Molecular dynamics studies of layered fluorite superionic conductors

A computer simulation by a molecular dynamics method at constant volume has been performed to a model material which is composed of accumulating two different fluorite conductors: ···BaF₂-CaF₂-BaF₂-CaF₂···. CaF₂ region is compressed and BaF₂ region is stretched along the c-axis (z-axis). It is obtained that the diffusion coefficient and ionic conductivity of F ions in the layered fluorite conductors increases with decreasing periods, namely with the number of interfaces. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Slow components of the emission decay in fluoride crystals doped with Ce3+

Spatially separated defects created by photons with energies 6–8 eV in alkali-earth fluoride crystals doped with cerium are investigated with the help of thermoluminescence. Measuring the spectra of creation of V_k and H peaks of thermostimulated luminescence inBaF ₂:Ce³⁺. we demonstrate that photons with energies higher than 6eV induce H centers (self-trapped holes captured by interstitialF ions), whereas the formation of self-trapped holes begins on exposure to photons with energies greater than 7 eV. The influence of photoionization on theCe ³⁺ luminescence inBaF ₂, SrF₂, CaF₂, andCeF ₃ crystals is investigated in the range of photon energies 4–8 eV. An exponentialCe ³⁺-emisson decay was observed for excitation energy lying in the range 4–6 eV. Slow and fast decay components were observed under excitation by photons with energies higher than 6 eV. We believe that the slow and fast components are due to the tunnel recombination of trapped electrons with hole centers. A. P. Vinogradov Institute of Geochemistry of the Siberian Branch of the Russian Academy of Sciences. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 43–49, March, 2000.     

Time-resolved spectroscopy of self-trapped excitons in fluorides of alkaline-earth metals under pulsed electron irradiation

Nanosecond-resolution absorption spectroscopy at room temperature was used to study the laws governing the creation and evolution of the primary defect structure in CaF₂, SrF₂, and BaF₂ crystals exposed to an accelerated electron pulse. It is shown that the spectral-kinetic characteristics of self-trapped excitons created in undamaged parts of the crystal lattice are qualitatively similar. Partial polarization of the absorption of self-trapped excitons is observed in CaF₂. The structure of the transient absorption spectra becomes more complex in the sequence CaF₂, SrF₂, BaF₂ because of the formation of excitons trapped in phase inclusions of homologous cationic impurities. The spectral characteristics of excitons trapped in undamaged parts of the CaF₂ and SrF₂ lattice and in their phase inclusions in BaF₂ are the same although the latter have a considerably shorter relaxation time. Short-lived (τ⩽100 ns) absorption of unknown defects was observed in the spectral range ⩾5 eV. Fiz. Tverd. Tela (St. Petersburg) 40, 1228–1234 (July 1998)     

Physical properties of multicomponent fluoride glasses for photonic and superionic applications

Heavy metal fluoride glasses are promising materials for ultra-low loss mid-infrared optical fibers. The fibers are applied in remote spectroscopy, laser surgery, and thermal imaging. Upon doping with rare earth ions, heavy metal fluoride fibers are suitable for a development of high power laser materials, up-conversion lasers, and optical amplifiers for telecommunications systems. As heavy metal fluorides are prospective fast fluoride ion conductors, fluoride glasses based on ZrF₄, BaF₂, LaF₃, AlF₃ and NaF (ZBLAN), PbF₂, InF₃, BaF₂, AlF₃, LaF₃ (PIBAL) or ZnF₂, BaF₂, InF₃, SrF₂, AlF₃, NaF (ZBISAN) are interesting for a development of glassy or fibrous ionic conductors. In this paper, the ionic conductivity and dielectric response of the abovementioned multicomponent fluoride glasses is studied. The influence of the glass composition on the glass transition temperature (T_g) and on the crystallization temperature (T_cr) is also reported. The optimum composition and drawing temperature for fluoride glass fibers is specified. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Study of Nd2+ absorption in x-irradiated CaF2, SrF2, BaF2 crystals

The absorption spectra of x-irradiated alkaline-earth fluoride (CaF₂, SrF₂, BaF₂) crystals doped with Nd³⁺ ions have been investigated. X-irradiation results in creating the absorption bands of inter-configuration 4fⁿ–4fⁿ⁻¹–5 d¹ transitions of Nd²⁺. The charge reduction of the neodymium by irradiation is not temperature-stable and the ions reoxidation (Nd²⁺ → Nd³⁺) occurs under heating to 570 K in CaF₂, 520 K in SrF₂ and 470 K in BaF₂.     

