Electron paramagnetic resonance of Dy3+ ions in lead thiogallate single crystals

The results of electron paramagnetic resonance (EPR) studies of Dy³⁺ ions in lead thiogallate PbGa₂S₄ single crystals have been presented. It has been shown that the ground state of these ions corresponds to the lowest Stark sublevel Γ₆ of the term ⁶ H _15/2. The spectra are well described by the axially symmetric spin Hamiltonian with the effective spin S = 1/2 with the factors g _‖ = 15.06 and g _⊥ = 2.47. The Dy³⁺ ions substitute Pb²⁺ ions in the crystal lattice of PbGa₂S₄. The observed hyperfine structure has allowed to unambiguously interpret the EPR spectra. The hyperfine interaction constants of two odd isotopes of dysprosium in lead thiogallate single crystals have been found to be A _‖ = 675 × 10^?4 cm^?1 and A _⊥ = 111 × 10^?4 cm^?1 for ¹⁶³Dy and A _‖ = 472 × 10^?4 cm^?1 and A _⊥ = 77 × 10^?4 cm^?1 for ¹⁶¹Dy.     

Trigonal and triclinic Fe3+ paramagnetic centers in ferroelectric Pb5Ge3O11

In the EPR spectra of iron-doped lead germanate single crystals, triclinic Fe³⁺ paramagnetic centers have been found in addition to trigonal centers. Their contribution increases upon annealing in a chlorine-containing atmosphere. The parameters of the spin Hamiltonian of three triclinic centers assigned to Fe³⁺-Cl^? dimeric complexes have been determined. The localization of iron and chlorine ions in Pb₅Ge₃O₁₁ has been discussed.     

EPR spectra of Fe centers in layered TlGaSe2 single crystal

A single-crystal TlGaSe₂ doped by paramagnetic Fe ions has been studied at room temperature by electron paramagnetic resonance (EPR) technique. The fine structure of EPR spectra of paramagnetic Fe³⁺ ions was observed. The spectra were interpreted to correspond to the transitions among spin multiplet (S=5/2, L=0) of Fe³⁺ ion, which are splitted by the local ligand crystal field (CF) of orthorhombic symmetry. Four equivalent Fe³⁺ centers have been observed in the EPR spectra and the local symmetry of crystal field at the Fe³⁺ site and CF parameters were determined. Experimental results indicate that the Fe ions substitute Ga at the center of GaSe₄ tetrahedrons, and the rhombic distortion of the CF is caused by the Tl ions located in the trigonal cavities between the tetrahedral complexes.     

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.     

Effect of the valence state of ce ions on the phase stability and mechanical properties of the crystals of ZrO<Subscript>2</Subscript>-based solid solutions

The structure and mechanical properties of the crystals of solid solutions of zirconium dioxide, which are stabilized by yttrium and cerium oxides, have been studied. The electron paramagnetic resonance technique has been used to identify Ce³⁺ ions and to determine their relative concentration in the crystals. It is shown that the presence of Ce³⁺ ions in the crystals is the main factor responsible for their high fracture toughness. The annealings carried out during investigations, which lead to a decrease in the concentration of Ce³⁺ ions, show that a change in the valence state of cerium ions lowers the fracture toughness of the crystals.     

Electron paramagnetic resonance study of exchange coupled Ce3+ ions in Lu2SiO5 single crystal scintillator

The Ce³⁺ ions incorporation inside lutetium oxyorthosilicate (Lu₂SiO₅) single crystals was studied by electron paramagnetic resonance. Already known Ce1 and Ce2 centers originating from the lattice peculiarity allowing two lutetium sites coordinated by different number of the oxygen ions were detected. Remarkably, for the Ce2 center, the determined g² tensor is asymmetric and could not be diagonalized as compared to the Ce1 center, for which the three principal values and corresponding axes orientation have been determined and reported previously. Besides, the much weaker resonance lines found in spectra close to those coming from the Ce1 and Ce2, and following them under crystal rotation with respect to the direction of an external magnetic field, have been revealed as well. They were classified as doublets produced by the exchange coupled Ce³⁺ ions, creating the Ce1–Ce1, Ce2–Ce2 and Ce1–Ce2-like dimers. The corresponding spin–spin coupling constants were estimated. They are in the range 0.04–0.4 cm⁻¹. The Ce1, Ce2 and total dimer centers populations were calculated as 89%, 4.5% and 6.5%, comparing integral intensities of corresponding resonance lines.     

In situ formation of magnetic–luminescent, bi-functional, polymer-stabilized cerium sulfide nanoparticles

Polymer-stabilized paramagnetic and fluorescent rare-earth metal sulfide (cerium sulfide, Ce₂S₃) nanoparticles have been synthesized by using an ??in situ polymerization and composite formation?? (IPCF) technique (Mallick et al. in J. Appl. Phys. 106:074303, 2009) at room temperature. Encapsulated cerium sulfide nanoparticles showed photoluminescence when excited with laser irradiation. The composite material exhibited a paramagnetic behavior due to the in situ formation of magnetic Ce³⁺ ionic species at the reaction condition.     

