Ionic conductivity of calcium and strontium fluorides
Ionic conductivity of single crystals of calcium and strontium fluorides
IONIC CONDUCTION↗
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Frequency non-degenerate sequential excitation of the impurity trapped exciton in strontium fluoride crystals doped with ytterbium
We model the dynamic behaviour observed for impurity-trapped excitons in SrF{sub 2}:Yb{sup 2+} using transient photoluminescence enhancement induced via a two-frequency, sequential excitation process employing an UV optical parametric amplifier synchronized to an IR free electron laser (FEL). We observe sharp transitions interpreted as a change of state of the localized hole and broad bands interpreted as a change of state of the delocalized electron. Our modeling indicates that the 4f crystal-field interaction is 25% smaller than in CaF{sub 2}. The photoluminescence enhancement transients are analyzed across a range of excitation frequencies using a system of rate equations. The temporal behavior is explained in terms of intra-excitonic relaxation, local lattice heating by the FEL, and liberation of electrons from trap states.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
A functional SrF 2 coated separator enabling a robust and dendrite-free solid electrolyte interphase on a lithium metal anode
An unstable solid electrolyte interphase (SEI) and accompanying Li metal dendrites are the key impediments to commercialization of high-energy lithium metal batteries (LMBs). We employ a strontium fluoride (SrF 2 ) microsphere coated polypropylene (PP) separator to stabilize the SEI and to prevent dendrites from growing. This approach is tested with Li∥Cu half-cells, Li∥Li symmetrical cells, and Li∥NMC full LMBs, there being a major improvement in each case. The Li∥Cu cell with SrF 2 maintains a stable coulombic efficiency (CE) of 80% after 100 cycles, when tested at 0.25 mA cm -2 to a capacity of 0.5 mA h cm -2 . By comparison, the uncoated PP reference has a CE of 10% in cycle 60. The Li∥Li cell with SrF 2 exhibits a markedly smaller voltage polarization and is able to stably cycle for approximately 340 h vs. the reference which begins to display severe voltage instability at 200 h. The Li∥NMC full LMB with SrF 2 shows an initial discharge capacity of 173 mA h g -1 , with 167 mA h g -1 (96.5%) being retained after 200 cycles at 200 mA g -1 (1C rate). The SrF 2 containing LMB also has a substantially improved rate capability over the reference, the difference being drastic even at the highest testing rate of 20C. First-principles calculations based on DFT indicate that lithium ions prefer to adsorb onto the SrF 2 surface, which should create a more uniform ion flux and reduce the propensity for dendrite nucleation. Finally in parallel, the SrF 2 spheres bind with the SEI layer, creating a tough in situ formed composite membrane that mechanically stabilizes a planar metal interface.
25 ENERGY STORAGE↗
Defect Structures of La{sub 1–y}Sr{sub y}F{sub 3–y}, La{sub 1–y}Ba{sub y}F{sub 3–y}, and Nd{sub 1–y}Ca{sub y}F{sub 3–y} (y = 0.05, 0.10) Nonstoichiometric Tysonite Phases
Characteristic features of defect structures of La{sub 1–y}Sr{sub y}F{sub 3–y}, La{sub 1–y}Ba{sub y}F{sub 3–y}, and Nd{sub 1–y}Ca{sub y}F{sub 3–y} (y = 0.05, 0.10) nonstoichiometric phases of different compositions are determined from X-ray diffraction data. Interest in subtle details of their structure is determined by the possibility of ion transport over fluorine vacancies and by a strong compositional dependence of the ionic conductivity. The La{sub 0.95}Sr{sub 0.05}F{sub 2.95}, La{sub 0.95}Ba{sub 0.05}F{sub 2.95}, and Nd{sub 0.95}Ca{sub 0.05}F{sub 2.95} phases, as well as the La{sub 0.9}Ba{sub 0.1}F{sub 2.9} phase, crystallize as β-LaF{sub 3} (sp. gr. P3̅c1, Z = 6). The La{sub 0.9}Sr{sub 0.1}F{sub 2.9} and Nd{sub 0.9}Ca{sub 0.1}F{sub 2.9} phases lose their superstructure and are described by a cell whose volume is three times smaller (sp. gr. P6{sub 3}/mmc, Z = 2). Defects of crystal structure R{sub 1–y}M{sub y}F{sub 3–y} are not exhausted by vacancies in fluorine positions. All crystals with a “large” cell are twinned according to the merohedral twin law. The majority of atomic positions in models with a “small” cell are split by group symmetry elements and are occupied statistically.