Microwave-sintered Pr<Superscript>3+</Superscript>, Sm<Superscript>3+</Superscript>, and Gd<Superscript>3+</Superscript> triple-doped ceria electrolyte material for IT-SOFC applications

The Pr³⁺, Sm³⁺, and Gd³⁺ triple-doped ceria Ce_0.76Pr_0.08Sm_0.08Gd_0.08O_2-δ material as solid electrolyte for IT-SOFC has been successfully synthesized by sol–gel auto-combustion route. The effect of microwave sintering (1300 °C for 15, 30, and 60 min, named as PSG-MS15, PSG-MS30, and PSG-MS60, respectively) on structural, electrical, and thermal properties of prepared electrolyte material has been studied. Powder X-ray diffraction, scanning electron microscope, energy dispersive spectroscopy, and Raman analysis revealed the single phase, microstructure, elemental confirmation, and structural oxygen vacancy formation of all the samples. Impedance spectroscopy analysis revealed the highest total ionic conductivity, i.e., 3.47 × 10^?2 S cm^?1 at 600 °C with minimum activation energy of 0.69 eV, in PSG-MS30 sample when compared to PSG-MS15 and PSG-MS60. The thermal expansion measurements have been carried out for PSG-MS30 specimen. The highest total ionic conductivity with minimum activation energy and moderate thermal expansion coefficient of PSG-MS30 sample makes the possibility of its use as solid electrolyte in IT-SOFC applications.     

Rare Earth Centered Hybrid Materials: Tb<Superscript>3+</Superscript> Covalently Bonded with La<Superscript>3+</Superscript>, Gd<Superscript>3+</Superscript>, Y<Superscript>3+</Superscript> Through Sulfonamide Bridge and Luminescence Enhancement

The organic ligand 5-sulfosalicylic acid (SSA) is grafted by (3-aminopropyl) triethoxysilane (APTES) to achieve functionalized sulfonamide bridge (SSA-Si) which can both coordinate to Ln³⁺ to form luminescent center and link inorganic Si-O network through hydrolysis and condensation reaction with tetraethoxysilane (TEOS). Thus the organic–inorganic hybrid is obtained with sol-gel method. The organic polymer poly-methyl methacrylate (PMMA) acts as another precursor is prepared through the direct addition polymerization of MMA monomer in the presence of the initiator BPO (benzoyl peroxide). The two kinds of precursors are coordinated to the Ln³⁺ simultaneously to form organic–inorganic-polymeric hybrids which contain both inorganic Si-O-Si net and organic periodic C–C chains. In these complicated compounds we intercalate different ratios of Tb³⁺ and inert lanthanide ion (La³⁺, Gd³⁺, Y³⁺) and find that the introduction of the inert lanthanide ions can enhance the luminescence intensity. This enhancement phenomenon is called co-luminescence effect which is studied by emission spectra in this paper.     

Photophysical Properties of Rare Earth (Eu<Superscript>3+</Superscript>, Sm<Superscript>3+</Superscript>, Tb<Superscript>3+</Superscript>) Complex Covalently Immobilized in Hybrid Si-O-B Xerogels

The molecular linkage (phenSi) from functionalized 5-amino-1,10-phenanthroline (PhenNH₂) by 3-(triethoxysilyl)-propyl isocyanate (TESPIC) is to construct the rare earth (Sm³⁺, Eu³⁺, Tb³⁺) center covalently immobilized in the hybrid xerogels of Si-O-B through the cohydrolysis and copolycondensation process between different alkoxide precursors of them (tetraethoxysilane (TEOS), tri-n-butylborate (TBB)). NMR, FTIR and ultraviolet absorption are measured to confirm the obtained materials. X-ray diffraction patterns revealed the hybrid materials are amorphous. Scanning electronic microscopy images show the stripe microstructure without phase separation phenomenon in the obtained hybrid materials. The covalently bonded Si-O-B hybrid xerogel presents the similar photoluminescent behavior to the pure Si-O-Si hybrid xerogels, which indicates that Si-O-B hybrid xerogel is a suitable system for the luminescence of RE³⁺.     

