Electron paramagnetic resonance of Ce3+ ions in lead thiogallate single crystals

The results of electron paramagnetic resonance (EPR) studies of Ce³⁺ impurity ions in single crystals of lead thiogallate PbGa₂S₄ have been reported. The Ce³⁺ ions substitute for Pb²⁺ ions in the crystal lattice of PbGa₂S₄. A number of paramagnetic cerium centers in lead thiogallate have been observed. The spectra are described by the spin Hamiltonian of rhombic symmetry with the effective spin S = 1/2. The g factors of the main cerium centers have been determined. A large number of paramagnetic centers are due to both nonequivalent positions of lead and local charge compensation under the substitution Ce³⁺ ?? Pb²⁺.     

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⁺.     

New sonochemiluminescence involving solvated electron in Ce(III)/Ce(IV) solutions

The moving single-bubble sonoluminescence of Ce³⁺ in water and ethylene glycol solutions of CeCl₃ and (NH₄)₂Ce(NO₃)₆ was studied. As found, a significant part of intensity of the luminescence (100% with cerium concentration less than 10^–4 M) is due to the sonochemiluminescence. A key reaction of sonochemiluminescence is the Ce⁴⁺ reduction by a solvated (or hydrated in water) electron: Ce⁴⁺ + e_s (e_aq) → *Ce³⁺. Solvated electrons are formed in a solution via electrons ejection from a low-temperature plasma periodically generated in deformable moving bubble at acoustic vibrations. Reactions of heterolytic dissociation of solvents make up the source of electrons in the plasma. In aqueous CeCl₃ solutions, the Ce⁴⁺ ion is formed at the oxidation of Ce³⁺ by OH radical. The latter species originates from homolytic dissociation of water in the plasma of the bubble, also penetrating from the moving bubble into the solution. The sonochemiluminescence in cerium trichloride solutions are quenched by the Br⁻ (acceptor of OH) and H⁺ ions (acceptor of e_aq). In water and ethylene glycol solutions of (NH₄)₂Ce(NO₃)₆, the sonochemiluminescence also quenched by the H⁺ ion. The sonochemiluminescence in CeCl₃ solutions is registered at [Ce³⁺] ≥ 10^–5 M. Then the sonochemiluminescence intensity increases with the cerium ion concentration and reaches the saturation plateau at 10^–2 M. It was shown that sonophotoluminescence (re-emission of light of bubble plasma emitters by cerium ions) also contributes to the luminescence of Ce³⁺ in solutions with [Ce³⁺] ≥ 10^–4 M. If the cerium concentration is more than 10^–2 M, a third source contributes to luminescence, viz., the collisional excitation of Ce³⁺ ions penetrating into the moving bubble.     

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.     

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.     

Luminescence and electronic excitations in Li<Subscript>6</Subscript>Gd(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>: Ce<Superscript>3+</Superscript> crystals

This paper reports on a study of the luminescence emitted by Li₆Gd(BO₃)₃: Ce³⁺ crystals under selective photoexcitation to lower excited states of the host ion Gd³⁺ and impurity ion Ce³⁺ within the 100–500-K temperature interval, where the mechanisms of migration and relaxation of electronic excitation energy have been shown to undergo noticeable changes. The monotonic 10–15-fold increase in intensity of the luminescence band at 3.97 eV has been explained within a model describing two competing processes, namely, migration of electronic excitation energy over chains of Gd³⁺ ions and vibrational energy relaxation between the ⁶ I _j and ⁶ P _j levels. It has been shown that radiative transitions in Ce³⁺ ions from the lower excited state 5d ¹ to ² F _5/2 and ² F _7/2 levels of the ground state produce two photoluminescence bands, at 2.08 and 2.38 eV (Ce1 center) and 2.88 and 3.13 eV (Ce2 center). Possible models of the Ce1 and Ce2 luminescence centers have been discussed.     