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Defect structure and ionic conductivity of as-grown R{sub 1–y}Sr{sub y}F{sub 3–y} (R = Ce, Pr, or Nd) crystals with high SrF{sub 2} content
The structure of defect nonstoichiometric phases of Ce{sub 0.88}Sr{sub 0.12}F{sub 2.88}, Pr{sub 0.85}Sr{sub 0.15}F{sub 2.85}, and Nd0.85Sr0.15F2.85 single crystals has been investigated by X-ray diffraction at room temperature. Crystals R{sub 1–y}Sr{sub y}F{sub 3–y} (R = Ce, Pr, or Nd) belong to the tysonite structural type (LaF{sub 3}), which has two forms (α and β). The morphotropic transition from the trigonal β form of the crystals to the hexagonal α form is confirmed, which was previously found for the first time when analyzing the nonstoichiometric phase of La{sub 1–y}Sr{sub y}F{sub 3–y} with a SrF2 content above 10 mol % (y ≥ 0.1). Temperature dependences of fluorine-ion conductivity are obtained. It is established that the conductivity of the α form of Ce{sub 0.88}Sr{sub 0.12}F{sub 2.88} and R{sub 0.85}Sr{sub 0.15}F{sub 2.85} crystals (R = Pr or Nd) is lower than that for the β form of R{sub 0.95}Sr{sub 0.05}F{sub 2.95} (R = La–Nd) by 1–2 orders of magnitude. The sublattice of fluorine atoms in the α-form crystals is characterized by an elevated (in comparison with the β form) content of vacancies and more uniform structural and dynamic properties, which leads to a decrease in the mean diffusion mobility of fluorine ions and an increase in the ion-transport activation enthalpy.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Selective laser spectroscopy of SrF{sub 2} crystal doped with Pr{sup 3+} ions
SrF{sub 2} crystals doped with Pr{sup 3+} ions with concentrations corresponding to 0.5, 1.0 and 2.0 wt % of PrF{sub 3} are studied by selective laser excitation. The absorption and luminescence spectra of Pr{sub 3} ions are measured at a temperature of 77 K. Three types of tetragonal centres (C, E, S) with the point symmetry group C{sub 4v} and three types of cluster centres (K{sub 1}, K{sub 2}, K{sub 3}) are found. Energy level diagrams of the {sup 3}H{sub 4}, {sup 3}P{sub 1} and {sup 3}P{sub 2} terms of Pr{sup 3+} ions in SrF{sub 2} crystals are plotted for the tetragonal (C) and cluster optical centres. The lifetimes of the tetragonal C centre [τ(300 K) ∼ 112 μs, τ(77 K) ∼108 μs] and cluster centres K{sub 1} (∼43 μs), K{sub 2} (∼7 μs) and K{sub 3} (∼48 μs) are measured at 77 K for the first time. (laser spectroscopy)
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Metal-to-metal charge transfer between dopant and host ions: Photoconductivity of Yb-doped CaF{sub 2} and SrF{sub 2} crystals
Dopant-to-host electron transfer is calculated using ab initio wavefunction-based embedded cluster methods for Yb/Ca pairs in CaF{sub 2} and Yb/Sr pairs in SrF{sub 2} crystals to investigate the mechanism of photoconductivity. The results show that, in these crystals, dopant-to-host electron transfer is a two-photon process mediated by the 4f{sup N−1}5d excited states of Y b{sup 2+}: these are reached by the first photon excitation; then, they absorb the second photon, which provokes the Y b{sup 2+} + Ca{sup 2+} (Sr{sup 2+}) → Y b{sup 3+} + Ca{sup +} (Sr{sup +}) electron phototransfer. This mechanism applies to all the observed Y b{sup 2+} 4f–5d absorption bands with the exception of the first one: Electron transfer cannot occur at the first band wavelengths in CaF{sub 2}:Y b{sup 2+} because the Y b{sup 3+}–Ca{sup +} states are not reached by the two-photon absorption. In