EPR study of clusters of rare-earth ions in mixed fluoride crystals

The EPR spectra of the (BaF₂)_{1 ? x} (CeF₃) _x system are studied for the concentrations x = 0, 0.001, 0.002, 0.005, 0.01, and 0.02. The appearance of new tetragonal centers is detected beginning from x = 0.002, the intensity of these centers being maximal at x = 0.01. The (CaF₂)_{1 ? x ? y} (CeF₃) _x (YF₃) _y double solutions with x = 0.001 and y from 0 to 0.02 are also studied. In addition to the ordinary tetragonal center, beginning from y = 0.001, a new tetragonal center appears with the same structure as in the previously studied mixed crystals based on BaF₂—namely, the Ce³⁺-□-R³⁺ chain elongated along the fourfold axis substitutes the Ca²⁺-Ca²⁺-Ca²⁺ and Ba²⁺-Ba²⁺-Ba²⁺ chains in regular CaF₂ and BaF₂ crystals (□ is the cation vacancy, and R³⁺ is the Ce³⁺, La³⁺, or Y³⁺ trivalent ion).     

Etude De La Conductivite Electrique Des Ferrites Oxyfluores A Structure Spinelle

An investigation of the electrical conductivity of some oxyfluoride spinels of formula Zn_x²⁺Fe_1?x³⁺[M²⁺ Fe³⁺]O_4?xF_x (M = Fe, Co, Ni) and Fe³⁺[N_x²⁺Fe²⁺Fe_1?x³⁺]O_4?xF_x (N = Fe, Ni) shows that the conduction depends on the composition of the B sites: the activation energy increases, the conductivity and the Fe₃O₄ transition temperature decrease as the substitution rate of Fe³⁺ by N²⁺ in the B sites increases. The authors conclude to a hopping mechanism between the B cations; the anionic sublattice and the cationic A sublattice do not participate in the conduction.     

Optical,magneto-optical and mössbauer spectroscopy on Co3+ substituted cobalt ferrite Co2+Fe2−xCo3+xO4(0 ⩽ x ⩽ 2)

The magneto-optical spectra of Co_1+xFe_2?xO₄ show with increasing Co³⁺ content an increasing intensity of the 4A₂ ? 4T₁(F) and 4A₂ ? 4T₁(P) transition of Co²⁺ at 0.8 and 2.0 eV. A decrease in the Co²⁺-Fe³⁺ charge transfer transitions on octahedral sites is found. In the optical spectra a strong increase in optical absorption is found with dominant transitions at 0.8, 1.6 and 2.6 eV due to Co³⁺ crystal field transitions on octahedral sites and a Co²⁺-Co³⁺ charge transfer. Conversion Electron Mössbauer Spectroscopy has been used to determine the cation distribution in the surface layer of the samples. The results indicate a shift of Co²⁺ from octahedral to tetrahedral sites when Co³⁺ is substituted in CoFe₂O₄. This results in enhanced optical absorption, enhanced magneto-optical effects and a lower Curie temperature.     

Nonradiative energy transfer from Mn2+ to Eu3+ in K2CaP2O7:Mn2+,Eu3+ phosphor

A series of color tunable phosphors K₂Ca_1?x?yP₂O₇:xMn²⁺, yEu³⁺ are synthesized by solid state reaction method. The energy transfer phenomenon from Mn²⁺ to Eu³⁺ has been observed in the Mn²⁺/Eu³⁺ codoped non-magnetic K₂CaP₂O₇ host, which was confirmed by PL spectra and decay curves. The Mn²⁺→Eu³⁺ energy transfer is controlled by quadrupole–quadrupole interaction between sensitizer and activator. The maximum efficiency of energy transfer is estimated to be 33% with x=0.125 and y=0.03 in K₂Ca_1?x?yP₂O₇:xMn²⁺, yEu³⁺ phosphor. The phosphors can emit light from green to yellow and eventually to orange under 400 nm excitation by changing the Mn²⁺/Eu³⁺ content ratio, indicating that K₂CaP₂O₇: Mn²⁺, Eu³⁺ would be potential candidates for use in lighting and displays applications.     