Photoactive lead ions in ferroelectric Pb<Subscript>5</Subscript>Ge<Subscript>3</Subscript>O<Subscript>11</Subscript> and paramagnetic resonance

The recharging of lead matrix ions upon exposure to light in pure, doped, and nonstoichiometric lead germanate crystals has been studied using electron paramagnetic resonance. It has been shown that the maximum concentration of metastable Pb³⁺ ions is achieved in crystals doped with chlorine, fluorine, titanium, and in samples with excess lead oxide. The annealing activation energy and the parameters of the superhyperfine interaction of Pb³⁺ paramagnetic centers have been determined.     

Birefringence of PbGa2S4 crystals

Birefringence of PbGa₂S₄ single crystals is studied in the spectral range of 0.45–0.8 μm at T = 300 K. The obtained results are analyzed, and conclusions on the bond character in lead thiogallate are drawn.     

EPR of Pb3+ ion in LiBaF3 crystals

Complex EPR spectra of paramagnetic centers Pb³⁺ formed in LiBaF₃:Pb²⁺ crystals under X-ray irradiation are studied in the temperature range of 10–150 K. It is shown that lead ions substitute Ba²⁺ ions in the LiBaF₃ crystal and are in the cubic-octahedral 12-fold environment of the fluorine ions. The hyperfine structure constants describing the observed spectrum are determined and parameters of superhyperfine interaction with the nearest fluorine ions are estimated.     

Spectral-kinetic studies of SrAlF5 doped by trivalent rare-earth ions

Photochemical properties of Ce³⁺:SrAlF₅ and Ce³⁺,Yb³⁺:SrAlF₅ single crystals together with spectroscopic and kinetic characteristics of several optically nonequivalent impurity centers and energy transfer between them are described. It is shown that co-activation by Yb³⁺ ions effectively suppresses color centers in Ce,Yb:SAF crystals. It was found out that in Ce,Yb:SAF crystals Yb ions exist simultaneously in 2+ and 3+ valent state. Three types of optically nonequivalent luminescent centers corresponding to the doublets in luminescence spectrum centered at 290, 305 and 370 nm (Ce^I, Ce^II, Ce^III, respectively) have been observed. Analysis of luminescence spectra and decays leads to the conclusion that there is no energy transfer between either cerium centers or from Ce³⁺ to Yb²⁺ apart from the Ce^III center which luminescence is slightly quenched by Yb²⁺.     

EPR of Ce<Superscript>3+</Superscript> ions in mixed yttrium-lutecium orthoaluminates

The results of EPR studies of Ce³⁺ ions incorporated into single crystals of mixed yttrium-lutecium orthoaluminates Y_1?xLu_xAlO₃ (YLuAP, x=0.1, 0.3) are reported. In compositionally disordered YLuAP compounds, in comparison to YAlO₃, new paramagnetic Ce³⁺ centers are found. These centers are caused by the changes in symmetry and in the crystal field magnitude due to the isomorphic substitution of Y³⁺ ions by Lu³⁺ in the yttrium sublattice of orthoaluminates. It is shown that the formation of 27 different types of centers is possible in YLuAP with variation of the Lu content. The probabilities of formation of new paramagnetic centers are calculated.     

Wide-band EPR spectroscopy of YAlO3: Tm3+ single crystals

The YAlO₃: Tm³⁺ single crystal has been studied on a wide-band EPR spectrometer. The EPR spectra of Tm³⁺ ions in the frequency range of 90–160 GHz have been detected for the first time. It has been confirmed that thulium ions substitute the position of Y³⁺ in the crystal lattice. The detected spectra have been described with the use of a spin Hamiltonian with the effective spin S = 1/2. A comparative analysis of the orientation of the magnetic axes of the Tm³⁺ paramagnetic center with earlier data on other rare-earth ions has been performed.     

Magnetic susceptibility study of Ce in PbCeA (A=Te,Se, S)

The magnetic susceptibility of Pb_1-xCe_xA (A=S, Se and Te) crystals with Ce³⁺ concentrations 0.006≤x≤0.036 was investigated in the temperature range from 2 K to 300 K. The magnetic susceptibility data was found to be consistent with a ²F_5/2 lowest manifold for Ce³⁺ ions with a crystal-field splitting Δ=E(Γ₈)−E(Γ₇) of about 340 K, 440 K and 540 K for Pb_1-xCe_xTe, Pb_1-xCe_xSe, and Pb_1-xCe_xS, respectively. For all the three compounds the doublet Γ₇ lies below the Γ₈ quadruplet which confirms the substitution of Pb²⁺ by Ce³⁺ ions in the host crystals. The observed values for the crystal-field splitting are in good agreement with the calculated ones based on the point-charge model. Moreover, the effective Landé factors were determined by X-band (∼9.5 GHz), electron paramagnetic measurements (EPR) to be g=1.333, 1.364, and 1.402 for Ce ions in PbA, A = S, Se and Te, respectively. The small difference with the predicted Landé factor g of 10/7 for the Γ₇ (J=5/2) ground state was attributed to crystal-field admixture.     