contrast, Yb-to-host electron transfer is possible in SrF{sub 2}:Y b{sup 2+} at the wavelengths of the first 4f–5d absorption band, but the mechanism is different from that described above: first, the two-photon excitation process occurs within the Y b{sup 2+} active center, then, non-radiative Yb-to-Sr electron transfer can occur. All of these features allow to interpret consistently available photoconductivity experiments in these materials, including the modulation of the photoconductivity by the absorption spectrum, the differences in photoconductivity thresholds observed in both hosts, and the peculiar photosensitivity observed in the SrF{sub 2} host, associated with the lowest 4f–5d band.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Neodymium-doped nanoparticles for infrared fluorescence bioimaging: The role of the host
The spectroscopic properties of different infrared-emitting neodymium-doped nanoparticles (LaF{sub 3}:Nd{sup 3+}, SrF{sub 2}:Nd{sup 3+}, NaGdF{sub 4}: Nd{sup 3+}, NaYF{sub 4}: Nd{sup 3+}, KYF{sub 4}: Nd{sup 3+}, GdVO{sub 4}: Nd{sup 3+}, and Nd:YAG) have been systematically analyzed. A comparison of the spectral shapes of both emission and absorption spectra is presented, from which the relevant role played by the host matrix is evidenced. The lack of a “universal” optimum system for infrared bioimaging is discussed, as the specific bioimaging application and the experimental setup for infrared imaging determine the neodymium-doped nanoparticle to be preferentially used in each case.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Role of Mg{sup 2+}, Sr{sup 2+}, and F{sup –} ions in octacalcium phosphate crystallization
We have synthesized octacalcium phosphate (OCP) in the presence of inorganic additives (magnesium, strontium, and fluoride ions) and studied the composition, morphology, thermal stability, and dynamic dissolution of the samples thus obtained. It has been shown that, in addition to OCP, magnesium and strontium ions favor the formation of brushite and hydroxyapatite (HA), whereas fluoride ions favor the formation of HA and fluorohydroxyapatite (FHA). We have proposed a process for the preparation of powder materials whose resorption kinetics in corrosive liquid media are corrected by adding dopants capable of activating the dissolution process.
36 MATERIALS SCIENCE↗
Ceramic planar waveguide structures for amplifiers and lasers
Ceramic and crystalline weakly guiding optical fibres with the core - cladding refractive index difference of 10{sup -2} - 10{sup -4} are fabricated by a hot pressing method. The waveguides with one or several cores for operation in the spectral range 0.2 - 5 {mu}m are produced. The waveguides are based on CaF{sub 2}, SrF{sub 2}, and BaF{sub 2} ceramics and crystals and their solid solutions doped with trivalent Pr, Nd, Tb, Dy, Yb, Ho, Er, and Tm ions, as well as on LiF ceramics and crystals with colour centres. The first results of investigation of the lasing properties of ceramic SrF{sub 2} : NdF waveguides under diode pumping are presented, and the prospects of further investigation are discussed. (lasers)
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Nanostructured Crystals of Fluorite Phases Sr{sub 1–x}R{sub x}F{sub 2+x} and Their Ordering: 12. Influence of Structural Ordering on the Fluorine-Ion Conductivity of Sr{sub 0.667}R{sub 0.333}F{sub 2.333} Alloys (R = Tb or Tm) at Their Annealing
