These results indicate that Nb doping can improve the ferroelectric properties of BLT ceramics. The Curie temperature, T_c, decreased with increasing Nb-content, and the ferroelectric phase transition of BLTNy is a second-order transition without thermal hysteresis. PACS 77.55.+f; 77.80.-e; 77.22.Jp     

EPR studies of highly pure,pure and doped chromium oxide powders

Abstract

EPR absorption measurements on ‘pure’, highly pure and A1₂O₃ doped Cr₂O₃ powder have been made. The EPR absorption in the ‘pure’ powders obtained below Ntel temperature is shown to be due to background magnetic impurities present in the powders and not due to superparamagnetism as suggested by earlier authors. No EPR absorption could be observed below Nkl temperature in highly pure powders (total background impurity concentration less than 5 ppm). ‘Pure’ powders or highly pure powders mixed with A1₂O₃ powder and annealed at high temperatures showed a symmetrical EPR absorption line at room temperature. The shape and the g value of this line are practically the same as those obtained for Cr³⁺ ions in Cr₂O₃ above Nee1 temperature or in other nonmagnetic crystals. It is concluded from these results that the impurities diffuse into Cr₂O₃ powder, the antiferro-magnetic coupling between some of the Cr³⁺ ions is broken and these Cr³⁺ ions become paramagnetic, even when the bulk of the material is in antiferromagnetic state. The variation of half-width of EPR lines with impurity concentration shows that the dipolar coupling between Cr³⁺ ions decreases with the increase in impurity concentration and when the impurity concentration is high the Néel temperature seems to shift to lower temperatures. A longer heat treatment of the ‘pure’ B powder resulted in the production of shining metal particles in the powder. The EPR of this powder showed excessive increase in the intensity of EPR absorption when the temperature of the powder was raised to a value just above the Néel temperature. A comparison of these reuslts with the work of earlier authors suggests that the shinning metal particles are those of chromium metal and are responsible for this increase in EPR absorption.     

Magnetic ordering and magnetoresistive effect in La1−x Srx(Mn1−y Mey)O3 perovskites (Me = Nb, Mg)

Perovskites of composition La_1?x Sr_x(Mn_1?x/2Nb _x/2)O₃ and La_0.49Sr_0.51(Mn_1?y Nb_y)O₃ have been synthesized and investigated. The substitution of nonmagnetic niobium ions for manganese was shown to lead to a transition from the metallic into the insulating state due to a decrease in the number of dissimilar (different-valence) manganese atoms in the lattice. In spite of the high resistivity, the niobium-containing perovskites exhibit a large magnetoresistive effect and ferromagnetic ordering. Small additions of Nb⁵⁺ to La_0.49Sr_0.51MnO₃ stimulate the transition from the antiferromagnetic into the ferromagnetic state, whereas the substitution of Mg²⁺ for Mn stabilizes the antiferromagnetic state. It is supposed that the ferromagnetism in the insulating perovskites at hand is due to the positive superexchange of the Mn³⁺-O-Mn³⁺ type, and the magnetoresistive effect owes to the intergranular transfer of spin-polarized charge carriers and the suppression of magnetic nonuniformities by an applied magnetic field near T _C.     

Effect of low-temperature annealing on the magnetization curve of YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6 + <Emphasis Type="Italic">x</Emphasis></Subscript> ceramics

The effect of low-temperature annealing on the magnetization curve of YBa₂Cu₃O_{6 + x} ceramics in the superconducting state (x ≈ 0.9) is investigated. When the annealing time is fairly long, the field dependence of magnetic moment M exhibits a feature in the form of a plateau, where the value of M remains almost constant. The evolution of this feature in the magnetization curves of annealed samples with annealing time and temperature is studied. It is assumed that low-temperature annealing gives rise to metastable ferromagnetic clusters in YBa₂Cu₃O_{6 + x} ceramics, the contribution of which to the magnetic moment accounts for the feature in the magnetization curves of the annealed samples.     

Effect of Ba-substitution on the structure and properties of Pb<Subscript>0.8</Subscript>Ba<Subscript>0.2</Subscript>[(In<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)<Subscript>1-x</Subscript>Ti<Subscript>x</Subscript>]O<Subscript>3</Subscript> ceramics

Ferroelectric ceramics with formula Pb_0.8Ba_0.2[(In_1/2Nb_1/2)_1-xTi_x]O₃ (PBINT) (x=0.0,0.1,0.2,0.3,0.4 and 0.5) were prepared via a two-step solid state reaction method. It was found that ceramics with compositions in the range of x=0.0∼0.3 showed a pseudo-cubic structure, whereas the ceramic with x=0.5 displayed a tetragonal structure. All compositions showed significant frequency dispersion in their dielectric properties. The remanent polarization P_r as well as the coercive field E_c, measured at room temperature, increases with the Ti content. The experimental results obtained in this system are summarized into a phase diagram, with the morphotropic phase boundary (MPB) located at x=0.4. Compared with the Pb[(In_1/2Nb_1/2)_1-xTi_x]O₃ solid solution system, incorporating Ba in the A-site leads to a significant decrease in the dielectric maximum temperature T_max, a suppression of the dielectric relaxation parameter γ, and a shift of the MPB composition to a higher Ti content. PACS 77.84.Dy; 77.80.Bh; 77.22.Ch