Optical absorption and electron spin resonance of Co2+ in cubic,hexagonal and 4H polytype zinc sulfide

Electron spin resonance and optical absorption measurements are reported for Co²⁺ in structurally pure single crystals of cubic, hexagonal, and 4H polytype ZnS. Co²⁺ spectra corresponding to the four different cation sites expected for these structures were observed, i.e. a cubic center from zinc blende, an axial center from wurtzite, and two different axial centers from the 4H polytype host. The energy of the optical ⁴A₂-⁴T₂ transition and the spin Hamiltonian parameters show characteristic differences for these four centers, which are discussed.     

Ionization of helium-like ions with excitation of nl states by high-energy photon scattering

The kinetic and spectral characteristics of the complex dielectric constant of a Ce: YAG crystal under laser irradiation in 250–275 nm spectral range are investigated. The lifetimes of free charge carriers and charge carriers, localized at the lattice defects (color centers), are estimated. It was established that photoconductivity signal of the sample is essentially caused by one-photon ionization processes from the ² F _5/2 ground state of Ce³⁺ ions.     

High-frequency tunable EPR spectroscopy of Cr3+ in synthetic forsterite

The electron paramagnetic resonance spectra of isolated and dimer impurity centers of trivalent chromium ions in the octahedral Ml sites in synthetic forsterite are studied in the frequency range of 65–90 GHz. The measurements are performed at 4.2 K in magnetic field from ?0.04 to 0.3 T. The zero-field splitting between spin doublets of the isolated Cr³⁺ ion Δ_s = 66.7 GHz and between spin sublevels of the Cr³⁺-Cr³⁺ dimer Δ_d1 = 71.5 GHz and Δ_d2 = 73.0 GHz is measured directly at zero field. The analysis of the spin Hamiltonian parameters shows that the dimer center consists of a pair of Cr³⁺ ions with an Mg²⁺ vacancy between them replacing three Mg²⁺ ions situated in a quasi-one-dimensional chain aligned parallel to the crystal c-axis. It is found that the exchange interaction in the dimer is ferromagnetic with parameters J_z = 0.47 GHz and J_t = 0.79 GHz.     

Theoretical studies of absorption spectra and microstructure of Ni2+ at the octahedral site of the NiFe2O4 nanoparticle

The optical absorption spectra, microstructure and electronic spin resonance parameters (electronic spin resonance (ESR) g factor) for Ni²⁺ ions at octahedral centers of nickel ferrite nanoparticles are calculated from the two-spin–orbit-parameter model. The effect of spin–orbital coupling of the central metal 3d⁸ ions and ligand oxygen ions has been taken into account in the full energy matrix and ESR g formula. The calculated results are in good agreement with the observed values. In addition, the microstructures of Ni²⁺ ions at octahedral centers in NiFe₂O₄ are reasonably determined from the calculations.     

EPR of Yb3+ ions in Ba1−xLaxF2+x mixed crystals

Electron paramagnetic resonance (EPR) spectra of impurity Yb³⁺ ions (about 0.1 at.%) in mixed crystals BaF₂(1-x) plus LaF₃(x) have been investigated for different values of the concentrationx at a frequency of about 9.5 GHz by both continuous-wave (CW) EPR and electron spin echo methods. A spectrum of trigonal symmetry with a complex hyperfine structure is observed in “pure” BaF₂:Yb³⁺ (x=0). Upon admixture of small amounts of LaF₃ (x=0.001), additional EPR lines arise with intensities increasing with the increase ofx up to 0.005. These lines are attributed to trigonal centers including two rare-earth ions and two compensating fluorine ions. A further increase ofx results in a decrease of the total EPR spectrum intensity, and atx≥0.05 the CW resonance becomes practically unobservable. This may be due to the formation of rare-earth ion clusters with paramagnetic Yb³⁺ ions occurring in domains with a disordered structure of surroundings resulting in very broad EPR lines, which cannot be registered by CW EPR. Indeed, very broad (not less than 1 KG) EPR lines were observed by the electron spin echo method for concentrationsx<-0.02.     