The ionic conductivity of Sr{sub 0.667}R{sub 0.333}F{sub 2.333} alloys (rational Sr{sub 2}RF{sub 7} compositions) in SrF{sub 2}–RF{sub 3} systems (R = Tb or Tm), prepared by spontaneous crystallization, has been investigated for the “as-grown” state and after annealing in CF{sub 4} at 900 ± 20°C for 96 h. As-grown samples of both compositions, prepared by fast (200°C/min) melt crystallization, exhibit partial (nonequilibrium) ordering, which increases from Tb to Tm. Annealing of Sr{sub 0.667}R{sub 0.333}F{sub 2.333} alloys yields strong ordering (equilibrium for the annealing temperatures) of the fluorite structure (CaF{sub 2} type, sp. gr. Fm3̅m, Z = 4) at the formation of t-Sr{sub 2}RF{sub 7} tetragonal compound (sp. gr. I4/m, Z = 30). It is established that ordering of the alloy fluorite structure reduces the fluorine-ion conductivity. After the annealing, the conductivity of Sr{sub 0.667}R{sub 0.333}F{sub 2.333} alloys with the initial (nonequilibrium) ordering stage of t-Sr{sub 2}RF{sub 7} phases with almost complete (equilibrium) ordering decreases by a factor of 3–4.5.
36 MATERIALS SCIENCE↗
Intervalence charge transfer luminescence: Interplay between anomalous and 5d − 4f emissions in Yb-doped fluorite-type crystals
In this paper, we report the existence of intervalence charge transfer (IVCT) luminescence in Yb-doped fluorite-type crystals associated with Yb{sup 2+}–Yb{sup 3+} mixed valence pairs. By means of embedded cluster, wave function theory ab initio calculations, we show that the widely studied, very broad band, anomalous emission of Yb{sup 2+}-doped CaF{sub 2} and SrF{sub 2}, usually associated with impurity-trapped excitons, is, rather, an IVCT luminescence associated with Yb{sup 2+}–Yb{sup 3+} mixed valence pairs. The IVCT luminescence is very efficiently excited by a two-photon upconversion mechanism where each photon provokes the same strong 4f{sup 14}–1A{sub 1g}→ 4f{sup 13}({sup 2}F{sub 7/2})5de{sub g}–1T{sub 1u} absorption in the Yb{sup 2+} part of the pair: the first one, from the pair ground state; the second one, from an excited state of the pair whose Yb{sup 3+} moiety is in the higher 4f{sup 13}({sup 2}F{sub 5/2}) multiplet. The Yb{sup 2+}–Yb{sup 3+} → Yb{sup 3+}–Yb{sup 2+} IVCT emission consists of an Yb{sup 2+} 5de{sub g} → Yb{sup 3+} 4f{sub 7/2} charge transfer accompanied by a 4f{sub 7/2} → 4f{sub 5/2} deexcitation within the Yb{sup 2+} 4f{sup 13} subshell: [{sup 2}F{sub 5/2}5de{sub g},{sup 2}F{sub 7/2}] → [{sup 2}F{sub 7/2},4f{sup 14}]. The IVCT vertical transition leaves the oxidized and reduced moieties of the pair after electron transfer very far from their equilibrium structures; this explains the unexpectedly large band width of the emission band and its low peak energy, because the large reorganization energies are subtracted from the normal emission. The IVCT energy diagrams resulting from the quantum mechanical calculations explain the different luminescent properties of Yb-doped CaF{sub 2}, SrF{sub 2}, BaF{sub 2}, and SrCl{sub 2}: the presence of IVCT luminescence in Yb-doped CaF{sub 2} and SrF{sub 2}; its coexistence with regular 5d-4f emission in SrF{sub 2}; its absence in BaF{sub 2} and SrCl{sub 2}; the quenching of all emissions in BaF{sub 2}; and the presence of additional 5d–4f emissions in SrCl{sub 2} which are absent in SrF{sub 2}. They also allow to interpret and reproduce recent experiments on transient photoluminescence enhancement in Yb{sup 2+}-doped CaF{sub 2} and SrF{sub 2}, the appearance of Yb{sup 2+} 4f–5d absorption bands in the excitation spectra of the IR Yb{sup 3+} emission in partly reduced CaF{sub 2}:Yb{sup 3+} samples, and to identify the broadband observed in the excitation spectrum of the so far called anomalous emission of SrF{sub 2}:Yb{sup 2+} as an IVCT absorption, which corresponds to an Yb{sup 2+} 4f{sub 5/2} → Yb{sup 3+} 4f{sub 7/2} electron transfer.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Preliminary Results of Material Flow Controlled MSR Depletion Calculations
