Fabrication and Luminescence Properties of Transparent Glass‐Ceramics Containing Eu3+‐Doped TbPO4 Nanocrystals

Eu³⁺‐doped transparent phosphate precursor glasses and glass‐ceramics containing TbPO₄ nanocrystals were successfully fabricated by a conventional high‐temperature melt‐quenching technique for the first time. The formation of TbPO₄ nanocrystals was identified through X‐ray diffraction, transmission electron microscopy, high‐resolution transmission electron microscopy, selected‐area electron diffraction, and photoluminescence emission spectra. The obvious Stark splitting of ⁵D₀‐⁷F_J (J = 1, 2, 4) transitions of Eu³⁺and the increase of internal quantum efficiency indicate the incorporation of Eu³⁺ into TbPO₄ nanocrystals. Energy transfer from Tb³⁺ ions to Eu³⁺ ions was investigated using excitation and emission spectra at room temperature. The glass‐ceramics obtained have more efficient Tb³⁺ to Eu³⁺ energy transfer than the glass, and so serve as good hosts for luminescent materials.     

Elaboration,Structure, and Luminescence of Eu3+‐Doped BaLuF5‐Based Transparent Glass‐Ceramics

Novel Eu³⁺‐doped transparent oxyfluoride glass‐ceramics containing BaLuF₅ nanocrystals were successfully fabricated by melt‐quenching technique for the first time. Analyses of XRD patterns prove that the new precipitated glass‐ceramics are crystallized in cubic BaLuF₅ based on isostructural BaGdF₅. Intense red emissions observed in glass ceramics are attributed to the enrichment of Eu³⁺ ions into BaLuF₅ nanocrystals. Besides, obvious stark splitting emissions, low forced electric dipole ⁵D₀→⁷F₂ transition, and long decay lifetimes of Eu³⁺ ions also evidence the partition of Eu³⁺ ions into BaLuF₅ nanocrystals with low phonon energy. Such transparent material may find applications in photonics.     

Novel Upconversion Behavior in Ho3+‐Doped Transparent Oxyfluoride Glass‐Ceramics Containing NaYbF4 Nanocrystals

Novel Ho³⁺ doped highly transparent NaYbF₄ glass‐ceramics were successfully fabricated by melt‐quenching technique. Their structural and luminescent properties were systemically investigated by XRD, TEM, absorption spectra, upconversion spectra, and lifetime measurements. Excited by 980‐nm laser, samples exhibit characteristic emissions of Ho³⁺. Impressively, the luminescent color can be tuned easily from red for precursor glass to green for glass‐ceramics. Such novel phenomenon was elaborately investigated and is owing to the reduced multiphonon nonradiative relaxation and enhanced cross‐relaxation of Ho³⁺ in NaYbF₄ nanocrystals after crystallization. Our results indicate that NaYbF₄ transparent glass‐ceramics is an excellent host for upconversion.     

Thermal,Structural, and Enhanced Photoluminescence Properties of Eu3+‐doped Transparent Willemite Glass–Ceramic Nanocomposites

The precursor glass in the ZnO–Al₂O₃–B₂O₃–SiO₂ (ZABS) system doped with Eu₂O₃ was prepared by the melt‐quench technique. The transparent willemite, Zn₂SiO₄ (ZS) glass–ceramic nanocomposites were derived from this precursor glass by a controlled crystallization process. The formation of willemite crystal phase, size, and morphology with increase in heat‐treatment time was examined by X‐ray diffraction (XRD) and field‐emission scanning electron microscopy (FESEM) techniques. The average calculated crystallite size obtained from XRD is found to be in the range 18–70 nm whereas the grain size observed in FESEM is 50–250 nm. The refractive index value is decreased with increase in heat‐treatment time which is caused by the partial replacement of ZnO₄ units of ZS nanocrystals by AlO₄ units due to generation of vacancies. Fourier transform infrared (FTIR) reflection spectroscopy was used to evaluate its structural evolution. Vickers hardness study indicates marked improvement of hardness in the resultant glass‐ceramics compared with its precursor glass. The photoluminescence spectra of Eu³⁺ ions exhibit emission transitions of ⁵D₀→⁷F_j (j = 0, 1, 2, 3, and 4) and its excitation spectra show an intense absorption band at 395 nm. These spectra reveal that the luminescence performance of the glass–ceramic nanocomposites is enhanced up to 17‐fold with the process of heat treatment. This enhancement is caused by partitioning of Eu³⁺ ions into glassy phase instead of into the willemite crystals with progress of heat treatment. Such luminescent glass–ceramic nanocomposites are expected to find potential applications in solid‐state red lasers, phosphors, and optical display systems.     

