Radiolysis of LaF<Subscript>3</Subscript> crystals with rare-earth impurities

The absorption spectra of LaF₃ crystals, both pure and doped with rare-earth fluorides (YF₃, CeF₃, NdF₃, PrF₃, SmF₃, EuF₃, GdF₃, TbF₃, DyF₃, HoF₃, ErF₃, TmF₃, YbF₃, and LuF₃) have been investigated. All these impurities can be separated into two groups with respect to the shape of the absorption spectra of irradiated crystals. The spectra of the crystals doped with Nd, Sm, Tm, and Yb exhibit, along with 200-nm hole band F₃^-, weak bands due to RE²⁺-anion vacancy centers. The spectra of LaF₃ crystals with Y, Ce, Pr, Gd, Tb, Dy, Ho, Er, and Lu impurities exhibit, along with the hole-center bands (F₃^- at 200 nm and V_kA at 320 nm), bands of comparable intensity, which can be attributed to RE³⁺–F centers. This conclusion is confirmed by preliminary quantum-chemical calculations and the estimation of the levels location in the energy-band diagram.     

Photoinduced toxicity of PrF<Subscript>3</Subscript> and LaF<Subscript>3</Subscript> nanoparticles

PrF₃ and LaF₃ nanoparticles were synthesized by the hydrothermal method. The size distribution of these nanoparticles in the colloidal solution produced was studied by photon correlation spectroscopy. The mean diameter of the nanoparticles was 42 ± 1 nm. During the study of the toxicity of the nanoparticles, the mixture of a colloidal solution of the nanoparticles with cells to be studied was irradiated by 30-mW continuous lasers at wavelengths of 532 and 473 nm. The concentration of salmonella cells in normal saline was 10⁶ cell/mL, while that of nanoparticles was 0.1 g/L. The cell survival percentage was 39, 34, and 20% for the irradiation times of 5, 10, and 15 min, respectively, at an optimal laser radiation power density of 0.4 W/cm at a wavelength of 532 nm. It was ascertained that LaF₃ nanoparticles do not possess the property of photoinduced toxicity and the apoptosing effect. Moreover, the property of photoinduced toxicity is not shared by microparticles, in contrast to nanoparticles.     

Electromagnetically induced transparency on Zeeman sublevels in Nd<Superscript>3+</Superscript>:LaF<Subscript>3</Subscript> crystals

The results of experimental observation of the electromagnetically induced transparency regime on the ⁴ I _9/2-⁴ G _5/2 transition in Nd³⁺ ions doping in LaF₃ are presented. The depth and width of the transparency are analyzed as functions of the control field intensity.     

Stimulated Low-Frequency Raman Scattering in LaF<Subscript>3</Subscript> Suspensions

We observe stimulated low-frequency Raman scattering (SLFRS) caused by laser pulse interaction with acoustic vibrations of nanoparticles in water suspensions of LaF₃ nanoparticles. We show that frequency shifts of the scattering correspond to the eigenfrequencies of nanoparticles vibrations. LaF₃ nanoparticles were synthesized in the presence of glycine by a double jet precipitation technique at various initial concentrations of reagents. We investigate the morphologies and particle sizes as well as size distributions of the particles prepared using transmission electron microscopy (TEM) and dynamical light scattering (DLS). In view of the absorption spectroscopy, we show that the reaction system components and products have no absorption in the visible region, including λ = 694.3 nm. From the luminescence spectroscopy, we find also that they do not emit at λ = 694.3 nm excitation.     

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.     

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.     

Qubits based on spectrally selected groups of Pr<Superscript>3+</Superscript> ions in a LaF<Subscript>3</Subscript> crystal

Spectral selection, i.e., the separation of a group of particles with a spread in resonance frequencies smaller than the hyperfine splitting of working levels has been implemented by the method of burning of long-lived spectral dips in the inhomogeneously broadened absorption line of Pr³⁺ in a LaF₃ crystal. The possibility of implementing qubits (basic elements of quantum computations) on ensembles of spectrally selected particles and the main operations with them, including the manipulation of the populations of hyperfine (qubit) levels and the controlled shift of the absorption line of one spectrally selected group of ions upon excitation of another group (two-qubit operations), has been demonstrated. The decay rates of the population of hyperfine sublevels of the ground state of the spectrally selected group of particles have been measured.     

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.     

Superradiant emission of LaF<Subscript>3</Subscript>:Pr<Superscript>3+</Superscript> in resonator

Experimental data concerning superradiant emission from the LaF₃ medium doped with impurity praseodymium ions are presented in the cases of a free medium and when the medium is placed into an optical resonator. The spike structure of superradiance is registered and studied. When the medium is placed inside a cavity, a new channel of energy removal by superradiance related to the cavity mode appears; the old noncavity channels are preserved. The duration of superradiance in the cavity channel is decreased, and regular modulation arises. These peculiarities of superradiance induced by the presence of an optical resonator are explained.     