First-principles calculations of the electronic structure of fluorite-type crystals (CaF2, BaF2, SrF2, and PbF2) containing Frenkel defects. Analysis of optical and transport properties

The electronic structure of the alkali-earth fluorides CaF₂, BaF₂, SrF₂, and PbF₂ with Frenkel defects is investigated in the tight-binding approximation by the LMTO method. The defect formation and migration energies are calculated. The electronic structure and optical excitations of a H center in a defective fluorite structure are examined. It is shown on the basis of calculations of the binding energies that CaF₂, BaF₂, and SrF₂ are ionic compounds, while the chemical bond in PbF₂ is partially covalent. Possible methods of displacement of interstitial fluorine atoms that lead to the observed optical spectra of an H center are investigated. Fiz. Tverd. Tela (St. Petersburg) 40, 2019–2025 (November 1998)     

Sol–gel template synthesis of luminescent glass–ceramic rods

We report an original way to prepare luminescent glass–ceramic microrods containing Eu³⁺ doped BaF₂ nanocrystals by sol–gel chemistry within the pores of a polycarbonate template membrane. Structural characterization by scanning electron microscopy and X-ray diffraction has shown the formation of glass–ceramic microrods with 0.8-m diameter of and 10 μm length in which BaF₂ nanocrystals of about 30 nm size are embedded. Photoluminescence measurements have indicated the incorporation of Eu³⁺ ions inside the BaF₂ nanocrystals in a broad range of sites with low coordination symmetry. The comparison made with the bulk glass–ceramic indicated an influence of the dimensional constraints imposed by the membrane pores during xerogel formation and subsequent glass ceramization.     

Formation of H<Subscript><Emphasis Type="Italic">a</Emphasis></Subscript><Superscript>-</Superscript> hydrogen centers upon additive coloration of alkaline-earth fluoride crystals

The mechanism of coloration of alkaline-earth fluoride crystals CaF₂, SrF₂, and BaF₂ in calcium vapors in an autoclave with a cold zone is studied. It was found that the pressure in the autoclave upon constant evacuation by a vacuum pump within the temperature range of 500–800°C increases due to evaporation of metal calcium. In addition to the optical-absorption bands of color centers in the additively colored undoped crystals or to the bands of divalent ions in the crystals doped with rare-earth Sm, Yb, and Tm elements, there appear intense bands in the vacuum ultraviolet region at 7.7, 7.0, and 6.025 eV in CaF₂, SrF₂, and BaF₂, respectively. These bands belong to the H_a ^- hydrogen centers. The formation of hydrogen centers is also confirmed by the appearance of the EPR signal of interstitial hydrogen atoms after X-ray irradiation of the additively colored crystals. Grinding of the outer edges of the colored crystals leads to a decrease in the hydrogen absorption-band intensity with depth to complete disappearance. The rate of hydrogen penetration inside the crystal is lower than the corresponding rate of color centers (anion vacancies) by a factor of tens. The visible color density of the outer regions of the hydrogen-containing crystals is several times lower than that of the inner region due to the competition between the color centers and hydrogen centers.     

Colloidal synthesis of BaF2 nanoparticles and their application as fillers in polymer nanocomposites

Nanoparticles of pure and Eu-doped BaF₂ have been prepared through sol-gel colloidal synthesis. In addition, BaF₂-filled PMMA polymer nanocomposites were fabricated and dielectric properties were measured. The as-synthesized pure and Eu-doped BaF₂ nanoparticles were analyzed by both X-ray diffraction and transmission electron microscopy and consisted of crystalline BaF₂ particles with an average diameter of 13.6 nm with a standard deviation of about ±2.4 nm. The photoluminescence properties of the pure and Eu-doped (2%, 4% and 8%) nanoparticles showed characteristic emission of Eu³⁺ (⁵D₀→⁷F _J (J=1–4) transitions). We also measured significantly enhanced dielectric breakdown strength of up to 30% for BaF₂ nanocomposites over the unfilled PMMA polymer. This study thus offers some promise of sol-gel synthesis of nanocomposite dielectrics with great potential for use as electrical insulation materials in cryogenic high-voltage applications.     