Luminescence of transparent glass ceramics containing Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> zirconate-titanate nanocrystals

Luminescence regularities have been studied in new erbium/ytterbium materials based on glasses and glass ceramics of a magnesium-aluminosilicate system containing nanoscale erbium/ytterbium zirconate titanate crystals with the pyrochlore structure. Lifetimes of Yb³⁺ and Er³⁺ ions in the ² F_5/2 state and in the ⁴I_11/2 and ⁴I_13/2 states, respectively, and the efficiency of Yb³⁺ → Er³⁺ energy transfer have been evaluated. The identified spectral-luminescent characteristics of the studied glasses and glass ceramics co-doped with erbium and ytterbium ions show that these materials are promising media for producing laser generation in the spectral range around 1.5 μm.     

Comparative Investigation on Nanocrystal Structure and Luminescence Properties of Gadolinium Molybdates Codoped with Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript>

This paper reports on the comparative investigation of nanocrystal structure and luminescence properties of Er³⁺/Yb³⁺-codoped gadolinium molybdate nanocrystals Gd₂(MoO₄)₃ and Gd₂MoO₆ synthesized by the Pechini method with citric acid and ethylene glycol. Their crystallization, structure transformation, and morphologies have been investigated by X-ray diffraction, thermogravimetric/differential scanning calorimetry, and transmission electron microscopy. It is noticed that Er³⁺/Yb³⁺-codoped monoclinic Gd₂(MoO₄)₃ nanocrystals have shown an intense upconversion through a sintering of the organic complex precursor at 600°C. Furthermore, it transforms to orthorhombic Gd₂(MoO₄)₃ when the precursor is sintered at 900°C. In counterpart of monoclinic Gd₂MoO₆, however, the monoclinic structure remains unchanged when the precursor is sintered at a temperature ranging from 600°C to 900°C. Intense visible emissions of Er³⁺ attributed to the transitions of ²H_11/2, ⁴S_3/2–⁴I_15/2 at 520 and 550 nm, and ⁴F_9/2–⁴I_15/2 at 650 nm have been observed upon an excitation with a UV source and a 980 nm laser diode, and the involved mechanisms have been explained. It is quite interesting to observe obvious differences both in the excitation and the upconversion emission spectra of Er³⁺/Yb³⁺-codoped Gd₂(MoO₄)₃ respectively with monoclinic and orthorhombic structure. The quadratic dependence of fluorescence on excitation laser power has confirmed that two-photons contribute to upconversion of the green–red emissions.     

On the Luminescence of Ce<Superscript>3+</Superscript>, Eu<Superscript>3+</Superscript>, and Tb<Superscript>3+</Superscript> in Novel Borate LiSr<Subscript>4</Subscript>(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>

This paper reports on the photoluminescence (PL) and time-resolved properties of Ce³⁺, Eu³⁺, and Tb³⁺ in novel LiSr₄(BO₃)₃ powder phosphors. Ce³⁺ shows an emission band peaking at 420 nm under 350-nm UV excitation. Energy transfer from Ce³⁺ to Mn²⁺ takes place in the co-doped samples. Eu³⁺ shows red emission under near UV excitation. LiSr₄(BO₃)₃:Eu³⁺ phosphor could be a suitable candidate for phosphor-converted solid state lighting. The luminescence lifetime is 2.13 ms for Eu³⁺ in LiSr₄(BO₃)₃:0.001Eu³⁺. As Eu³⁺ concentration increasing, the decay curves deviate from exponential behavior. Tb³⁺ shows the strongest ⁵D₄→⁷ F₅ emission line at 540 nm. Decay curves of ⁵D₄→⁷ F₅ and ⁵D₃→⁷ F₅ emission with different Tb³⁺ concentrations were also measured. Cross-relaxation process is discussed based on the decay curves.     

Luminescence and energy transfer mechanism in Eu<Superscript>3+</Superscript>/Tb<Superscript>3+</Superscript>-co-doped ZrO<Subscript>2</Subscript> nanocrystal rods