The influence of local distortions on the static and dynamic properties of copper and silver eightfold-coordinated Jahn-Teller complexes in mixed crystals with a fluorite-type structure

The influence of local distortions on the structure and properties of copper and silver impurity Jahn-Teller complexes in mixed crystals, namely, Ca_xSr_1?x F₂: Me ²⁺ and Sr_1?x Ba_xF₂: Me ²⁺ (0≤x≤1, Me ²⁺=Cu²⁺ or Ag²⁺), is investigated using electron paramagnetic resonance (EPR) spectroscopy at frequencies of 9.3 and 37 GHz in the temperature range 4.2–250 K. Local distortions of the tensile and compressive types are induced by Ca²⁺, Sr²⁺, and Ba²⁺ impurity ions incorporated into the first or second coordination sphere of the cationic environment of the Me ²⁺ impurity ion during crystal growth.     

Emission-tunable phosphors Ca9MgM′ (PO4)7: Eu2+,Mn2+ (M′=Li,Na, K) for white light-emitting diodes

A series of single-composition phosphors Ca₉MgM′(PO₄)₇:xEu²⁺, yMn²⁺ (CMM′ P:Eu²⁺, Mn²⁺; M′=Li, Na, K; 0.003≤x≤0.03; 0 ≤y≤0.1) were synthesized by solid state reactions. Upon excitation at 337 nm, phosphors Ca₉MgM′ (PO₄)₇: Eu²⁺ exhibit strong blue emissions centered at 417 (Ca₉MgLi(PO₄)₇:Eu²⁺), 457 (Ca₉MgNa(PO₄)₇:Eu²⁺), and 453 (Ca₉MgK(PO₄)₇:Eu²⁺) nm respectively, which correspond to the 4f⁶5d¹→4f⁷ transitions of Eu²⁺ ions, Through an effective resonance-type energy transfer, CMM′P:Eu²⁺,Mn²⁺ phosphors exhibit a series of colors by adjusting the concentration of Mn²⁺. The result indicates that CMM′P:Eu²⁺,Mn²⁺ can be potentially used as a UV excited phosphor for white light-emitting diodes (LEDs).     

Co-reduction synthesis of new LnxSb2−xS3 (Ln: Nd, Lu, Ho) nanomaterials and investigation of their physical properties

New Ln_xSb_2−xS₃ (Ln: Lu³⁺, Ho³⁺, Nd³⁺)-based nanomaterials were synthesized by a co-reduction method. Powder XRD patterns indicate that the Ln_xSb_2−xS₃ crystals (Ln=Lu³⁺, Ho³⁺, x=0.00−0.1 and Ln=Nd³⁺, x=0.00−0.08) are isostructural with Sb₂S₃. SEM images show that doping of Lu³⁺ and Ho³⁺ ions in the lattice of Sb₂S₃ results in nanorods while that in Nd³⁺ leads to nanoflowers. UV-vis absorption and emission spectroscopy reveal mainly electronic transitions of the Ln³⁺ ions in case of Ho³⁺ and Nd³⁺ doped nanomaterials. Emission spectra show intense transitions from excited to ground state of Ln³⁺. Emission spectra of doped materials, in addition to the characteristic red emission peaks of Sb₂S₃, show other emission bands originating from f-f transitions of the Ho³⁺ ions. TGA curves indicated that Sb₂S₃ has the highest thermal stability. The electrical conductance of Ln-doped Sb₂S₃ is higher than undoped Sb₂S₃, and increase with temperature.     

Xanes (X-ray absorption near edge structure) of V in vanadium-iron phosphate glasses

The X-ray Absorption Near-Edge Structure (XANES) of V in vanadium-iron glasses (50P₂O₅ + (50?x)FeO + xV₂O₅) have been measured. The effective charge of V ions in glasses has been determined. At low V₂O₅ concentration (x ～ 5) only V⁴⁺ with 6-fold coordination is present on the contrary a static mixed valence state (V⁴⁺, V⁵⁺) has been found at high concentrations 20?x?50. The results explain the electron hopping conductivity effects at high V₂O₅ concentration (x ～ 50) involving V⁴⁺ ? V⁵⁺ pairs and at low V₂O₅ concentration (x?10) involving V⁴⁺ ? Fe³⁺ pairs.     

