Electrical properties and scaling behaviour of Sm<Superscript>3 + </Superscript> doped CaF<Subscript>2</Subscript>-bismuth borate glasses

The electrical properties for 20Bi₂O₃–60B₂O₃ (20−x)–CaF₂–xSm₂O₃ glasses (0 ≤ x ≤ 2) were measured in the temperature range 297 K up to 629 K and in the frequency range 0·1–100 kHz. The d.c. and a.c. conductivity values and the dielectric loss (tan δ) values were found to increase with increasing Sm₂O₃ content, whereas the activation energy of conductivities and the dielectric constant decreased. These results were attributed to the introduction of the rare earth ions; promote the formation of a high number of non-bridging oxygen atoms, which facilitate the mobility of charge carriers. The frequency dependence of the a.c. conductivity follows the power law σ _ac(ω) = Aω ^s . The frequency exponent (s) values (0·64 < s < 0·8) decrease with increasing temperature. This suggested that the a.c. conduction mechanism follows the correlated barrier hopping model (CBH). The dielectric constant (ε ^′) and dielectric loss (tan δ values) were found to increase with increasing temperature and increasing Sm₂O₃ concentration in the glass. The a.c. conductivities as a function of frequency at different temperatures of a given glass superimposed onto a master curve (Roling scaling model). Furthermore, we have performed to scale the data as a function of composition. Two master curves were obtained, which suggested that there are differences in dominant charge carriers between glasses having Sm₂O₃ concentration ≥1 and glass of Sm₂O₃ concentration <1.     

Estimating the effect of C<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> and C<Stack><Subscript>3</Subscript><Superscript>+</Superscript></Stack> radicals and neutral clusters on the fullerene formation

The mass spectrum of the products of arc discharge in helium between graphite electrodes has been studied for various values of the gas flow rate. As the gas flow rate increases, the intensity of C₆₀^±, C₇₀^±, C₈₄^± and C₉₀^± fullerene peaks increases and that of the C₂⁻ and C₃⁺ cluster radicals decreases, but the total decay in radicals amounts to only 21% of the total growth of fullerenes. From this it follows that a contribution to the formation of fullerenes from the neutral clusters (which are taken into account for the first time) significantly exceeds the contribution due to small radical species.     

Structural and electrical properties of Ho<Superscript>3+</Superscript>-modified Pb(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>–9PbTiO<Subscript>3</Subscript> single crystals

Ho³⁺-modified Pb(Zn_1/3Nb_2/3)O₃–9PbTiO₃ (PZN–9PT) single crystals were grown through a flux method. Phase structure and microstructural morphology of the as-grown single crystals were performed by X-ray diffraction analysis and scanning electron microscopy. The refinement of the lattice parameters were obtained by the Rietveld method. The electrical properties of PZN–9PT single crystals were improved significantly by the modification of Ho³⁺ ions. The rhombohedral–tetragonal phase transition temperature, Curie temperature, coercive field at 15 kV cm^?1, and remnant polarization of Ho³⁺-modified PZN–9PT single crystals were increased by 14, 42 K, 2.4 kV cm^?1, and 7.5 μC cm^?2, respectively (i.e., 375.45, 448.45 K, 5.9 kV cm^?1, and 38.40 μC cm^?2, respectively). Furthermore, Lorentz-type law was used to describe the dielectric relaxor behavior of the as-grown single crystals.     

Synthesis,electronic state,and particle size stabilization of nanoparticulate [Co(OH)<Subscript>2</Subscript>(H<Subscript>3</Subscript>O)<Stack><Subscript>δ</Subscript><Superscript>+</Superscript></Stack>]<Superscript>δ+</Superscript>

