A Study of Mechanochemical Doping of Fluoride Crystals with a Fluorite Structure by Er3+ Ions via Electron Paramagnetic Resonance Spectra

Using electron paramagnetic resonance (EPR) spectroscopy, we have shown that, upon mecha- noactivated doping of powders of compounds CaF₂, SrF₂, and BaF₂ with Er³⁺ ions, impurity centers of single erbium ions with cubic symmetry are formed. Investigations of dependences of EPR spectra intensities on the particle size show that the process of mechanochemical doping with Er³⁺ ions proceeds differently for CaF₂, SrF₂, and BaF₂ host matrices. In the case of CaF₂, impurity centers are localized in a very thin near-surface layer of CaF₂ particles, in SrF₂, the impurity is distributed over the volume of particles, while, in BaF₂, there is a layer of a finite thickness for which the probability of doping in the course of mechanosynthesis is very small and the impurity of the rare-earth element is localized in the core of large particles. These data can be explained assuming that the result of mechanosynthesis of particles of fluorides with a fluorite structure doped with Er3+ ions at room temperature is governed by two processes—mechanoactivated diffusion of rare-earth ions into particles and segregation of impurity ions at grain boundaries. In this case, the typical scales for compounds CaF₂, SrF₂, and BaF₂ considerably differ from each other.     

EPR Spectroscopy of Impurity Thulium Ions in Yttrium Orthosilicate Single Crystals

The frequency-field and orientation dependences of the electron paramagnetic resonance (EPR) spectra are measured for impurity Tm³⁺ ions in yttrium orthosilicate (Y₂SiO₅) single crystals by stationary EPR spectroscopy in the frequency range of 50–100 GHz at 4.2 K. The position of the impurity ion in the crystal lattice and its magnetic characteristics are determined. The temperature dependences of the spin–lattice and phase relaxation times are measured by pulse EPR methods in the temperature range of 5–15 K and the high efficiency of the direct single-phonon mechanism of spin–lattice relaxation is established. This greatly shortens the spin–lattice relaxation time at low temperatures and makes impurity Tm³⁺ ions in Y₂SiO₅ a promising basis for the implementation of high-speed quantum memory based on rare-earth ions in dielectric crystals.     

Study of the Defect Structure and Crystal-Field Parameters of α-Al2O3:Yb3+

The methods currently used for studying the defect structure of laser host crystals doped with transition metal or rare-earth ions have several drawbacks or limitations. This study proposes an alternative approach for obtaining optimized impurity structures using molecular dynamics calculation in conjunction with the superposition model. This new approach is specifically applied to a system named α-Al₂O₃:Yb³⁺, in which the simulated defect structure is used to fit the superposition model parameters directly onto the observed energy levels. Such an approach provides predicted values of crystal-field parameters, Zeeman splitting g-factor, and hyperfine structure constants. Moreover, the C_3v site symmetry is found to be a good approximation for the actual C₃ site of Yb³⁺, as doped in an α-Al₂O₃ crystal.     

Investigations of the defect structures and the EPR parameters for the substitutional Mo5+ centers in rutile type crystals

The defect structures and the electron paramagnetic resonance parameters for the substitutional Mo⁵⁺ centers in rutile type SnO₂, TiO₂ and GeO₂ crystals are theoretically investigated from the perturbation formulas of these parameters for a 4d¹ ion in rhombically compressed octahedra. The [MoO₆]^7? clusters suffer the Jahn–Teller effect and transform the ligand octahedra from original elongation on host tetravalent sites to compression in the impurity centers, with additional smaller rhombic (perpendicular) distortions when compared with those in the hosts. The defect structures and the importance of the ligand contributions are discussed.     

