Energy levels of rare-earth ions in Gd<Subscript>2</Subscript>O<Subscript>2</Subscript>S

The energies of the ground 4f ⁿ levels of tri- and divalent rare-earth ions with respect to the conduction and valence bands of Gd₂O₂S crystal has been determined. It is shown that the Pr³⁺, Tb³⁺, and Eu³⁺ ions can be luminescence centers in Gd₂O₂S. The levels of the Nd³⁺, Dy³⁺, Er³⁺, Tm³⁺, Sm³⁺, and Ho³⁺ ions lie in the valence band; therefore, these ions cannot play the role of activators. The ground 4f level of the Ce³⁺ ion is near the midgap, due to which Ce³⁺ effectively captures holes from the valence band and electrons from the conduction band and significantly decreases the afterglow level of the Gd₂O₂S:Pr and Gd₂O₂S:Tb phosphors.     

Spectral-kinetic characteristics of crystals and nanoceramics based on BaF<Subscript>2</Subscript> and BaF<Subscript>2</Subscript>: Ce

Optical characteristics of BaF₂ and BaF₂: Ce single crystals and nanoceramic materials prepared from these single crystals by uniaxial hot pressing have been studied. It has been shown that the introduction of Ce₃₊ ions into BaF₂ hardly affects the ultrafast (∼0.9 ns) luminescence component. The integrated luminescence intensity of the BaF₂: Ce nanoceramics is higher than that of the corresponding single crystal and considerably higher that the intensity of the undoped BaF₂ crystal. It has been demonstrated that the slow (several hundred nanoseconds) component of the luminescence decay of BaF₂: Ce is due to the energy transfer from excitons to Ce³⁺ ions.     

Optical properties of CdF<Subscript>2</Subscript> in a wide energy range

For either of the two reflection spectra of cadmium difluoride that are known from experiments, a complete set of the fundamental optical functions is calculated in the energy range 4–45 eV with the Kramers-Kronig relationships. The basic features of the optical spectra are established, and a hypothesis for their origin is suggested based on the known theoretical results for the band structure.     

Defect entropies and enthalpies in BaF<Subscript>2</Subscript>

Various experimental techniques have revealed that the predominant intrinsic point defects in BaF₂ are anion Frenkel defects. Their formation, enthalpy and entropy, as well as the corresponding parameters for the fluorine vacancy and fluorine interstitial motion have been determined. In addition, low temperature dielectric relaxation measurements in BaF₂doped with uranium leads to the parameters τ₀, E in the Arrhenius relation τ = τ₀ exp(E/k _B T) for the relaxation time τ. For the relaxation peak associated with a single tetravalent uranium, the migration entropy deduced from the pre-exponential factor τ₀ is smaller than the anion Frenkel defect formation entropy by almost two orders of magnitude. We show that, despite their great variation, the defect entropies and enthalpies are interconnected through a model based on anharmonic properties of the bulk material which have been recently studied by employing density-functional theory and density-functional perturbation theory.     

Divalent rare-earth ions in LaF<Subscript>3</Subscript> crystals

The optical spectra and electric conductivity of LaF₃ crystals doped with 0.01, 0.1, and 0.3 mol % YbF₃, where Yb was partly or completely recharged to the divalent state, are studied. The long-wavelength absorption band of 370 nm is caused by electrons transitioning from state 4f ¹⁴ to the level of anion vacancies. The remaining bands at 300–190 nm are caused by 4f ¹⁴–5d ¹4f ¹³ transitions in Yb²⁺. The bulk electric conductivity and peaks of the dielectric losses of LaF₃–Yb²⁺ crystals are caused by Yb²⁺–anion vacancy dipoles. The activation energy of the reorientation of Yb dipoles is 0.58 eV. The optical and dielectric properties of Yb²⁺ centers are compared to those of Sm²⁺ and Eu²⁺ centers studied earlier in LaF₃ crystals.     

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.     

Luminescence of Eu<Superscript>3+</Superscript> rare-earth ions in Lu<Subscript>2</Subscript>O<Subscript>3</Subscript> nanospheres

The kinetics of luminescence of Eu³⁺ ions in Lu₂O₃:Eu nanospheres with diameters of 100–270 nm and a small standard deviation of the size distribution <15% has been studied. A sharp decrease in the decay time of luminescence of Eu³⁺ ions in the red range with an increase in the diameter of nanospheres has been attributed to the appearance of a photon mode accelerating spontaneous luminescence, which is confirmed by the calculation of ranges of existence of whispering-gallery modes in studied nanospheres.     