We have synthesized nanoparticulate cobalt(II) hydroxide containing Co²⁺ in tetrahedral oxygen coordination (Co _Td ²⁺ ), atypical of such systems: nano- [Co(OH)₂(H₃O) _δ ⁺ ]^δ+. The (Co _Td ²⁺ ) coordination in the hydroxide is inferred from its electronic diffuse reflectance spectrum, which shows a multiplet of strong absorption bands at 14500, 15000, and 16000 cm^?1 (⁴ A ₂(F)-⁴ T ₁(P) transition). Nanoparticulate cobalt(II) hydroxide forms in a weakly acidic medium under essentially nonequilibrium conditions due to supersaturation (by three to four orders of magnitude) with the starting reagents (CoCl₂ and LiOH) at the instant of the formation of the poorly soluble phase Co(OH)₂. Presumably, colloidal particles of nanoparticulate cobalt(II) hydroxide in a weakly acidic aqueous medium have a positive surface charge, compensated by a counter-ion (Cl^?) layer: nano-[Co(OH)₂(H₃O) _δ ⁺ ]^δ+ · δCl^?. The XRD patterns of pastes (gels) containing this hydroxide show three broad-ened lines with d = 5.31 (2θ = 16.7°), 2.77 (2θ = 32.3°), and 2.32 Å (2θ = 38.8°). According to small-angle X-ray scattering data, nano-[Co(OH)₂(H₃O) _δ ⁺ ]^δ+ has a narrow particle size distribution (1.0–2.0 nm). Synthesis and storage conditions are identified which ensure stabilization of the electronic state and particle size of nano-[Co(OH)₂(H₃O) _δ ⁺ ]^δ+ for a long time.     

Stability of the LaCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> and LuCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> Ions Studied by Mass Spectrometry

The enthalpy stability of the LaCl ₄ ^? and LuCl ₄ ^? ions is assessed using high-temperature mass spectrometry. The enthalpy of Cl^? detachment is determined to be Δ_rH⁰(298.15 K) = 332 ± 10 kJ/mol for LaCl ₄ ^? and 359 ± 10 kJ/mol for LuCl ₄ ^? .     

Luminescent properties of single-phase Ba<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>:Tb<Superscript>3+</Superscript>, R (R = Eu<Superscript>2+</Superscript>, Ce<Superscript>3+</Superscript>) phosphors for white LED

The Ba₂P₂O₇:Tb³⁺, R (R?=?Eu²⁺, Ce³⁺) phosphors were synthesized by use of a co-precipitation method. Crystal phase, excitation and emission spectra of sample phosphors are analyzed by means of XRD and FL, respectively. The emission spectra of Ba₂P₂O₇:Ce³⁺, Tb³⁺ phosphors exhibit four linear peaks attributed to the ⁵D₄?→?⁷F_J (J?=?6–3) transition of Tb³⁺ while four broad emission bands are observed in the emission spectra of Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors. The effects of Eu²⁺ concentration on the luminescent properties of Ba₂P₂O₇:Tb³⁺, R (R?=?Eu²⁺, Ce³⁺) are studied. Ce³⁺ affects the luminescent properties of Ba₂P₂O₇:Ce³⁺, Tb³⁺ phosphors just as the sensitizer. However, Eu²⁺ is considered both as the sensitizer and the activator in Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors. The chromaticity coordinates of Eu²⁺ and Tb³⁺ co-doped phosphors gather around the white light field with the CCT approximate to 5000 K, indicating that the luminescent property of Ba₂P₂O₇:Eu²⁺, Tb³⁺ phosphors may approach to a desired level needed for white LED application.     

Cathodoluminescence properties of SiO<Subscript>2</Subscript>:Pr<Superscript>3+</Superscript>and ZnO·SiO<Subscript>2</Subscript>:Pr<Superscript>3+</Superscript> phosphor nanopowders

The successful incorporation of ZnO nanoparticles in Pr³⁺-doped SiO₂ using a sol–gel process is reported. SiO₂:Pr³⁺ gels, with or without ZnO nanoparticles, were dried at room temperature and annealed at 600 °C. On the basis of the X-ray Diffraction (XRD) results, the SiO₂ was amorphous regardless of the incorporation of Pr³⁺ and nanocrystalline ZnO or annealing at 600 °C. The particles were mostly spherical and agglomerated as confirmed by Field Emission Scanning Electron Microscopy. Thermogravimetric analysis of dried gels performed in an N₂ atmosphere indicated that stable phases were formed at ≥900 °C. Absorption bands ascribed to ³H₄-³P_{(J = 0,1,2)}, ¹I₆ and ¹D₂ in the UV–VIS region were observed from SiO₂:Pr³⁺ colloids. The red cathodoluminescent (CL) emission corresponding to the ³P₀ → ³H₆ transition of Pr³⁺ was observed at 614 nm from dried and annealed SiO₂:Pr³⁺ powder samples. This emission was increased considerably when ZnO nanoparticles were incorporated. The CL intensity was measured at an accelerating voltage of 1-5 keV and a fixed beam current of 8.5 μA. The effects of accelerating voltage on the CL intensity and the CL degradation of SiO₂:Pr³⁺ and ZnO·SiO₂:Pr³⁺ were also investigated using Auger electron spectroscopy coupled with an Ocean Optics S2000 spectrometer.     