Investigation of gain characteristics in mixed crystals LiMeF4 (Me = Y,Lu, Yb) doped by Ce3+ ions

Differential gain spectra in the range 295–335 nm were measured in crystals of scheelite structure LiY_{1 ? x} Lu _x F₄ (x = 0–1), doped by Ce³⁺ ions. It is shown that variation of Lu³⁺ and Y³⁺ ions relative content in LiY_{1 ? x} Lu _x F₄ crystals allows to manipulate the spectral width of the amplification band. Cross-sections of excited-state absorption at the wavelengths of Ce³⁺ luminescence, probability ratios of formation and thermal destruction of color centers depending on the Y³⁺ ions content in LiY_{1 ? x} Lu _x F₄ crystals were estimated. Even better gain characteristics have been demonstrated by LiLuF₄:Ce³⁺, doped by Yb³⁺ ions. The highest optical gain coefficient with a wide amplification band among studied samples was observed in LiLuF₄:Ce³⁺ crystal, codoped by Yb³⁺ ions.     

Anisotropy of hexagonal ferrites with M,W and Y structures containing Fe3+ and Fe2+ as magnetic ions

The ferrimagnetic saturation moment and hexagonal anisotropy constant K₁ have been measured at 4K on a Zn₂Y single crystal and on polycrystalline BaFe²⁺₂W and SrFe²⁺₂W samples. The moment of Fe₂W is in agreement with a collinear spin coupling and with the known site occupation for the Fe²⁺ ions. The moment of Zn₂Y is 9% lower than the value for a collinear configuration.The uniaxial anisotropy of Fe²⁺ in hexagonal ferrites is discussed and compared with that of Co²⁺. No noticeable Fe²⁺ anisotropy is found in Fe₂W in contrast to LaM = LaFe²⁺Fe³⁺₁₁O₁₉, in which the Fe²⁺ anisotropy is strong. The difference is attributed to the symmetry difference of the sites occupied by the Fe²⁺ ions in both compounds. The current theory does not satisfactorily explain the anisotropy and quadrupole splitting of Fe²⁺ in LaM. From this it is concluded that admixing of ⁵E states and (or) the influence of a dynamical Jahn-Teller effect cannot be neglected.The dipole-dipole anisotropy is computed for the M, W and Y structure and some deviation from the literature data is found. Using these results, a mean anisotropy of 1.3 to 2.3 cm^?1 per Fe³⁺ ion is found for the three structures.     

Paramagnetic defects in manganese-doped lead tungstate

In manganese-doped PbWO₄ crystals, low-intensity signals of triclinic clusters Mn⁴⁺-V _O and Fe³⁺-V _Pb have been revealed in addition to signals of Mn²⁺ tetragonal centers. The Mn⁴⁺-V _O cluster is formed by a Mn⁴⁺ ion in the W⁶⁺ position, which is associated with a vacancy of the nearest neighbor O^2?ion, and the Fe³⁺-V _Pb cluster consists of a Fe³⁺ ion substituting for Pb²⁺ with a local compensation of by a lead vacancy. It has been shown that, in PbWO₄: Mn, there is also a small amount of Mn⁴⁺ tetragonal centers located in the Pb²⁺ position with a nonlocal compensation of an excess charge.     

Study on the luminescence behavior of lanthanide ions using luminol as probe

Using luminol as the probe, the luminescence behavior of trivalent lanthanide ions (Ln³⁺=La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺, Tm³⁺, Yb³⁺ and Lu³⁺) in aqueous solution was first investigated by fluorescence, and the sensitivity enhanced by 3–5 orders of magnitude compared with the Ln³⁺ intrinsic fluorescence. It was found that Ln³⁺ with luminol could form a 1:1 association complex which remarkably enhanced the fluorescence signal of luminol. The increment of fluorescence intensity was proportional to the concentration of Ln³⁺ in the range of 1.0–70.0 nmol L^?1, and the linear correlation equation, ΔI_F=AC_Ln+B, was given. The relationships of A (defined as sensitivity factor) with some physical parameters (atomic number Z, ionic radius γ_±, standard redox potential E^o and hydration enthalpy ΔH_hyd) were discussed. The good symmetry of A vs. Z plot for light lanthanides (LLG) and the heavy lanthanides (HLG) and linear relations of A with Z, γ_±, E^o and ΔH_hyd should originate in the special features of Ln³⁺ electronic configurations [Xe]4fⁿ (n=0–14). Using the proposed model of Ln³⁺–luminol interaction, lg[ΔI_F/(I_Fo–ΔI_F)]=rlg[Ln]+lg k, the association constant k was obtained over the range of 1.95×10⁶–2.63×10⁷ L mol^?1.     