Silica gel glasses with a high efficiency of luminescence sensitization in the Ce<Superscript>3+</Superscript>-Tb<Superscript>3+</Superscript> system

Terbium-and (Ce, Tb)-containing glasses prepared using the direct sol-gel-glass transition are studied. It is shown that glasses doped with one activator contain two main types of optical centers, namely, isolated and complex centers, which are characterized by weak and strong cross-relaxation quenching of luminescence from the ⁵D₃ state of Tb³⁺ ions, respectively. The Ce⁴⁺-Tb³⁺ (Tb⁴⁺) complex centers are formed during sintering of coactivated xerogels in oxygen and can be transformed into Ce³⁺-Tb³⁺ centers through saturation of the samples with hydrogen. The Ce³⁺-Tb³⁺ centers exhibit efficient luminescence from the ⁵D₄ state upon excitation into the absorption bands of Ce³⁺ ions.     

Growth and the luminescence properties of a lutetium gadolinium garnet doped with Ce3+ and Pr3+ ions

Crystals of lutetium gadolinium garnet solid solutions (Lu_{1 − x} Gd _x )Al₅O₁₂ (0 ≤ x ≤ 0.6) doped with Ce³⁺ and Pr³⁺ ions have been prepared by the horizontal directional crystallization method, and their optical and luminescence properties have been investigated. It has been established that the introduction of gadolinium into the lutetium garnet lattice leads to a decrease in the antisite luminescence (Lu_Al centers) in the UV spectral range and to sensitization of the Ce³⁺ ion luminescence. By contrast, the presence of gadolinium results in the quenching of the Pr³⁺ luminescence due to the nonradiative excitation transfer from Pr³⁺ ions to Gd³⁺ ions.     

Electron paramagnetic resonance in mixed crystals (BaF<Subscript>2</Subscript>)<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>(LaF<Subscript>3</Subscript>)<Subscript>x</Subscript> activated by Ce<Superscript>3+</Superscript> ions

The electron paramagnetic resonance (EPR) spectra of mixed crystals (BaF₂)_{1?x? y}(LaF₃)_x(CeF₃)_y (y = 0.001 = 0.1%, x = 0–0.02) are investigated in a magnetic field H‖C₄ at a frequency of 9.5 GHz. The angular dependence of the EPR spectrum is measured for the sample with x = 0.02. The lines attributed to Ce³⁺ impurity centers with tetragonal symmetry and g factors (g_‖ = 0.75, g_⊥ = 2.4) close to those measured for the KY₃F₁₀: Ce³⁺ compound are separated in the complex EPR spectrum. The assumption is made that the aforementioned impurity centers are cubooctahedral clusters of the La₆F₃₇ type in which one of the La³⁺ ions is replaced by the Ce³⁺ ion.     

Determination of the Position of the Impurity Yb3+ ion in the CsCaF3 crystals

CsCaF₃ crystals doped with Yb³⁺ ions have been studied using the electron paramagnetic resonance and optical spectroscopy methods. Several types of paramagnetic Yb³⁺ centers were found, among which a paramagnetic center in the unusual position was established. The parameters of the corresponding spin Hamiltonians and schemes of the energy levels of the observed centers were determined.     

Elektronenspin-Resonanz und Photochemie des U2-Zentrums in Alkalihalogenid-Kristallen

The photochemical reactions involved in the production and in the bleaching of U₂ centers (interstitial hydrogen atoms) in KCl, KBr and NaCl crystals are investigated by measuring the optical absorption spectra of the crystals at low temperatures. The U₂ centers are prepared by UV irradiation of hydroxide- and hydride-doped crystals. The electron spin resonance of KCl, KBr and NaCl crystals with U₂ centers at low temperatures reveals a well-resolved hyperfine splitting due to interactions of the hydrogen atom with four neighbouring halogen ions. The U₂ center can be described as a tetrahedal [HX₄]^4?-molecule ion, in which one hole, bound mainly at the hydrogen atom and partially at the surrounding halogen ions, gives rise to the spin resonance.     