Nanocrystal rods of Eu³⁺/Tb³⁺-co-doped ZrO₂ were synthesized using a simple chemical precipitation technique. Both ions were successfully doped into the Zr⁴⁺ ion site in a mixed structure containing both monoclinic and tetragonal phases. The Eu³⁺ or Tb³⁺ singly doped zirconia produced red and green luminescence which are characteristics of Eu³⁺ and Tb³⁺ ions, respectively. The co-doped zirconia samples produced blue emission from defect states transitions in the host ZrO₂, red and green luminescence from dopant ions giving cool to warm white light emissions. The phosphors were efficiently excited by ultraviolet and near-ultraviolet/blue radiations giving white and red light, respectively. The decay lifetime was found to increase with increasing donor ion concentration contrary to conventional observations reported by previous researchers. Weak quadrupole–quatdrupole multipolar process was responsible for energy transfer from Tb³⁺ (donor) ion to Eu³⁺ ion. No energy back-transfer from Eu³⁺ to Tb³⁺ ion was observed from the excitation spectra. Temperature-dependent photoluminescence shows the presence of defects at low temperature, but these defects vanished at room temperature and beyond. The Eu³⁺/Tb³⁺-co-doped ZrO₂ nanocrystal rod is a potential phosphor for white light application using UV as an excitation source. Thermoluminescence measurements show that the inclusion of Tb³⁺ ion increases trap depths in the host zirconia.     

Sensitizing of Sm<Superscript>3+</Superscript> fluorescence by silver dopant in the TiO<Subscript>2</Subscript> films

Composite material based on a TiO₂ matrix doped with Sm³⁺ ions and co-doped with silver was investigated. Samarium ions together with nano- and micro-aggregates of silver were incorporated into the titanium alkoxide during the sol-gel process. Samarium ions were excited either directly (λ _exc = 488 nm) or through the TiO₂ host (λ _exc = 355 nm). It was revealed that samarium fluorescence (λ _exc = 488 nm) in gelled TiO₂ films is enhanced by up to 20 times in the vicinity of silver inclusions. Sensitizing and plasmonic mechanisms of enhancement in Sm³⁺ fluorescence are discussed.     

Re-dispersible Li<Superscript>+</Superscript> and Eu<Superscript>3+</Superscript> co-doped CdS nanoparticles: Luminescence studies

Re-dispersible CdS, 5 at.% Eu³⁺-doped CdS, 2 at.% Li⁺ and 5 at.% Eu³⁺ co-doped CdS nanoparticles in organic solvent are prepared by urea hydrolysis in ethylene glycol medium at a low temperature of 170°C. CdS nanoparticles have spherical shape with a diameter of ∼80 nm. The asymmetric ratio (A ₂₁) of the integrated intensities of the electrical dipole transition to the magnetic dipole transition for 5 at.% Eu³⁺-doped CdS is found to be 3.8 and this ratio is significantly decreased for 2 at.% Li⁺ and 5 at.% Eu³⁺ co-doped CdS (A ₂₁ = 2.6). It establishes that the symmetry environment of Eu³⁺ ion is more favored by Li-doping. Extra peak at 550 nm (green emission) could be seen for 2 and 5 at.% Eu³⁺ co-doped CdS. Also, the significant energy transfer from host CdS to Eu³⁺ is found for 5 at.% Eu³⁺-doped CdS compared to that for 2 at.% Li⁺ and 5 at.% Eu³⁺ co-doped CdS.      

Intense Upconversion Luminescence of Yb<Superscript>3+</Superscript>-Er<Superscript>3+</Superscript> in Li<Subscript>2</Subscript>O Content Tungsten-tellurite Glasses

The Er³⁺ -Yb³⁺ codoped in Li₂O content tungsten -tellurite (TWL) transparent glasses are synthesized and measured the absorption, Raman and upconversion luminescence (UPL) spectra. At room temperature intense green emission peak at 560 nm ( ⁴S_3/2→⁴I_15/2) and red emission peak at 670 nm ( ⁴F_9/2→⁴I_15/2) of Er³⁺ observed even at minimum 86 mW pumping power of infrared 980 nm excitation. For structure of the TWL glass, Raman spectrum result revealed that an important role of WO₃ in the formation of glass network linkage with Li₂O. Under this influence estimated lifetime of the ⁴I_11/2 of Er³⁺ was 1.89 μs and due to lower phonon energy of the glass produce strong upconversion signal. The effect of Er₂O₃ concentration on emission intensity result indicated that green emission intensity initially increase in compare to red emission. Under the 980 nm pump power variation measured the relatively increases the red emission to the green emission intensity and analyze the possible upconversion mechanism and process.     

Luminescence of Eu<Superscript>3+</Superscript> ions in ultradisperse diamond powders

The luminescence of Eu³⁺ ions implanted in ultradisperse diamond powders, activated by impregnating with a solution of Eu(NO₃)₃·6H₂O and heat-treated at various temperatures, is studied. A multiple increase in the efficiency of excitation in the charge-transfer band is observed for the ⁵D₀ state of Eu³⁺ ions as compared to europium nitrate heat-treated similarly. This effect is explained by an increase in the degree of Eu-O bond covalency and a change in the activator coordination polyhedron due to the formation of chemical bonds Eu-O-C.     