Energy transfer from Ce3+toNd3+ in pentaphosphate crystals

An excitation band at 300 nm corresponding to Ce³⁺absorption is observed in pentaphosphate crystals containing Ce³⁺ and Nd³⁺ when the Nd³⁺ luminescence is monitored. The decay of excitation of Ce³⁺ in crystals of pure cerium pentaphosphate, CeP₅O₁₄, follows single exponential kinetics with a 22 ± 2 nsec lifetime. In Ce_0.5Nd_0.5P₅O₁₄ crystals, the Ce³⁺ lifetime is shortened to 3.8 ± 0.4 nsec as a result of efficient nonradiative energy transfer to the Nd³⁺ ions.     

Mössbauer spectra of Fe3+ and Fe2+ ions in hexagonal ferrite with w-structure

The hexagonal ferrite Fe₂W = BaFe₂²⁺Fe³⁺₁₆O₂₇ exhibits a sharp ⁵⁷Fe Mössbauer spectrum at 300 and 78 K. All seven sublattices in this complicated crystal structure are detected. Fast electron exchange between Fe²⁺ and Fe³⁺ ions gives rise to sharp lines and makes them indistinguishable. At 5 K the exchange is slow and the Fe²⁺ ions are detected from the presence of a weak subspectrum with broadened lines separated from the main spectrum of the Fe³⁺ ions. Analysis shows that the Fe²⁺ ions reside exclusively on one of the seven sublattices, which is occupied statistically by Fe²⁺ and Fe³⁺ ions in the ratio of 2 : 1. For SrFe²⁺₂Fe³⁺₁₆O₂₇ the situation is the same.     

Concentration dependence of the Ce3+ and Tb3+ luminescence of Ce1-xTbxMgAl11O19

The quenching of the Ce³⁺ emission and the increase of the Tb³⁺ emission with increasing x of Ce_1-xTb_xMgAl₁₁O₁₉ for x ? 0.35 is ascribed to energy transfer from Ce³⁺ to Tb³⁺, which is restricted to nearest rare earth neighbours. This transfer is almost complete at x ? 0.35. The decrease of the Tb³⁺ emission at higher Tb³⁺ concentrations is not due to Tb³⁺ concentrational quenching, but due to the limited solubility of Tb³⁺ in the CeMgAl₁₁O₁₉ phase.     

π−Electroproduction off deuterium above the resonance region

The reactionse + d → e' + p_S + p + π^?ande + d → e' + n_S + n + π⁺ were measured detecting electron and pion in coincidence at an invariant hadronic mass of 2.19 GeV. The measurements were performed at electron four-momentum transfer squared of f² = 0.70 and 1.35 GeV² in the range of t = (γ_v?π)² between t_minand ?1.0 GeV². The cross section d²σ/dtdφ of the reaction e + n → e' + p + π^? was determined.     

Research on La–Co-substituted strontium ferrite magnets for high intrinsic coercive force

M-type strontium ferrites with substitution of Sr²⁺ by rare-earth La³⁺, and a little amount of Fe³⁺ by Co²⁺ according to the formula Sr_1−xLa_xFe_12−xCo_xO₁₉, are prepared by the ceramic process. Effects of the substituted amount of La³⁺ and Co²⁺ on structure and magnetic properties of Sr_1−xLa_xFe_12−xCo_xO₁₉ compounds have systematically been investigated by X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and B–H hysteresis curve measurements. In our results, the suitable amount of La³⁺–Co²⁺ substitution may remarkably increase saturation magnetization. Intrinsic coercive force (H_cj) of Sr ferrite magnets is evidently increased without significant decrease in residual flux density (B_r) by La³⁺–Co²⁺ substitution.     