Structure,electrical, and optical properties of ZnO-substituted PbO for the Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> co-doped Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–GeO<Subscript>2</Subscript>–Na<Subscript>2</Subscript>O glass system

Glasses of the 0.5Er³⁺/2.5Yb³⁺ co-doped (40Bi₂O₃–20GeO₂–(30 − x)PbO–xZnO–10Na₂O system where x = 0.0, 5, 10, 15, 20, 25, and 30 mol%) have been characterized by FT-IR spectroscopy measurements to obtain information about the influence of ZnO-substituted PbO on the local structure of the glass matrix. The density and the molar volume have been determined. The influences of the ZnO-substituted PbO on the structure of glasses have been discussed. The dc conductivity measured in the temperature range 475–700 K obeys Arrhenius law. The conductivity decreases while the activation energy for conduction increases with increase ZnO content. The optical transmittance and reflectance spectrum of the glasses have been recorded in the wavelength range 400–1100 nm. The values of the optical band gap E _opt for all types of electronic transitions and refractive index have been determined and discussed. The real and imaginary parts ε₁ and ε₂ of dielectric constant have been determined.     

Probe Mössbauer Spectroscopy of BiNi<Subscript>0.96</Subscript><Superscript>57</Superscript>Fe<Subscript>0.04</Subscript>O<Subscript>3</Subscript>

This paper presents results of a ⁵⁷Fe probe Mössbauer spectroscopy study of the BiNi_0.96⁵⁷Fe_0.04O₃ nickelate. The spectra measured above its TN demonstrate that Fe³⁺ cations heterovalently substitute for Ni²⁺ nickel (←Fe³⁺), being stabilized on four sites of the nickel sublattice in the structure of BiNiO₃. Calculations in an ionic model with allowance for monopole and dipole contributions to the electric field gradient indicate that the parameters of electric hyperfine interactions between ⁵⁷Fe probe atom nuclei reflect the specifics of the local environment of the nickel in the structure of the unsubstituted BiNiO₃ nickelate. Below T^N, Mössbauer spectra transform into a complex Zeeman structure, which is analyzed in terms of first-order perturbation theory with allowance for electric quadrupole interactions as a small perturbation of the Zeeman levels of the ⁵⁷Fe hyperfine structure, as well as for specific features of the magnetic ordering of the Ni²⁺ cations in the nickelate studied.     

Characterization of <Superscript>4</Superscript>I<Subscript>9/2</Subscript> ↔ <Superscript>4</Superscript>F<Subscript>3/2</Subscript> optical transitions in trivalent Nd<Superscript>3+</Superscript> ions in GaLaS glass

The positions of Stark levels have been determined, using a step-by-step procedure, in the ⁴I_9/2 and ⁴F_3/2 manifolds of Nd³⁺ ions from absorption and photoluminescence measurements in the 12–293 K temperature range. This data has been used to calculate the emission cross-section for which the maximum value turns out to be ～2.3 × 10^?20 cm². The radiative recombination time, calculated using Judd–Ofelt analysis, of the ⁴F_3/2 manifold is in close vicinity to the experimentally determined times that were measured by the conventional decay of PL after interruption of excitation and by QFRS. Moreover, the peak time defined by QFRS is independent of temperature. Therefore, the dominant relaxation mechanism from the ⁴F_3/2 excited manifold of Nd³⁺ ions in GaLaS glass is believed to be by radiative emission.     

Synthesis and characterization of the M<Superscript>II</Superscript>U<Subscript>3</Subscript>O<Subscript>10</Subscript> · 6H<Subscript>2</Subscript>O (M<Superscript>II</Superscript> = Ni,Zn) triuranates

We have developed a process for the synthesis of Ni(II) and Zn(II) triuranates with the general formula M^IIU₃O₁₀ · 6H₂O through reaction of schoepite, UO₃ · 2.25H₂O, with aqueous solutions of nickel and zinc nitrates under hydrothermal conditions. Using chemical analysis, X-ray diffraction, IR spectroscopy, and thermal analysis, we have determined the composition and structure of the triuranates and investigated their dehydration and thermal decomposition.     