Trapping mechanism in the afterglow process of the rare-earth activated Y2O2S phosphors

Phosphorescence properties are investigated in Y₂O₂S phosphors doped with rare-earth (lanthanoid, Ln) ions. Luminescence afterglow with a decay time of several ten milliseconds is observed at room temperature in the phosphors activated by Nd, Sm, Eu, Dy, Ho, Tm, Er, and Yb. The depths (thermal activation energies) of the traps causing the afterglow are measured with the transient luminescence method.It is concluded that the excited electron and the hole in the conduction and valence bands are trapped separately in the states (impurity levels) located in the vicinity of the Ln³⁺ ion. The trapping depths of the level range from 0.3 to 1.1 eV and are dependent on the electron affinity of the Ln³⁺ ion estimated from the energy difference between the 4fⁿ⁺¹ and the 4fⁿ configurations in the 4f shell of the ion.     

Specific heat of Ce x La1 − x B6 in the low cerium concentration limit (x ≤ 0.03)

The specific heat of high-quality Ce _x La_{1 ? x} B₆ (x = 0, 0.01, 0.03) single crystals is studied in the temperature range 0.4–300 K. LaB₆ samples with various boron isotope compositions (¹⁰B, ¹¹B, ^nat B) are analyzed to estimate the effect of boron vacancies. The experimental data are used to take into account the electron component correctly under the renormalization of the density of states at T < 8 K, the contribution of the quasi-local vibrational mode of a rare-earth ion with the Einstein temperature Θ_E ≈ 152 K, the Debye contribution from the rigid cage of boron atoms with the Debye temperature Θ_D ≈ 1160 K, and the low-temperature Schottky contribution related to the presence of 1.5?2.3% boron vacancies in the rare-earth hexaborides. The detected low-temperature anomalies in the specific heat are shown to be interpreted in terms of the formation of two-level systems with an energy ΔE = 92–98 K caused by the displacement of rare-earth ions from their centrosymmetric positions. A scenario of heavy fermion formation that is alternative to the Kondo mechanism is proposed for the systems with a magnetic impurity.     

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.     

Electron paramagnetic resonance and luminescence of chromium in calcium germanate crystals

The luminescence of Ca₂GeO₄: Cr⁴⁺ single crystals at wavelengths in the range of 1.3 μm upon excitation with a 1-μ m semiconductor laser is investigated in the temperature range up to 573 K. At T<110 K, the Ca₂GeO₄: Cr⁴⁺ crystals are characterized by the electron paramagnetic resonance, which is attributed to the Cr⁴⁺ ions substituted for Ge⁴⁺ ions. The components of the g tensor and its principal axes are determined. It is revealed that the Cr⁴⁺ impurity centers in calcium germanate affect the crystal symmetry to a lesser degree compared to Cr⁴⁺ ions in forsterite. The observed deviation of the temperature dependence of the electron paramagnetic resonance from the Curie law is explained by the transition to the excited state with a low activation energy, as is the case in impurity 3d ions in diamond-like semiconductors. The inference is made that the giant effective degeneracy multiplicity of the excited state is associated with the initiation of soft phonon modes in the crystal upon excitation of the defect.     

Optically induced gate voltage spectroscopy in a GaAs/AlGaAs heterostructure

We report on measurements of optically induced gate voltage spectroscopy in a GaAs/AlGaAs heterostructure with a high mobility 2-dimensional electron gas (2DEG) in a thin (55 nm) GaAs layer. The optically induced gate voltage between the front gate and the 2DEG is sensitive to excess electron concentrations below 10⁷ cm⁻². In the gate voltage spectrum we observe a peak below the bandgap energy of GaAs, which is not observed in the photocurrent, luminescence or excitation spectra. Due to the extremely high sensitivity of this technique we attribute this below bandgap signal to very weak absorption lines below the GaAs bandgap energy by impurity bands or defect absorption. The fall-off of the below bandgap signal varies as exp (hω/E₀), where E₀ is an indicative for the quality of the heterostructure.     