Ferroelectric properties of the LaF<Subscript>3</Subscript> superionic conductor nanocluster

We report on the results of quantum-chemical calculation of the lattice energy in a LaF₃ superionic crystal of size 3.5 × 2.0 × 2.2 nm that contains 1200 ions with different structural configurations of fluorine ions. It has been shown that the most energetically disadvantageous configurations of fluorine ions correspond to arbitrarily (randomly) disordered nanolattices in the case when fluorine ions of all three types (F₁, F₂, and F₃) participate in their melting. It has been found that unidirectionally disordered nanolattices that contain a large number of defect dipoles of the anion vacancy–interstitial fluorine atom type with parallel dipole moments is energetically more advantageous than nanolattices with randomly disordered structure. It has been proposed that the electric field produced by a large number of parallel defect dipoles is formed in disordered LaF₃ nanolattices even at room temperatures. This makes it possible to classify microscopically small LaF₃ crystallites as promising functional materials that can be used, e.g., in modern solid-state technologies.     

On the distribution coefficient of Ce<Superscript>3+</Superscript> ions in LiF-LuF<Subscript>3</Subscript>-YF<Subscript>3</Subscript> solid-solution crystals

The optimum ratio of the numbers of the Y³⁺ and Lu³⁺ ions in LiF-LuF₃-YF₃ solid solutions at which the distribution (introduction) coefficient of Ce³⁺ ions is three to five times larger than that in LiYF₄ and LiLuF₄ crystals has been determined by the EPR and optical spectroscopy methods.     

Spectroscopic properties of Er<Superscript>3+</Superscript> ions in LiNbO<Subscript>3</Subscript> crystals codoped with HfO<Subscript>2</Subscript>

The results of the spectroscopic analysis of transition strengths for Er³⁺ ions in a series of Hf:Er:LiNbO₃ crystals with variable Hf content and fixed Er content are reported. Unpolarized UV-VIS-NIR absorption spectra, upconversion fluorescence spectra excited at 800 nm, and microsecond time-resolved spectra excited at 400 nm and 800 nm by 800 nm femtosecond laser were measured at room temperature. The HfO₂ incorporation has influence on Er³⁺ radiative lifetimes, and fluorescence branching ratios. For Hf(4 mol %):Er(1 mol %):LiNbO₃, Ω₂=2.63×10^-20 cm², Ω₄=2.86×10^-20 cm², and Ω₆=0.72×10^-20 cm². Ω₂<Ω₄ is contrary to the Er³⁺ general trend of Ω₂>Ω₄>Ω₆ when the Hf content is below its threshold concentration. In addition, the sum of Ω increases with the Hf content when the HfO₂ content below 6 mol % is unfamiliar. The upconversion mechanism is discussed in this work. PACS 71.20.Eh; 77.84.Dy; 42.62.Fi; 42.65.Ky     

Electron paramagnetic resonance of Mn<Superscript>2+</Superscript> ions in single crystals of yttrium aluminum borate YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Single crystals of yttrium aluminum borate YAl₃(BO₃)₄ doped with manganese ions are studied using electron paramagnetic resonance spectroscopy. It is shown that manganese ions introduced at low concentrations into the sample predominantly occupy yttrium ion sites in the crystal structure. The shape of the electron paramagnetic resonance spectrum unambiguously indicates that the valence of manganese ions in this case is equal to 2+. The parameters of the spin Hamiltonian of Mn²⁺ ions in the YAl₃(BO₃)₄ matrix are determined at room temperature. The magnitude and sign of the fine structure parameter D allow the conclusion that the YAl₃(BO₃)₄ single crystals doped with manganese ions have a strong crystal field at the yttrium ion sites and easy-axis anisotropy.     

VUV luminescence of Er<Superscript>3+</Superscript> ions in LiYF<Subscript>4</Subscript> and BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals

Vacuum ultraviolet luminescence of Er³⁺ ions in LiYF4 and BaY₂F₈ crystals has been investigated. It is revealed that under excitation by 193 nm radiation from an ArF excimer laser the interconfigurational 5d–4f radiative transitions in Er³⁺ ions are observed. It is shown that from the LiYF₄:Er crystal only the spin-forbidden luminescence (λ = 165 nm) is detected, whereas both the spin-forbidden (λ = 169 nm) and spin-allowed (λ = 160.5 nm) components are observed from the BaY₂F₈:Er crystal.     