铈掺杂氧化铝薄膜的蓝紫色发光特性

应用中频反应磁控溅射技术制备了Al₂O₃:Ce³⁺的非晶薄膜.X射线光电子谱(XPS)检测显示薄膜中有Ce³⁺生成.这些薄膜的光致发光峰是在374nm附近,它来自于Ce³⁺离子的5d¹激发态向基态4f¹的两个劈裂能级的跃迁.发光强度强烈地依赖于薄膜的掺杂浓度,但发光峰位置不随掺杂浓度而变化.Ce³⁺含量和薄膜的化学成分是通过X射线散 关键词： 光致发光 2O₃')" href="#">Al₂O₃ 薄膜 稀土元素     

Family of paramagnetic centers of Ce3+ ions in yttrium aluminum garnet

The electron paramagnetic resonance (EPR) spectra of Ce³⁺ ions in single crystals of yttrium aluminum garnet have been investigated. It has been found that, in addition to the usually observed EPR signals of Ce³⁺ ions located in the regular environment at dodecahedral sites of the crystal lattice, the spectra contain a group of less intense anisotropic lines with g-factors close to the corresponding parameters of Ce³⁺ ions in the regular environment. It has been concluded that the observed satellite lines belong to the family of Ce³⁺ ions in the immediate vicinity of which there are permutation defects that lead to a change in the strength and symmetry of the crystal field in the vicinity of the paramagnetic center.     

Energy band structure and Frenkel excitons in PbGa2S4

Optical reflection spectra are measured and calculated in PbGa₂S₄ crystals in the region of resonances related to excitons with large oscillator strength and binding energy (Frenkel excitons). The splitting of the upper valence band in the center of the Brillouin zone due to crystal field (Δ_cf) and spin orbit (Δ_so) interaction are determined. Optical reflection spectra are measured and calculated according to Kramers-Kronig relations in the region of 3-6 eV in Е⊥с and Е∥с polarizations, and the optical constants n, k, ε₁ and ε₂ are determined. The observed electronic transitions in PbGa₂S₄ crystals are discussed in the frame of theoretical energy band structure calculation for thiogallate crystals.     

High-Frequency EPR Spectroscopy of Tb3+ Ions in Synthetic Forsterite

Paramagnetic centers formed by the impurity Tb³⁺ ions in synthetic forsterite Mg₂SiO₄ have been studied by high-frequency tunable electron paramagnetic resonance spectroscopy in the frequency range of 150–300 GHz. These centers represent single Tb³⁺ ions and dimer associates of the Tb³⁺ ions. It has been found that the integral intensity of resonance transitions belonging to the dimer centers is much higher than that to be expected for the statistical distribution of the impurity Tb ions in the forsterite host. Therefore, there is a mechanism favoring the self-organization of the Tb ions in dimer associates during the crystal growth. The parameters of the effective spin Hamiltonian describing the dependence of electron-nuclear sublevels on the magnetic field have been determined for all observed paramagnetic centers and the possible structures of the centers have been discussed.     

Luminescence characteristics of Pb centres in undoped and Ce-doped Lu3Al5O12 single-crystalline films and Pb→Ce energy transfer processes

At 4.2-350 K, the steady-state and time-resolved emission and excitation spectra and luminescence decay kinetics were studied under excitation in the 2.5-15 eV energy range for the undoped and Ce³⁺-doped Lu₃Al₅O₁₂ (LuAG) single-crystalline films grown by liquid phase epitaxy method from the PbO-based flux. The spectral bands arising from the single Pb²⁺-based centres were identified. The processes of energy transfer from the host lattice to Pb²⁺ and Ce³⁺ ions and from Pb²⁺ to Ce³⁺ ions were investigated. Competition between Pb²⁺ and Ce³⁺ ions in the processes of energy transfer from the LuAG crystal lattice was evidenced especially in the exciton absorption region. Due to overlap of the 3.61 eV emission band of Pb²⁺ centres with the 3.6 eV absorption band of Ce³⁺ centres, an effective nonradiative energy transfer from Pb²⁺ ions to Ce³⁺ ions takes place, resulting in the appearance of slower component in the luminescence decay kinetics of Ce³⁺ centres and decrease of the Ce³⁺-related luminescence intensity.     

Energy transfer mechanisms in the KCaLa1−x−yCexTby(PO4)2 phases

The various mechanisms involved in the green emission of KCaLa_1?x?yCe_xTb_y(PO₄)₂ under UV excitation are analyzed for a weak terbium concentration (y = 0.05). Ce³⁺ → Tb³⁺ transfer can be described by the Dexter model, but only for a weak cerium concentration. For higher cerium contents the cerium lifetime temperature dependence can be fitted by using a model involving energy migration between Ce³⁺ ions before Ce³⁺ → Tb³⁺ transfer. The investigation of the variation of the terbium emission vs temperature involves the presence of energy-trapping defects in the material.