Synthesis and Structure of Mixed-Cation Salts with [PuO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>]<Superscript>3–</Superscript> Anions

Mixed-cation salts of the composition NaM₂[PuO₄(OH)₂]·4H₂O, where M = Rb (I) and Cs (III), and NaRb₅[PuO₄(OH)₂]₂·6H₂O (II) were synthesized and structurally characterized. The central Pu atom in [PuO₄(OH)₂]^3– anions has oxygen surrounding in the form of a tetragonal bipyramid with oxygen atoms of hydroxide ions in apical positions. The hydrated Na⁺ cations have oxygen surrounding in the form of a distorted octahedron. In the structure of I, there are two independent Rb⁺ cations with 10- and 12-vertex coordination polyhedra (CPs), and in the structure of II, three independent Rb⁺ cations with the 12-, 11-, and 13-vertex CPs. In the structure of III, the Cs⁺ cation has a 12-vertex CP. Frameworks of large Rb⁺ or Cs⁺ cations can be distinguished in the structure. The CPs of the Pu and Na atoms (I, III) sharing a common edge or the isolated CPs of the Pu and Na atoms (II) are incorporated in these frameworks. Hydrogen bonds influence the crystal packing and the geometric characteristics of the [PuO₄(OH)₂]^3– anions.     

Intense 2.0 µm emission from Ho<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> co-doped Na<Subscript>5</Subscript>Lu<Subscript>9</Subscript>F<Subscript>32</Subscript> single crystal excited by 980 nm

This paper reported on optical spectra of Na₅Lu₉F₃₂ single crystals co-doped with ~?0.91 mol% Ho³⁺ and various Yb³⁺ concentrations by using an improved Bridgman method. The emission spectra and fluorescence decay curves were measured to investigate the luminescent properties of the Ho³⁺/Yb³⁺ co-doped Na₅Lu₉F₃₂ and the energy transfer process from Yb³⁺ to Ho³⁺ ion. Compared with the Ho³⁺ singly doped Na₅Lu₉F₃₂ crystal, the Ho³⁺/Yb³⁺ co-doped crystal had an obviously enhanced emission at 2.0 µm via the 980 nm laser diode excitation because of the efficient energy transfer from Yb³⁺ to Ho³⁺ ion. The maximum emission intensity at 2.0 µm was obtained at about 6.99 mol% Yb³⁺ concentration when the concentration of Ho³⁺ ions is fixed at ~?0.91 mol% in the current research. The maximum emission cross section of the above sample at 2.0 µm was calculated to be 1.23?×?10^?20 cm² according to the measured emission spectrum. The energy transfer efficiency from Yb³⁺:²F_5/2 to Ho³⁺:⁵I₆ for the crystal was estimated up to 90.8% indicating that Yb³⁺ ions can efficiently sensitize the Ho³⁺ ions.     

Lewis and Brønsted acids in super-acid catalyst SO<Subscript>4</Subscript><Superscript>2−</Superscript>/ZrO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript>

Super-acid catalyst, SO₄ ^2?/ZrO₂–SiO₂, with high zirconium loading was synthesized and the nature of the surface acid was investigated by FT-IR of pyridine adsorption. With the increasing ZrO₂ content, the Lewis and Brønsted acid sites increased and reached the maximum when Zr/Si (molar ratio) = 1.3. The sample with Zr/Si = 1.3 showed the strongest IR adsorption band in the S=O stretching region (1,300–1,400 cm^?1). Pyrosulfate and monosulfate species existed on the surface of the catalysts and the acidic strength could be enhanced by induction effect of their S=O groups. And there were two kinds of Brønsted acid sites on the surface of the catalysts.     

Phase formation and microstructure of Nd<Superscript>+3</Superscript> doped Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> prepared by sol–gel method

The aim of this study was to investigate the effects of the rare earth element neodymium on the phase formation and microstructural development of relaxor ferroelectric lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN) system. Perovskite phase PMN powders were prepared using the sol–gel method and the effect of neodymium doping was investigated at different doping levels ranging from 0.1 mol% to 30 mol%. The precursors employed in the sol–gel process were lead (II) acetate, magnesium ethoxide, and niobium (V) ethoxide. All the experiments were performed at room temperature while the calcination temperatures ranged between 800 °C and 1,100 °C. Results showed that it was possible to obtain the pure perovskite phase at 950 °C using the sol–gel method. Nd⁺³ addition influenced the phase formation and microstructure of the multicomponent system. Pyrochlore was detected along with the perovskite phase above 10 mol% Nd. Results also demonstrated that grain size of the synthesized powders depended on the Nd⁺³ concentration.     