Effect of an electron beam on CaF<Subscript>2</Subscript> and BaF<Subscript>2</Subscript> epitaxial layers on Si

Atomically smooth CaF₂ and BaF₂ layers have been sequentially grown on Si(111) substrates by molecular beam epitaxy. Pore macrodefects have been revealed at the points of the action of an electron beam from a diffractometer when analyzing the crystal structure of the surface during the growth with the subsequent observation using atomic force microscopy. The formation of these macrodefects is associated with the decomposition of fluorides by high-energy electrons, which is accompanied by the desorption of fluorine and the drift current of positive ions from the electron charge drains.     

Spin-dimerization in rare-earth substituted La<Subscript>2</Subscript>RuO<Subscript>5</Subscript>

The Ru-Ru spin-singlet formation in La_2 ? x L n _x RuO₅ (Ln = Pr, Nd, Sm, Gd, Dy) was investigated by measurements of the specific heat and magnetic susceptibility. After subtraction of the lattice contribution from the specific heat (C _p ), similar excess entropy values were obtained for all compounds. These entropies can be explained by the formation of antiferromagnetic Ru-spin dimers at low temperatures and provide a lower estimate for the intradimer exchange strength. Pronounced changes in the transition temperatures and a broadening of the corresponding peak in C _p were observed. These changes depend on the rare-earth element and are due to local structural changes and heterogeneities caused by the substitution. The magnetic susceptibilities can be described by the sum of a rare-earth paramagnetic moment and the susceptibility of the unsubstituted La₂RuO₅. Density functional theory (DFT) calculations were performed for various compounds to investigate the origin of the magnetic transition and the relationship between structural changes and the spin-dimerization temperature. The combination of the present results with previous structural investigations supports the model of a spin-pairing of the Ru moments which occurs as a reason of the structural phase transition in La_2 ? x L n _x RuO₅.     

Microwave measurements of electrical conductivity of CdF<Subscript>2</Subscript> semiconductor crystals

The electrical conductivity of CdF₂ semiconductor crystals is measured using the microwave intracavity technique at a frequency of ～35 GHz. The crystals are activated with yttrium donor impurities and indium and gallium ions forming bistable one-electron donor impurity and two-electron DX centers. The conclusion is drawn that the concentration of electrons in the conduction band of CdF₂: Ga crystals has an anomalously high value. This confirms the results obtained in earlier NMR investigations of CdF₂ semiconductor crystals at room temperature.     

Comparative spectroscopic and laser properties of Yb<Superscript>3+</Superscript>-doped CaF<Subscript>2</Subscript>, SrF<Subscript>2</Subscript> and BaF<Subscript>2</Subscript> single crystals

We present the spectroscopic properties and room-temperature cw tunable laser operation of Yb³⁺-doped CaF₂, SrF₂ and BaF₂ single crystals grown and studied in the same conditions. Emission cross sections, lifetimes, laser thresholds, laser slope efficiencies and laser wavelength tuning ranges are compared. It appears that Yb³⁺-doped BaF₂ might be more promising for diode-pumped high power laser operation. PACS 42.55.Rz; 42.70.Hj     

Spectroscopic Properties and Energy Transfer Analysis of Tm<Superscript>3+</Superscript>-Doped BaF<Subscript>2</Subscript>-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript>-La<Subscript>2</Subscript>O<Subscript>3</Subscript> Glass

This paper reports on the spectroscopic properties and energy transfer analysis of Tm³⁺-doped BaF₂-Ga₂O₃-GeO₂-La₂O₃ glasses with different Tm₂O₃ doping concentrations (0.2, 0.5, 2.0, 2.5, 3.0, 3.5, 3.5, 4.0 wt%). Mid-IR fluorescence intensities in the range of 1,300 nm−2,200 nm have been measured when excited under an 808 nm LD for all the samples with the same pump power. Energy level structure and Judd-Ofelt parameters have been calculated based on the absorption spectra of Tm³⁺, cross-relaxation rates and multi-phonon relaxation rates have been estimated with different Tm₂O₃ doping concentrations. The maximum fluorescence intensity at around 1.8 μm has been obtained in Tm₂O₃-3 wt% sample and the maximum value of calculated stimulated emission cross-section of Tm³⁺ in this sample is about 0.48 × 10⁻²⁰ cm² at 1,793 nm, and there is not any crystallization peak in the DSC curve of this sample, which indicate the potential utility of Tm³⁺-doped BaF₂-Ga₂O₃-GeO₂- La₂O₃ glass for 2.0-μm optical fiber laser.     