Defect Structure and Up-conversion Luminescence Properties of ZrO<Subscript>2</Subscript>:Yb<Superscript>3+</Superscript>,Er<Superscript>3+</Superscript> Nanomaterials

The up-converting ZrO₂:Yb³⁺,Er³⁺ nanomaterials were prepared with the combustion and sol–gel methods. FT-IR spectroscopy was used for analyzing the impurities. The crystal structures were characterized with X-ray powder diffraction and the mean crystallite sizes were estimated with the Scherrer formula. Up-conversion luminescence measurements were made at room temperature with IR-laser excitation at 977 nm. The IR spectra revealed the conventional and OH⁻ impurities for the combustion synthesis products. The structure of the ZrO₂:Yb³⁺, Er³⁺ nanomaterials was cubic except for the minor monoclinic and tetragonal impurities obtained with the sol–gel method. The materials showed red (650–700 nm) and green (520–560 nm) up-conversion luminescence due to the ⁴F_9/2→⁴I_15/2 and (²H_11/2, ⁴S_3/2)→⁴I_15/2 transitions of Er³⁺, respectively. The products obtained with the combustion synthesis exhibited the most intense luminescence intensity and showed considerable afterglow.     

Optical spectra and excited state relaxation dynamics of Sm<Superscript>3+</Superscript> in Gd<Subscript>2</Subscript>SiO<Subscript>5</Subscript> single crystal

Single crystals of gadolinium orthosilicate Gd₂SiO₅ containing 0.5 at% and 5 at% of Sm³⁺ were grown by the Czochralski method. Optical absorption spectra, luminescence spectra and luminescence decay curves were recorded for these systems at 10 K and at room temperature. Comparison of optical spectra recorded in polarized light revealed that the anisotropy of this optically biaxial host affects the intensity distribution within absorption and emission bands related to transitions between multiplets rather than the overall band intensity. It has been found that among four bands of luminescence related to the ⁴G_5/2→⁶H_J (J=5/2–11/2) transitions of Sm³⁺ in the visible and near infrared region the ⁴G_5/2 →⁶H_7/2 one has the highest intensity with a peak emission cross section of 3.54×10⁻²¹ cm² at 601 nm for light polarized parallel to the crystallographic axis c of the crystal. The luminescence decay curve recorded for Gd₂SiO₅:0.5 at% Sm³⁺ follows a single exponential time dependence with a lifetime 1.74 ms, in good agreement with the ⁴G_5/2 radiative lifetime τ _rad=1.78 ms calculated in the framework of Judd-Ofelt theory. Considerably faster and non-exponential luminescence decay recorded for Gd₂SiO₅:5 at% Sm³⁺ sample was fitted to that predicted by the Inokuti-Hirayama theory yielding the microparameter of Sm³⁺–Sm³⁺ energy transfer C _da=1.264×10⁻⁵² cm⁶×s⁻¹.     

Effect of Sr<Superscript>2+</Superscript> ion substitution with trivalent ions (Sc<Superscript>3+</Superscript>, In<Superscript>3+</Superscript>, La<Superscript>3+</Superscript>, Bi<Superscript>3+</Superscript>) on its ferroelectric instability in SrTiO<Subscript>3</Subscript>

The vibration frequencies of unstable ferroelectric and antiferrodistortion modes and the dependences of the energy on the ion displacement amplitude have been calculated within the generalized Gordon-Kim model for distortions along eigenvectors of these modes in the mixed compounds Sr_{1 − x} A _x Ti_{1 − x} /₄□ _x/4O₃ and Sr_{1 − y} A _2y /₃□ _y/3TiO₃ (A = Sc³⁺, In³⁺, La³⁺, Bi³⁺; □ is the vacancy). To compensate an excess positive charge, vacancies are introduced into the Ti⁴⁺ or Sr²⁺ site. Calculations have been performed in the “daverage” crystal approximation for impurity concentrations of 0.25 and 0.50. To this end, a set of 40 atomic superlattices with various orderings of heterovalent ions Sr²⁺ and impurity A ³⁺ has been considered. It has been found that each impurity type, independently of charge balance, induces ferroelectric instabilities in doped compounds. In the case of doping with In³⁺ and La³⁺ for concentration x = 0.25, the possibility of rotating the polarization vector has been shown.     