Enhanced Sunlight Excited 1‐μm Emission in Cr3+–Yb3+ Codoped Transparent Glass‐Ceramics Containing Y3Al5O12 Nanocrystals

Cr³⁺–Yb³⁺ codoped transparent glass‐ceramics containing Y₃Al₅O₁₂ nanocrystals were prepared by heat treatment of as‐prepared glass sample and characterized by X‐ray diffraction and transmission electron microscopy. The efficient energy transfer from Cr³⁺ to Yb³⁺ ions through multi‐phonon‐assisted process was confirmed by the luminescence spectrum and fluorescent lifetime measurements. When excited by the lights from a solar simulator in the wavelength region of 400–800 nm, greatly enhanced near‐infrared emission around 1 μm was achieved from Cr³⁺–Yb³⁺ codoped glass ceramic compared with that from as‐prepared glass and Ce³⁺–Yb³⁺ codoped glass ceramic. These results demonstrate that the Cr³⁺–Yb³⁺ codoped glass ceramic is a promising material for enhancement of the efficiency of solar energy utilization.     

Impact of Eu3+ Dopants on Optical Spectroscopy of Ce3+: Y3Al5O12‐Embedded Transparent Glass‐Ceramics

Transparent glass‐ceramics containing Ce³⁺: Y₃Al₅O₁₂ phosphors and Eu³⁺ ions were successfully fabricated by a low‐temperature co‐sintering technique to explore their potential application in white light‐emitting diodes (WLEDs). Microstructure of the sample was studied using a scanning electron microscope equipped with an energy dispersive X‐ray spectroscopy. The impact of co‐sintering temperature, Ce³⁺: Y₃Al₅O₁₂ crystal content and Eu³⁺ doping content on optical properties of glass‐ceramics were systematically studied by emission, excitation spectra, and decay curves. Notably, the spatial separation of these two different activators in the present glass‐ceramics, where Ce³⁺ ions located in YAG crystalline phase while the Eu³⁺ ones stayed in glass matrix, is advantageous to the realization of both intense yellow emission assigned to Ce³⁺: 5d→4f transition and red luminescence originating from Eu³⁺: 4f→4f transitions. As a result, the quantum yield of the glass‐ceramic reached as high as 93%, and the constructed WLEDs exhibited an optimal luminous efficacy of 122 lm/W, correlated color temperature of 6532 K and color rendering index of 75.     

Processing and Properties of Eu3+‐Doped Barium Bismuth Titanate (BaBi4Ti4O15) Glass–Ceramic Nanocomposites

Precursor glasses for the ferroelectric barium bismuth titanate (BaBi₄Ti₄O₁₅) (BBiT) have been prepared by the melt‐quench technique in the SiO₂–K₂O–BaO–Bi₂O₃–TiO₂ (SKBBT) glass system with and without Eu₂O₃ doping. BBiT glass–ceramic (GC) nanocomposites have been derived from these glasses by controlled heat treatment. The structural properties of the GCs have been investigated using X‐ray diffraction (XRD), electron microscopy (FE‐SEM, TEM), and FT‐IR reflectance spectroscopy. FE‐SEM images show the formation of randomly oriented hexagonal rod‐shaped crystals of 200–400 nm and TEM images show 10–20 nm crystallites. FT‐IR spectra exhibit the characteristic bands of BBiT at 480, 585, and 680 cm^?1. The activation energy of crystallization (E_c) varies from 295 to 307 kJ/mol. The dielectric constants (ε_r) of glass and GC nanocomposites increase with an increase in frequency up to 3.0 MHz and then decrease up to 5.0 MHz. Heat‐treated GCs show higher ε_r values, in the range 25–55, compared to the precursor glasses (20–37). Dielectric losses (tan δ) for all the samples increase from 0.005 to 1.0 with an increase in frequency from 100 Hz to 5.0 MHz. Excitation spectra were recorded by monitoring emission at 613 nm corresponding to the ⁵D₀ → ⁷F₂ transition. An intense 466 nm excitation band corresponding to the ⁷F₀ → ⁵D₂ transition was observed. Emission spectra were then recorded by exciting the glass samples at 466 nm. Longer heat‐treatment times led to a 15‐fold increase in the intensity of the red emission at 612 nm, attributed to the segregation of Eu³⁺ ions into the low phonon energy BBiT crystallites. The hardness (3.8–5.1 GPa) and fracture toughness (1.8–3.5 MPam^0.5) values obtained in the GCs are high and suitable for structural applications.     