EPR study of impurity iron ion clusters in BaF<Subscript>2</Subscript> crystals

Tetragonal paramagnetic centers with spin S = 7/2 were detected in x-ray-irradiated BaF₂: Fe (c_Fe ≈ 0.002 at. %) crystals using the EPR method. Electronic transitions between the |±1/2〉 states of a Kramers doublet were observed in the X and Q ranges. In the EPR spectra of the tetragonal centers, a ligand hyperfine structure (LHFS) was observed corresponding to the interaction of the electron magnetic moment of the tetragonal center with eight equivalent ligands. The large spin moment, significant anisotropy of the magnetic properties, and the characteristic LHFS indicate that the tetragonal center is a Fe^1.5+?Fe^1.5+ dimer in which the two iron ions are bound via superexchange interaction. It is assumed that, before crystal irradiation, this dimer was in the Fe³⁺(3d⁵)?Fe⁺(3d⁷) state.     

Backward-wave four-wave mixing and coherent oscillation in CdF<Subscript>2</Subscript>:Ga,Y

Cadmium fluoride doped with Ga and Y is shown to be a suitable medium for backward-wave four-wave mixing with a grating decay time of a few seconds at room temperature. A 3-mm-thick sample ensures amplified phase-conjugate reflectivity and can therefore be used for building a coherent oscillator with a conventional mirror. PACS 42.65.Hw; 42.70.Mp; 42.70.Nq     

Recording dynamic holograms in a semiconductor crystal CdF<Subscript>2</Subscript>:In

The kinetics of decay of a phase hologram in a semiconductor CdF₂ crystal with bistable In centers is studied. Kinetic constants of the hologram decay are found, and the potential relief of the bistable center is plotted. The resolving power of the crystal is evaluated and recording of a transparency is demonstrated.     

Recording of dynamic information holograms in a CdF<Subscript>2</Subscript>:In crystal

It is shown that CdF₂:In crystals can be used to record amplitude-phase information holograms in real time. The diffraction efficiency of these holograms is several percent, but they are characterized by a much higher sensitivity in comparison with phase holograms recorded in the transparency region of the crystal. A model experiment on pattern recognition is performed.     

Relaxation processes upon photoexcitation of semiconductor CdF<Subscript>2</Subscript> by laser pulses

The microwave-cavity-based technique is used to study the processes of photoionization of electrons from donor levels to the conduction band in semiconductor CdF₂ crystals doped with Y, In, or Ga. The samples were excited by periodic pulses of Nd-laser (λ = 1.06 μm, pulse width ～10 ns) in the temperature range 6–77 K. The transient processes were detected in the absorption and dispersion modes related to variation of the imaginary and real parts of the complex permittivity ?₁ ? i?₂ induced by the light pulses. The observed signals consisted of short peak at t ～ 0, approximately 40–70 ns in length, and a long tail with a duration of ～100 ms. The short peak is likely to be related to the stay of the photoexcited carriers in the conduction band, while the long tail is associated with the processes of excitation relaxation after the electrons coming back to the donor levels of the impurity band. The weak temperature dependence of the width of the peak at t ～ 0 is explained by the tunneling mechanism of relaxation of electrons through the energy (or, probably, spatial) barrier separating the bound and free states of the carriers in the semiconductor CdF₂.     

Multi-range high-frequency EPR spectroscopy of LiYF<Subscript>4</Subscript> and LiLuF<Subscript>4</Subscript> crystals doped by rare-earth ions

EPR spectra of isostructural LiYF₄ and LiLuF₄ crystals doped by Dy³⁺, Er³⁺, and Ho³⁺ ions are measured at 4.2 K in the frequency range 40–800 GHz. The effects caused by isotopic disorder in the lithium sublattice, the random crystal field, and the interaction between paramagnetic impurity ions are detected and studied. The results of the measurements are used to determine the spectral characteristics of the compounds and the crystal field parameters. It is demonstrated that the formation of the isotope structure of the EPR signal is dominated by local deformations of the crystal lattice induced by mass defects.     

Nonlinear rotation of the polarization of the intense femtosecond laser radiation in BaF<Subscript>2</Subscript>

The dependence of the polarization plane rotation angle in the BaF₂ crystal on the intensity of the femtosecond laser radiation with 0.62 μm wavelength in the ω = ω + ω ? ω process on cubical nonlinearity χ⁽³⁾ is investigated. An anomalous increase in the efficiency of the cross-polarized radiation generation at I > 2 × 10¹² W cm² is observed for the first time. The 10% efficiency of the orthogonal component generation at the ～3 × 10¹² W cm² intensity is obtained.