Intensity of the <Emphasis Type="Italic">f-f</Emphasis> transitions of Nd<Superscript>3+</Superscript>, Er<Superscript>3+</Superscript>, and Tm<Superscript>3+</Superscript> rare-earth ions in calcium niobium gallium garnet crystals

This paper reports on the results of the investigation into the intensities of the f-f transitions of Nd³⁺, Er³⁺, and Tm³⁺ ions in calcium niobium gallium garnet (CNGG) crystals. The values of the oscillator strengths and line strengths obtained for hypersensitive transitions and the intensity parameters Ω _t of the rare-earth ions in the CNGG crystals are compared with the corresponding quantities for crystals of other garnets and some oxide and fluoride crystals. The assumption is made that an increase in the oscillator strengths and line strengths for the hypersensitive transitions and the intensity parameters Ω₂ of the Nd, Er, and Tm ions in the CNGG crystals as compared to those for crystals of other garnets is associated with the specific features revealed in the crystal structure of the calcium niobium gallium garnet, in particular, with the lowering of the symmetry of the positions occupied by rare-earth ions in the crystal structure.     

Luminescence characteristics of energy transfer between Ce<Superscript>3+</Superscript> and Eu<Superscript>2+</Superscript> in NaMgPO<Subscript>4</Subscript> phosphor

Powder samples of NaMgPO₄ doped with Eu²⁺ and Ce³⁺ were prepared and their photoluminescence spectra were systemically studied. Energy transfer from Ce³⁺ to Eu²⁺ in NaMgPO₄ phosphor was observed by investigating the optical properties from photoluminescence spectra in Eu²⁺ or Ce³⁺ singly doped and Eu²⁺–Ce³⁺ codoped sodium magnesium orthophosphates, NaMgPO₄. The enhancement of UV excitation is attributed to energy transfer from Ce³⁺ to Eu²⁺, and Ce³⁺ plays a role as a sensitizer. Ce³⁺–Eu²⁺ codoped NaMgPO₄ phosphors in which Eu²⁺ can be efficiently excited by 390 nm are potential candidates for phosphor-converted LEDs.     

Luminescence in Dy<Superscript>3+</Superscript> and Eu<Superscript>3+</Superscript> Activated K<Subscript>3</Subscript>Al<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

The Dy³⁺ and Eu³⁺ activated K₃Al₂ (PO₄)₃ phosphors were prepared by a combustion synthesis. From a powder X-ray diffraction (XRD) analysis the formation of K₃Al₂ (PO₄)₃ was confirmed. In the photoluminescence emission spectra, the K₃Al₂(PO₄)₃:Dy³⁺ phosphor emits two distinctive colors: blue and yellow whereas K₃Al₂(PO₄)₃:Eu³⁺ emits red color. Thus the combination of colors gives BYR (blue–yellow–red) emissions can produce white light. These phosphors exhibit a strong absorption between 340 and 400 nm which suggest that present phosphor is a promising candidate for producing white light-emitting diodes (LED).     

Green,blue, red,near-infrared up-conversion luminescence of Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>/Tm<Superscript>3+</Superscript> co-doped YVO<Subscript>4</Subscript> nanoparticles

YVO₄:Yb³⁺,Er³⁺; YVO₄:Yb³⁺,Tm³⁺; and YVO₄:Yb³⁺,Er³⁺,Tm³⁺ were all synthesized via sol-gel method with a subsequent thermal treatment. Specifically, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ phosphors were prepared with different annealing temperatures to study the influence of temperature. The transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffractometer (XRD), and photoluminescent (PL) spectrofluorometer were used to investigate the morphology, crystal structure, and up-conversion luminescent properties of all samples. In summary, all samples were granular-like nanoparticles and well crystallized with the same tetragonal phase as YVO₄. Under the irradiation at 980 nm, YVO₄:Yb³⁺,Er³⁺ phosphors can generate green emission at 525 and 553 nm and red emission at 657 nm, while YVO₄:Yb³⁺,Tm³⁺ phosphors can generate blue emission at 476 nm, red emission at 648 nm, and near-infrared emission at 800 nm. Notably, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ samples can exhibit green emission, blue emission, red emission, and near-infrared emission at the same time, which might endow the as-prepared samples with potential applications in many fields, such as luminous paint, infrared detection, and biological label.