A versatile, parallelizable Python 2.7 library was developed in order to simulate once-through molten salt reactor depletion in a realistic manner via the coupled neutronics/depletion code Serpent 2. Realistic in this sense entails two aspects: reactivity of the core, and oxidation potential of the fuel. The core reactivity should be maintained near zero as with any nuclear reactor. Gross reactivity control is provided by variations of the refuel rate of the reactor. Fine reactivity adjustments are expected to be done with control mechanisms in real-life power operation. The Python library developed allows a user to set bounds on the desired ke f f value. Fuel oxidation potential must be controlled for any liquid fueled reactor. As a simple example, consider this fission where the fuel becomes more oxidizing: UF{sub 4} → SrF{sub 2} + Xe + 2F{sup -} It can be shown using expected fission product oxidation state data that for these reactors, the fuel will become more oxidizing over time as a result of accumulation of excess fluoride ion. Addition of a reducing agent to reactor fuel will be necessary in the operation of molten salt reactors.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Structural changes and self-activated photoluminescence in reductively annealed Sr{sub 3}AlO{sub 4}F
White light emission of self-activated photoluminescence (PL) in Sr{sub 3}AlO{sub 4}F under 254 nm light is only observed after annealing in a reducing atmosphere of 5%H{sub 2}/95%Ar. High-resolution neutron powder diffraction reveals that the FSr{sub 6} octahedrons and AlO{sub 4} tetrahedrons in this anti-perovskite structure are closer packed in reduced than in air-annealed samples which show no PL. Careful analysis of temperature-dependent neutron powder diffraction data establishes smaller isotropic displacement parameters for Sr(1) and O in Sr{sub 3}AlO{sub 4}F annealed in a reducing atmosphere indicating that the denser packing of the polyhedral sub-units leads to a slightly deeper potential for the Sr(1) and O atoms. Both the air- and reductively-annealed samples have identical thermal expansion within the temperature range between 3 and 350 K. The Debye temperatures were calculated using the atomic displacement parameters and show no significant differences between the air and reductively annealed samples making the Debye temperature a bad proxy for self-activated PL. - Graphical abstract: Annealing Sr{sub 3}AlO{sub 4}F under reducing conditions results in an intense self-activated photoluminescence which is correlated with a denser packing of FSr{sub 6} and AlO{sub 4} polyhedra. - Highlights: • Sr{sub 3}AlO{sub 4}F made in air does not show self-activated photoluminescence. • Only when annealing Sr{sub 3}AlO{sub 4}F in a reducing gas is photoluminescence observed. • FSr{sub 6} and AlO{sub 4} polyhedra in reduced Sr{sub 3}AlO{sub 4}F structure are packed more efficient. • Smaller displacement parameters are found for under-bonded Sr(1) and O sites.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A novel blue luminescent material Sr{sub 6}Ca{sub 4}(PO{sub 4}){sub 6}F{sub 2}:Eu{sup 2+}
Graphical abstract: - Highlights: • Novel Eu{sup 2+} doped Sr{sub 6}Ca{sub 4}(PO{sub 4}){sub 6}F{sub 2} phosphors was synthesized for the first time. • The Sr{sub 6}Ca{sub 4}(PO{sub 4}){sub 6}F{sub 2}:Eu{sup 2+} phosphors produced blue light when irradiated at 368 nm. • The emission band of the sample could be decomposed into two Gaussian profiles. - Abstract: For the first time, a series of novel blue light-emitting phosphors Sr{sub 6}Ca{sub 4}(PO{sub 4}){sub 6}F{sub 2}:Eu{sup 2+} were synthesized by a traditional solid-state reaction. The phosphors exhibited a broad and intense excitation band that could be pumped by near ultraviolet to exhibit a broad photoluminescence band ranging from 400 nm to 530 nm peaking at 452 nm. Quenching concentration was 0.05 mol. Furthermore, the mechanism of concentration quenching involving SCPF:Eu{sup 2+} was demonstrated to be a dipole–dipole interaction with critical distance of 27.95 Å. Decay time curves were also measured to validate energy transfer, and quantum efficiency is investigated. The chromaticity diagram of Commission Internationale de l’Eclairage indicated that SCPF:Eu{sup 2+} may be used as a blue-emitting component for white light-emitting diode applications.