Near infrared fluorescence and energy transfer in Ce/Nd Co-doped CaxSr1−xS

Novel near infrared (NIR) phosphors Ca_xSr_1−xS:Ce³⁺,Nd³⁺ were synthesized by a solid state reaction. The NIR emission was realized through an efficient absorption by the allowed 4f-5d transition of Ce³⁺ and efficient energy transfer to Nd³⁺ via well-matched energy levels. Ce³⁺ and Nd³⁺ content in CaS/SrS was optimized. It was found that CaS:Ce³⁺,Nd³⁺ gave much stronger NIR emission than that of SrS:Ce³⁺,Nd³⁺. Further studies on Ca_xSr_1−xS:Ce³⁺,Nd³⁺ indicated that both visible emission of Ce³⁺ and NIR emission of Nd³⁺ were observably affected by Ca/Sr ratio. The energy transfer efficiency, which can be estimated from fluorescence lifetime of Ce³⁺, increased from 52% to 74% for the Ca_xSr_1−xS:Ce³⁺,Nd³⁺ (x=0 to 1) series, accompanied with a shift of maximal emission wavelength of Ce³⁺ from 482 to 505 nm. The results showed that overlap between emission spectrum of Ce³⁺ and excitation spectrum of Nd³⁺ plays an important role in the energy transfer efficiency, and Ce³⁺ emitting in green or blue-greenish region sensitized the Nd³⁺ NIR fluorescence emission more efficiently than that in blue region.     

UV and VUV spectroscopic study of Na0.4Y0.6F2.2 crystals doped with rare-earth ions

The short-wavelength transmission spectra of Na_0.4 R _0.6F_2.2 crystals with R = Y, Yb, or Lu have been investigated. For these crystals, the VUV transmission cutoffs are 78750, 58820, and 75200 cm^?1, respectively. The 4f ⁿ–4f ^n?15d absorption and excitation spectra of Na_0.4Y_0.6F_2.2 crystals activated with Ce³⁺, Pr³⁺, Nd³⁺, Er³⁺, Tm³⁺, and Yb³⁺ ions have been analyzed in the range 30000–80000 cm^?1. The energy positions of the lowest levels of the 4f ^n?15d configurations of these ions in the fluorite crystal matrix Na_0.4Y_0.6F_2.2 are determined. The absorption band in the spectral range 60600–70000 cm^?1 in Na_0.4(Y, Yb)_0.6F_2.2 crystals is due to the charge transfer from F^? to Yb³⁺. It is shown that the environmental symmetry of Ce³⁺ ions in Na_0.4R_0.6F_2.2 (R = Y, Yb, Lu) crystals is almost identical.     

Theoretical calculations of the optical band positions and spin-Hamiltonian parameters for Yb at the tetragonal Y site of KY3F10 crystal

The six optical band positions and six spin-Hamiltonian parameters [g factors g_∥, g_⊥ and hyperfine structure constants A_∥(¹⁷¹Yb³⁺), A_⊥(¹⁷¹Yb³⁺), A_∥(¹⁷³Yb³⁺), A_⊥(¹⁷³Yb³⁺)] for Yb³⁺ ion at the tetragonal Y³⁺ site of KY₃F₁₀ crystal are calculated from a diagonalization (of energy matrix) method. In the method, the Hamiltonian of energy matrix contains the free-ion, crystal-field interaction, Zeeman (or magnetic) interaction and hyperfine interaction terms and so a 14×14 complete energy matrix for 4f¹³ ion in tetragonal crystal-field and under an external magnetic field is constructed. Diagonalizing the energy matrix, these optical and EPR spectral data are calculated together and the calculated results are in reasonable agreement with the experimental values. The signs of hyperfine structure constants A_∥, A_⊥ for the isotopes ¹⁷¹Yb³⁺ and ¹⁷³Yb³⁺ in KY₃F₁₀ are suggested. The results are discussed.