On the magnetic hyperfine interaction in Ga2Se3:EuSe defect crystals

The electron structure impurity nuclei ¹⁵¹Eu of Ga₂Se₃ defect compounds have been investigated by electron spin resonance and Mössbauer spectroscopy at temperatures between 77 and 300 K. Mössbauer spectra in samples were recorded at MS 700 M set up with Sm₂O₃ as the sources and isomer shift values were determined relative to EuF₃. The microscopic properties of Ga₂Se₃:EuSe single crystals defect compounds have been studied by atomic absorption analysis and X-ray fluorescence analysis at room temperature. The temperature dependence of the magnetic hyperfine fields was also analyzed by using the spin-wave theory and the molecular-field model. We determined the Debye temperature Θ_D and the charge states for ¹⁵¹Eu which turned out to be Eu²⁺(f⁷) ion with spin 7/2.     

Effect of Ag substitution on the electromagnetic property and microwave absorption of LaMnO3

La_1−xAg_xMnO₃ perovskites with different doping Ag-content were prepared by the sol–gel method. The electromagnetic characteristics and microwave loss behavior of these ion-doped rare-earth manganites were studied in the 2–18 GHz frequency range. The microstructure and morphology of the samples were characterized by X-ray diffraction (XRD), and scanning electron microscopy (SEM) techniques. The complex permittivity spectra, the complex permeability spectra and microwave reflection loss were measured by a microwave vector network analyzer system. The XRD patterns show that the crystalline perovskite main phase ABO₃ is formed and impurity phases disappear when calcined at 1100 °C, and Ag metal as an impurity phase appears when excessive Ag⁺ is doped. The SEM image indicates that many of the La_0.85Ag_0.15MnO₃ particles are fiber-like or ellipsoidal. Magnetic loss and dielectric loss coexist and cooperate in microwave attenuation by moderate substitution of Ag⁺ for La³⁺. The microwave absorption property of the La_0.85Ag_0.15MnO₃ sample is enhanced with the bandwidth below −10 dB at about 6 GHz and the peak value of reflection loss is near −25.0 dB at the layer thickness of 2 mm.     

Rabi Oscillations of Paramagnetic Ions in Solids: Role of Electrostatic Interactions

We study the decay of Rabi oscillations of magnetically coupled impurity ions diluted in the solid. Electrostatic interactions between the ions treated as charged defects shift their g-factors and result in valuable correlations of their Larmor frequencies if the ions are close enough. We find an increase in the decay time of Rabi oscillations in comparison with the case of uncharged defects. The magnitude of the effect depends on the ratio between the impurity and the total defect concentrations, as well as on the type of the electron paramagnetic resonance line broadening mechanism (by random electric fields, electric field gradients, etc.). We present results in the arbitrary order of multipole expansion with respect to valence electron coordinates of the paramagnetic ion. Corresponding corrections to the decay times of Rabi oscillations of Nd³⁺ ions in CaWO₄ crystal are obtained.     

EPR and spin-lattice relaxation of rare-earth ions in LiLuF4 monocrystals

The EPR and spin-lattice relaxation are studied of impurity rare-earth ions in LiLuF₄ crystals at liquid-helium temperatures. It is detected that paramagnetic relaxation of Er³⁺ ions is retarded by the effect of the phonon throat. The effect of resonance attenuation of the phonon throat is clarified in two-phonon resonance relaxation processes of Er³⁺ ions. The Debye temperature of the crystal is determined from an analysis of experimental results.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 24–27, February, 1988.     

A theoretical study of alkaline-earth cations in crystalline sodium chloride,potassium chloride and potassium bromide

Theoretical methods, based on Mott-Littleton techniques are used to investigate the defect structures of alkali-halide crystals doped with divalent ions. The systems studied are those having Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ as impurity ions in NaCl, KCl and KBr crystals. Our calculations find comparable stability of the (110) nearest-neighbour and (200) next-nearest-neighbour complexes whereas the (211) complex is found to be less stable. Significant trends in the variation of binding energy with dopant ion radius are predicted. We also consider the activation energies for the w₁, w₂, w₃ and w₄ type jumps which occur in the vicinity of the impurity ion. The results are, where possible, compared with experimentally determined defect energies and their implications in diffusion processes of M²⁺ impurities in the alkali halides are discussed.     