Study of crystals in medium-and long-wavelength IR ranges by surface-electromagnetic-wave spectroscopy

First observation of excitation of surface electromagnetic waves (SEW) is reported in the reststrahlen region in for biaxial crystal KTiOPO₄ (KTP) using a tunable CO₂ laser around 10 μm, and for CaF₂, BaF₂, MgO (cubic crystals), and LiNbO₃ (uniaxial crystal) in the far IR using ith a free-electron laser. The parameters of SEW propagation in these crystals have been obtained by the interference method of SEW phase spectroscopy, and the possibility of determining the complex dielectric permittivity of crystals from the SEW propagation parameters demonstrated in the range of SEW existence. Fiz. Tverd. Tela (St. Petersburg) 40, 237–241 (February 1998)     

New scintillators based on barium fluoride crystals and ceramics

Experimental studies on the optical properties of new crystals and ceramics based on CeF₃- and CdF₂-doped barium fluoride were aimed at producing scintillators with a higher light yield level (particularly in the ultra-short wavelength range with a luminescence time of 0.6–0.8 ns) that could be used in the development of fast and low-cost optical sensors for positron emission tomography (PET). Ceramics manufactured on the basis of BaF₂ single crystals with various concentrations of Ce and Cd are transparent in the 300–600 nm wavelength range; this is comparable to BaF₂ single crystals.     

5d-4f luminescence of Nd3+, Gd3+, Er3+, Tm3+, and Ho3+ ions in crystals of alkaline earth fluorides

The vacuum ultraviolet emission spectra of alkaline-earth fluoride (CaF₂, SrF₂, BaF₂) crystals with rare earth impurity ions (Nd, Gd, Er, Tm, Ho) have been investigated. The main luminescence bands are described well by the transitions from the lowest excited 5d state to different 4f levels of rare earth ions.     

Effect of group velocity dispersion on supercontinuum generation and filamentation in transparent solids

We experimentally investigate the spectral extent and spectral profile of the supercontinuum (SC) generated in transparent solids: barium fluoride, calcium fluoride, and fused silica upon irradiation by intense femtosecond-long pulses of 800, 1,380, and 2,200 nm light. These wavelengths correspond to the normal and anomalous group velocity dispersion (GVD) regimes in fused silica calcium fluoride and barium fluoride. We observe an isolated (anti-Stokes) wing on the blue side most prominently in fused silica but also in CaF₂. The SC conversion efficiency is measured for the long wavelengths used in our experiments. We also present results on filamentation in BaF₂ in the anomalous GVD regime, including visualization of focusing–refocusing events within the crystal; the size of a single filament is also determined. The 15-photon absorption cross section in BaF₂ is deduced to be 6.5 × 10^?190 cm³⁰ W^?15 s^?1.     

Transmission spectra of epitaxial layers of Pb1 ? xEuxTe (0 ≤ x ≤ 0.37) solid solutions in the frequency range 7–4000 cm?1

The spectra of epitaxial Pb_{1 − x} Eu _x Te (0 ≤ x ≤ 0.37) solid solution layers grown on BaF₂ and Si substrates have been investigated over a wide frequency range 7–4000 cm⁻¹ at temperatures of 5–300 K. Apart from the phonon and impurity absorption lines, the absorption in a local mode in PbEuTe layers of substrates and buffer layers has been observed in the frequency range 110–114 cm⁻¹. As the temperature decreases from 300 to 5 K, the transverse phonon mode softens from 33.0 to 19.5 cm⁻¹.     

Formation of Eu<Superscript>2+</Superscript> and Eu<Superscript>3+</Superscript> centers in synthesis of CaF<Subscript>2</Subscript>:Eu luminophores

We have studied the effect of CaF₂:Eu luminophore synthesis methods on the charge state of europium. We have shown that Eu³⁺ predominates over Eu²⁺ in samples obtained by coprecipitation of europium with calcium fluoride, and the ratio Eu³⁺/Eu²⁺ grows as the total amount of europium increases. Partial charge conversion of the europium occurs during calcination of the samples, due to changes in the excess fluorine balance. We studied the luminescence, magnetic susceptibility, and EPR of the synthesized samples. We have shown that in a solid solution, europium forms large ordered clusters, determining both the luminescent and the magnetic properties of the material. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 773–779, November–December, 2007.     