Irregular Ceand defect-related luminescence in YAlO3 single crystal

Using the methods of time-resolved and steady-state luminescence spectroscopies, the luminescence and defects creation processes were studied at 4.2-300 K under excitation in the 3.0-10.5 eV energy range for an YAlO₃:Ce crystal with very low concentration of Ce³⁺ ions. The results were compared with those obtained at the study of YAlO₃:Ce crystals with large Ce³⁺ content coming from the same technological laboratory. Three irregular Ce³⁺ centers were found and two intrinsic defect luminescence centers related to the cation and oxygen vacancies were evidenced. The origin and structure of luminescence centers are discussed.     

Luminescence properties of solid solutions of borates doped with rare-earth ions

The structural and luminescence properties of Lu _x Y_{1 ? x} BO₃ solid solutions doped with Ce³⁺ or Eu⁺³ have been investigated. It has been found that the solid solutions crystallize in the vaterite phase with a lutetium concentration x < 0.5. For a higher lutetium concentration x, the solid solutions contain an additional calcite phase with a content less than 5 wt %. The luminescence spectra are characterized by intensive impurity emission under excitation with the synchrotron radiation in the X-ray and ultraviolet spectral ranges. It has been shown that, as the lutetium concentration x in the Lu _x Y_{1 ? x} BO₃: Ce³⁺ solid solutions increases, the emission intensity smoothly decreases, which is associated with a gradual shift of the Ce³⁺ 5d(1) level toward the bottom of the conduction band, as well as with a decrease in the band gap. It has been established that, in the Lu _x Y_{1 ? x} BO₃: Eu³⁺ solid solutions with intermediate concentrations x, the efficiency of energy transfer to luminescence centers increases. This effect is explained by the limited spatial separation of electrons and holes in the solid solutions. It has been demonstrated that the calcite phase adversely affects the luminescence properties of the solid solutions.     

Crystal structure and photoluminescence of (Y1−xCex)2Si3O3N4

Oxonitridosilicate phosphors with compositions of (Y_1−xCe_x)₂Si₃O₃N₄ (x=0−0.2) have been synthesized by solid state reaction method. The structures and photoluminescence properties have been investigated. Ce³⁺ ions have substituted for Y³⁺ ions in the lattice. The emission and excitation spectra of these phosphors show the characteristic photoluminescence spectra of Ce³⁺ ions. Based on the analyses of the diffuse reflection spectra and the PL spectra, a systematic energy diagram of Ce³⁺ ion in the forbidden band of sample with x=0.02 is given. The best doping Ce content in these phosphors is ∼2 mol%. The quenching temperature is ∼405 K for the 2 mol% Ce content sample. The luminescence decay properties were investigated. The primary studies indicate that these phosphors are potential candidates for application in three-phosphor-converted white LEDs.     

EPR investigation of the trivalent chromium complexes in SrTiO3

The trivalent chromium centers were investigated by means of electron paramagnetic resonance (EPR) in SrTiO₃ single crystals grown using the Verneuil technique. It was shown that the charge compensation of the Cr³⁺-V_O dominant centers in octahedral environment is due to the remote oxygen vacancy located on the axial axis of the center. In order to provide insight into spin-phonon relaxation processes the studies of axial distortion of Cr³⁺-V_O centers have been performed as function of temperature. The analysis of the trigonal Cr³⁺ centers found in SrTiO₃ indicates the presence of the nearest-neighbor strontium vacancy. The next-nearest-neighbor exchange-coupled pairs of Cr³⁺ in SrTiO₃ has been analyzed from the angular variation of the total electron spin of S=2 resonance lines.