Photoluminescence of bulk Eu-doped GaN crystals

A study of the variation of photoluminescence spectra of bulk Eu-doped GaN samples revealed that the dopant can reside in the crystal in various charge states depending on the total defect concentration in the starting semiconductor host matrix. In crystals with the lowest concentration of shallow-level defects, the ion can exist only in one charge state, Eu³⁺. At higher concentrations of such defects, Eu can be observed in two charge states, Eu²⁺ and Eu³⁺. A rare-earth impurity was found to act as a getter of defects in the starting GaN matrix.     

HT-6M托卡马克等离子体紫外-可见谱

利用光学多道分析仪(OMA)拍摄了HT-6M托卡马克等离子体近紫外可见谱.系统分析了杂质行为,给出了主要杂质碳和氧的朝内的通量,在简化模型下计算了碳氧的化学溅射率,并由此得出碳氧杂质产生机制和可能的循环途径.结果表明,氧杂质在循环途径中起关键性的作用,控制氧杂质尤其重要.     

First-principles calculations of the amplitudes of the electron transition from a ligand to the 5d shell of Yb3+: KZnF3

The expressions describing the amplitudes of a transition of an electron from a ligand to vacant shells of the central ion of an impurity center are derived. The amplitudes of a transition of an electron from a ligand to the 5d shell of a rare-earth ion are calculated from first principles. The calculations are performed in the basis set of orbitals taken in the form of 5s, 5p, 4f, 5d, and 6s electron shells of the central ion and 2s and 2p electron shells of the ligands. No expansion in terms of overlap integrals is employed in the calculations. The matrix elements of the (I + S)^?1 matrix are determined in the chosen basis set of orbitals. The amplitudes thus calculated are in good agreement with those obtained by fitting of the experimental data.     

Deep impurity-center ionization by far-infrared radiation

An analysis is made of the ionization of deep impurity centers by high-intensity far-infrared and submillimeter-wavelength radiation, with photon energies tens of times lower than the impurity ionization energy. Within a broad range of intensities and wavelengths, terahertz electric fields of the exciting radiation act as a dc field. Under these conditions, deep-center ionization can be described as multiphonon-assisted tunneling, in which carrier emission is accompanied by defect tunneling in configuration space and electron tunneling in the electric field. The field dependence of the ionization probability permits one to determine the defect tunneling times and the character of the defect adiabatic potentials. The ionization probability deviates from the field dependence e(E) ∝ exp(E ²/E _c ² ) (where E is the wave field, and E _c is a characteristic field) corresponding to multiphonon-assisted tunneling ionization in relatively low fields, where the defects are ionized through the Poole-Frenkel effect, and in very strong fields, where the ionization is produced by direct tunneling without thermal activation. The effects resulting from the high radiation frequency are considered and it is shown that, at low temperatures, they become dominant. Fiz. Tverd. Tela (St. Petersburg) 39, 1905–1932 (November 1997)     

Mössbauer studies of interstitial intermetallics

After an introduction to interstitial incorporation of 2p elements in iron-based alloys, the main physical effects of these interstitials on the intrinsic properties of rare-earth intermetallics are outlined. Then follows a survey of the results obtained using the⁵⁷Fe and several rare-earth resonances for rare-earth intermetallics with the Th₂Zn₁₇, Th₂Ni₁₇, ThMn₁₂ and BaCd₁₁ structures in which nitrogen or carbon has been interstitially incorporated. The results of Mössbauer studies in this area are discussed, and future prospects are assessed.     

Point defect parameters for β-PbF2 from a computer analysis of measurements of ionic conductivity

The conductivity of four crystals of β-PbF₂ has been measured. The results for three of these crystals, one doped with La³⁺ and two doped with Na ⁺ impurity, have been analysed with a non-linear least squares programme to yield the thermodynamic parameters of defect formation and migration below the superionic transition. These parameters are compared with previous values and are used to provide estimates of the defect concentrations in the superionic phase. This work suggests that the superionic phase is not massively disordered and that β-PbF₂ is not significantly different from other fluorites.