Ion-molecular interactions in the methylsulfonic acid—methanol system according to the IR spectral data

The methylsulfonic acid (MSA)—methanol (MeOH) liquid binary system was studied over the whole concentration range by the MBTIR IR spectroscopy method at 30°C. Quasi-ion pairs with the 1: 1 composition formed by a strong symmetrical H-bond were only present in solutions with an equimolar acid: base ratio. The addition of methanol caused the solvation of quasi-ion pairs by MeOH molecules, and, in the presence of the base in a substantial excess (C _MeOH⁰: C _MSA⁰ > 2), proton disolvates (Me(H)O⋯H⋯O(H)Me)⁺ with strong symmetrical H-bonds were formed; that is, there was B⋯H⋯A + B ↔ (B⋯H⋯B)⁺ + A⁻ equilibrium, where B is the base molecule and HA is the acid. In the presence of excess acid, methanol was protonated, and negatively charged proton disolvates were formed, B⋯H⋯A + HA ↔ BH⁺ + (AHA)⁻. This equilibrium was fully shifted to the right.     

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.     

Visualization of focusing–refocusing cycles during filamentation in BaF<Subscript>2</Subscript>

Filamentation occurs within a 1.5 cm-long crystal of BaF₂ during the propagation of intense, ultrashort (40 fs) pulses of 800 nm light; a systematic study as a function of incident power enables us to extract quantitative information on laser intensity within the condensed medium, the electron density and the six-photon absorption cross section. At low incident power, a single filament is formed within the crystal; two or more filaments are observed along the direction transverse to laser propagation at higher incident powers. Further, due to fluorescence from six-photon absorption (6PA), we are able to map the intensity variation in the focusing–refocusing cycles along the direction of laser propagation. At still higher incident powers, we observe splitting of multiple filaments. By measuring the radius (L _min) of single filament inside BaF₂, we obtain estimates of peak intensities (I _max) and electron densities (ρ _max) to be 3.26×10¹³ W cm⁻² and 2.81×10¹⁹ cm⁻³, respectively. Use of these values enables us to deduce that the 6PA cross-section in BaF₂ is 0.33×10⁻⁷⁰ cm¹² W⁻⁶ s⁻¹.     

Ionic conductivity of epitactic MBE-grown BaF2 films

We studied parallel conductivities of pure BaF₂ films with thicknesses ranging from 35 to 300 nm, epitaxially grown on Al₂O₃(0 1 2) substrates by molecular beam epitaxy technique. The overall conductivities of the films are found to increase with decreasing thickness. The detailed investigation of the overall conductance as a function of the thickness permits the deconvolution of bulk and boundary effects, the latter being attributed to distinct space charge effects in the interface between BaF₂ film and Al₂O₃ substrate. The (extrinsic) Debye length (λ) is estimated to be about 8 nm at T=593 K, which corresponds to an impurity content of 10¹⁸/cm³ (singly ionized dopant assumed). This is consistent with the fact that we observed a constant boundary contribution for all investigated films (film thickness >4λ). It is also consistent with the Debye length observed in a previous report on CaF₂/BaF₂ heterolayers fabricated by the same technique, in which the low temperature enhancement was also attributed to space charges in BaF₂ [Nature 408 (2000) 946]. Only at low temperatures (below 370 °C), the conductance seems to be influenced by strain effect.     

Electronic and electronic-vibrational phenomena in the new organic conductor ϰ-(ET)2[Hg(SCN)2Cl] with a metal-insulator transition

The reflection spectra and optical conductivity spectra of the new organic conductor ϰ-(ET)₂[Hg(SCN)₂Cl] with a metal-insulator transition in the spectral regions 700–5500 and 9000–40 000 cm⁻¹ have been studied in polarized light at 300 K. A comparisonis made between the spectra obtained and the corresponding spectra of related isostructural conductors based on the ET molecule, and also the properties of the crystal structure of the investigated compounds. An electronic transition between the ET molecules of the dimer (ET) ₂ ⁺ in the spectral region 700–5500 cm⁻¹ has been identified, as have the features of the electronic-vibrational structure arising as a consequence of the interaction of this transition with the completely symmetric intramolecular vibrations of the ET molecule. It is found that the conductor with the stronger dimer interaction between the ET molecules has the higher the transition temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1313–1319 (August 1997)