Controllable white light emission from Dy<Superscript>3+</Superscript>–Eu<Superscript>3+</Superscript> co-doped KCaBO<Subscript>3</Subscript> phosphor

Potassium calcium borate, KCaBO₃:Eu³⁺ phosphors with various Dy³⁺ concentrations (0–3 wt%) were synthesized by solid state reaction and studied for the first time. Under various UV–violet excitations, the obtained single monoclinic phased Dy³⁺–Eu³⁺ co-doped KCaBO₃ polycrystalline phosphors emit a combination of yellow–blue and red–orange wavelength giving intense white light, which can easily be controlled by varying the concentration of Dy³⁺. The increase in white light emission with the increase of Dy³⁺ concentration indicates the efficient energy inter-ion transfer from Dy³⁺ to Eu³⁺ ions. Furthermore, the observed emission lifetimes and the intense white light emission are suggestive exploration for the present phosphor for potential optoelectronic applications such as white light-emitting phosphor for blue LEDs chips.     

Synthesis and Structure of Mixed-Cation Salts with [NpO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>]<Superscript>3–</Superscript> Anions

Mixed-cation salts of the general composition NaM₂[NpO₄(OH)₂]·4H₂O, where M = Rb (I, II) and Cs (III), were synthesized and structurally characterized. The compounds differ from each other in the structural organization. The Np central atom in [NpO₄(OH)₂]^3– anions has oxygen surrounding in the form of a tetragonal bipyramid with the O atoms of hydroxide ions in the apical positions. The hydrated Na⁺ cations have oxygen surrounding in the form of a distorted octahedron. In the structure of I, there are two independent Rb cations with 10- and 12-vertex coordination polyhedra, and in the structures of II and III the framework of large cations is built of 12-vertex Rb and Cs polyhedra. The coordination polyhedra of the Np and Na atoms, sharing a common edge (I, III), or chains of the coordination polyhedra of the Np and Na atoms, sharing common vertices (II), are accommodated in the channels of the frameworks. Hydrogen bonds influence the crystal packing and the geometric characteristics of the [NpO₄(OH)₂]^3– anions.     

Tunable luminescence and energy transfer properties in Ca<Subscript>2−x</Subscript>NaMg<Subscript>2</Subscript>V<Subscript>3</Subscript>O<Subscript>12</Subscript>:xEu<Superscript>3+</Superscript> phosphors

Novel broadband luminescence phosphors Ca_2?xNaMg₂V₃O₁₂:xEu³⁺ have been successfully prepared via the conventional high-temperature solid-state reaction. The effects of concentrations of doped Eu³⁺ and introducing Li⁺, K⁺ on the luminescent properties of phosphor were studied. X-ray diffraction, GSAS structural refinement and photoluminescence spectra were used to characterize the samples. The refinement data ensured where the doped Eu³⁺ ions occupied the lattice site in the host. Under 355 nm excitation, the emission peak of Ca₂NaMg₂V₃O₁₂:Eu³⁺ phosphors are located at 610 nm (red) ascribed to the electric dipole transition of Eu³⁺ from ⁵D₀ → ⁷F₂. In the range of 400–575 nm, Ca₂NaMg₂V₃O₁₂:Eu³⁺ phosphors have broad emission bands attributed to charge transfer of \({\text{VO}}_4^{3 - }\) group. Energy transfer mechanism, energy transfer efficiency and critical distance (R_c) of \({\text{VO}}_4^{3 - }\) → Eu³⁺ would be analyzed. The emitting color of Ca₂NaMg₂V₃O₁₂:Eu³⁺ could be tunable from blue-green to near white light.     

Y<Subscript>2</Subscript>O<Subscript>2</Subscript>S:Er<Superscript>3+</Superscript>,Ce<Superscript>3+</Superscript>—A new “invisible” IR phosphor

Ce³⁺ doping of Y₂O₂S:Er³⁺ can be used to suppress the visible anti-Stokes luminescence of the phosphor under excitation in the range 0.90–0.98 μm. We take advantage of this effect to create a new, efficient “invisible” IR phosphor emitting in the range 1.5–1.6 μm.