36 MATERIALS SCIENCE↗
Photoluminescence properties of Tb-Eu-Mn-codoped fluoroborate glasses under γ-irradiation
We report here an energy transfer from Tb{sup 3+} to Eu{sup 3+}, Mn{sup 2+} and Eu{sup 2+} to Tb{sup 3+} and Mn{sup 2+} for an un-irradiated and γ-irradiated B{sub 2}O{sub 3}-Al{sub 2}O{sub 3}-Na{sub 2}O-SrF{sub 2} glass samples, respectively. The blue emission from Eu{sup 2+} ions as well as green and red emission from Tb{sup 3+}, Eu{sup 3+}, and Mn{sup 2+} ions will contribute to the generation of white light while excited at 339 nm using a xenon lamp. Furthermore, the chromaticity color coordinates, correlated color temperature, and quantum efficiency parameters are calculated for all the glass samples, and their relative variations with respect to γ-irradiation dose are presented.
36 MATERIALS SCIENCE↗
Enhanced Pr{sup 3+} photoluminescence by energy transfer in SrF{sub 2} : Eu{sup 2+}, Pr{sup 3+} phosphor
Efficient energy transfer was demonstrated in the SrF{sub 2} : Eu{sup 2+}, Pr{sup 3+} phosphor synthesized by the co-precipitation method. Results obtained with X-ray diffraction (XRD), scanning electron microscopy (SEM), x-ray spectroscopy (XPS), photoluminescence (PL) and decay curves proposed the UV-Vis energy transfer process. The energy transfer process between the Eu{sup 2+} and Pr{sup 3+} ions in SrF{sub 2} was investigated to evaluate the potential of the Eu{sup 2+} ion as a sensitizer for the Pr{sup 3+} ion. The results proposed that Eu{sup 2+} could be a good sensitizer for absorbing the UV photons and efficiently enhancing the Pr{sup 3+} emission intensity. The energy transfer process was effective until concentration quenching for the Pr{sup 3+} ions occurred. The concentration quenching was attributed to cross-relaxation between the Pr{sup 3+} ions.
36 MATERIALS SCIENCE↗
Epitaxial growth of diluted magnetic semiconductor Ge{sub 1−x}Cr{sub x}Te with high Cr composition
IV–VI diluted magnetic semiconductor Ge{sub 1−x}Cr{sub x}Te layers up to x = 0.1 were grown on SrF{sub 2} substrates by molecular beam epitaxy. In situ reflection high-energy electron diffraction shows a streaky pattern with a sixfold symmetry in the plane for the Ge{sub 1−x}Cr{sub x}Te layer, implying an epitaxial growth of Ge{sub 1−x}Cr{sub x}Te (111)/SrF{sub 2} (111). A clear hysteresis loop is observed in the anomalous Hall effect measurements due to the strong spin-orbit interaction in the host GeTe. The Curie temperature increases with increasing Cr composition up to 200 K, but there is no clear dependence of the Curie temperature on the hole concentration, implying that the mechanism of the ferromagnetic interaction among Cr ions is different from Mn doped diluted magnetic semiconductors.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