EPR study of copper ions in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals

The EPR spectra of Cu²⁺ ions (² D _5/2) located at two structurally nonequivalent positions Cu1 and Cu2 in crystals of lithium heptagermanate Li₂Ge₇O₁₅ are recorded. The angular dependences of the EPR spectrum are measured in the paraelectric phase of the Li₂Ge₇O₁₅ compound (T = 300 K). The components of the g factor and the hyperfine interaction tensor A are determined, and the orientation of the magnetic axes with respect to the crystallographic basis is established. The EPR spectra are recorded in the temperature range in the vicinity of the temperature T _C = 283 K of the transition from the paraelectric phase to the ferroelectric phase. The position symmetry of the Cu1 and Cu2 centers is determined at temperatures above and below the phase transition temperature T _C . The localization of paramagnetic centers in the structure is discussed, An analysis of the results obtained demonstrates that the Cu1 and Cu2 centers in the Li₂Ge₇O₁₅ crystal lattice replace lithium ions located at two structurally nonequivalent positions with the symmetries described at temperatures above T _C by the triclinic C _i and monoclinic C ₂ point groups, respectively.     

Low-temperature magnetic behavior of the rare-earth cobaltites GdCoO<Subscript>3</Subscript> and SmCoO<Subscript>3</Subscript>

The temperature and magnetic field dependences of the static magnetization of the polycrystalline rare-earth cobaltites GdCoO₃ and SmCoO₃ have been measured. It is shown that, below room temperature, the magnetization of both compounds derives primarily from the rare-earth ion paramagnetism. The GdCoO₃ and SmCoO₃ compounds have been found to differ substantially in magnetic behavior, which can be traced to differences in their electronic shell structures. The magnetic behavior of GdCoO₃ is close to that of an array of free Gd³⁺ ions, whereas in SmCoO₃ the deviation from the free-ion properties is very large because of the Sm³⁺ ground state being crystal-field split. Van Vleck magnetic susceptibility measurements of SmCoO₃ suggest that the splitting is ～10 K.     

Transient hole-polaron optical absorption in Li<Subscript>6</Subscript>Gd(BO<Subscript>3</Subscript>)<Subscript>3</Subscript> crystals

Results of a study of transient optical absorption (TOA) and luminescence of lithium gadolinium orthoborate Li₆Gd(BO₃)₃ (LGBO) in the visible and UV spectral regions are presented. As revealed by absorption optical spectroscopy with nanosecond time resolution, the LGBO TOA derives from optical transitions in hole centers, with the optical density relaxation kinetics being mediated by interdefect tunneling recombination involving these centers and neutral lithium atoms acting as electronic Li⁰ centers. At 290 K, the Li⁰ centers are involved in thermostimulated migration, which is not accompanied by carrier transfer to the conduction or valence band. The slow components of the TOA decay kinetics, with characteristic times ranging from a few milliseconds to seconds, have been assigned to diffusion-limited annihilation of lithium interstitials with vacancies. The mechanisms responsible for the creation and relaxation of short-lived Frenkel defect pairs in the LGBO cation sublattice have been analyzed.     

Location of the energy levels of the rare-earth ions in BaF<Subscript>2</Subscript> and CdF<Subscript>2</Subscript>

The location of the energy levels of rare-earth (RE) elements in the energy band diagram of BaF₂ and CdF₂ crystals is determined. The role of RE ³⁺ and RE ²⁺ ions in the capture of charge carriers, luminescence, and the formation of radiation defects is evaluated. It is shown that the substantial difference in the luminescence properties of BaF₂: RE and CdF₂: RE is associated with the location of the excited energy levels in the band diagram of the crystals.     

Photoconductivity in LiNbO<Subscript>3</Subscript> crystals codoped with MgO and Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>

Polymer stabilized cholesteric texture cells with various chiral and monomer concentrations were fabricated. Electro-optical measurement indicates that the chiral concentration and the monomer concentration significantly influence the hysteresis, threshold voltage and field-on and field-off response times of the cell. The chiral dopant is found to increase the hysteresis width and to decrease the field-off response time of the cell. The monomer is found to decrease the hysteresis width and to increase the field-off response time of the cell. The field-on response time is independent of the monomer concentration and the chiral concentration of the cell. A thinner cell has a smaller hysteresis width. PACS 61.30.-v; 42.70.Df; 42.79.Kr     

Quadrupole spin-echo envelopes for Bi<Subscript>4</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> single crystals doped with the atoms of transition and rare-earth elements

The influence of a weak (below 50 Oe) constant magnetic field on a quadrupole spin-echo envelope was studied for an undoped single crystal Bi₄Ge₃O₁₂, in which local magnetic fields on the order of 20–30 G were previously found, as well as for single Bi₄Ge₃O₁₂ crystals doped with the atoms of transition and rare-earth elements. In all of these cases, the spin-echo envelopes were strongly influenced. A considerable increase in the nuclear spin-spin relaxation time T ₂ was observed for the undoped sample upon the switching of weak external magnetic fields. For the doped samples, the spin-echo envelope decay became much slower already in the zero field. The external magnetic fields exhibited a markedly weaker influence on the spin-echo envelope for the doped samples. The text was submitted by the authors in English.