Er3+ Ions‐Doped Germano‐Gallate Oxyfluoride Glass‐Ceramics Containing BaF2 Nanocrystals

Er³⁺ ions‐doped germano‐gallate oxyfluoride glass‐ceramic containing BaF₂ nanocrystals was prepared through conventional melt quenching and subsequent thermal treatment method. X‐ray diffraction patterns and transmission electron microscope images confirmed the formation of BaF₂ nanocrystals in glass‐ceramics. Preferential incorporation of Er³⁺ ions into the BaF₂ nanocrystals were confirmed by the absorption spectra and emission spectra, and enhanced upconversion emission and infrared emission were observed. Relatively high transmittance in the mid‐infrared region indicated great potential of this germano‐gallate oxyfluoride glass‐ceramics as host materials for the efficient mid‐infrared emission from rare‐earth ions.     

Luminescence of Eu‐Doped Transparent LuPO4 Glass‐Ceramics

Dual valence Eu‐doped transparent glass‐ceramics containing LuPO₄ nanocrystals were fabricated by melt‐quenching technique in air atmosphere. Their luminescent properties were systematically investigated by excitation, emission spectra, and decay lifetime measurements. The prominent Stark splitting, low forced electric‐dipole ⁵D₀ – ⁷F₂ transition and long decay lifetimes of Eu^{3 +} emission for glass‐ceramics reveal the incorporation of Eu^{3 +} into LuPO₄ nanocrystals. The enhanced Eu^{2 +} emission and reduction mechanism of Eu^{3 +} to Eu^{2 +} after crystallization are discussed briefly. Our results indicate that transparent LuPO₄ glass‐ceramics may find applications in photonics.     

Spectral Properties of Pr3+‐Doped Transparent‐Glass‐Ceramic Containing Ca5(PO4)3F Nanocrystals

A Pr³⁺‐doped transparent oxyfluoride glass‐ceramic containing Ca₅(PO₄)₃F nanocrystals was prepared by melt quenching and subsequent thermal treatment. The crystallization phase and morphology of the Ca₅(PO₄)₃F nanocrystals were investigated by X‐ray diffraction and transmission electron microscope, respectively. The volume fraction of the Ca₅(PO₄)₃F nanocrystals in the glass‐ceramic is about 10% and the fraction of Pr³⁺ ions incorporated into the Ca₅(PO₄)₃F nanocrystals is about 22%. The peak absorption cross sections at 435 and 574 nm increase up to 128% and 132% after crystallization, respectively. The peak stimulated emission cross sections of the ³P₀→³H₄ blue laser channel and ³P₀→³F₂ red laser channel for the glass‐ceramic are 4.95 × 10^?20 and 29.8 × 10^?20 cm², respectively. The spectral properties indicate that the glass‐ceramic is a potential visible laser material.     

Fabrication and Characterization of Glass‐Ceramic Fiber‐Containing Cr3 + ‐Doped ZnAl2O4 Nanocrystals

Glass‐ceramic fibers containing Cr³⁺‐doped ZnAl₂O₄ nanocrystals were fabricated by the melt‐in‐tube method and successive heat treatment. The obtained fibers were characterized by electro‐probe micro‐analyzer, X‐ray diffraction, Raman spectrum and high‐resolution transmission electron microscopy. In our process, fibers were precursor at the drawing temperature where the fiber core glass was melted while the clad was softened. No obvious element interdiffusion between the core and the clad section or crystallization was observed in precursor fiber. After heat treatment, ZnAl₂O₄ nanocrystals with diameters ranging from 1.0 to 6.3 nm were precipitated in the fiber core. In comparison to precursor fiber, the glass‐ceramic fiber exhibits broadband emission from Cr³⁺ when excited at 532 nm, making Cr³⁺‐doped glass‐ceramic fiber a promising material for broadband tunable fiber laser. Furthermore, the melt‐in‐tube method demonstrated here may open a new gate toward the fabrication of novel glass‐ceramic fibers.     

Influence of the Eu2+ on the Silver Aggregates Formation in Ag+–Na+ Ion‐Exchanged Eu3+‐Doped Sodium–Aluminosilicate Glasses

Europium‐doping sodium–aluminosilicate glasses are prepared by melt‐quenching method, in which europium ions were spontaneously reduced from their trivalent to divalent state. The silver was introduced into glasses by Ag⁺–Na⁺ ion exchange and the interactions between europium ions and silver species were investigated. Owing to energy transfer (ET) from Ag⁺/silver aggregates to Eu³⁺, significant enhancements of Eu³⁺ emission were observed for 285/350‐nm excitation, respectively. The divalent europium ions promote the formation of silver aggregates in the process of ion exchange.     

Optical Thermometry Based on Up‐Conversion Luminescence Behavior of Er3+ ‐Doped Transparent Sr2YbF7 Glass‐Ceramics

Transparent novel glass‐ceramics containing Sr₂YbF₇:Er³⁺ nanocrystals were successfully fabricated by melt‐quenching technique. Their structural and up‐conversion luminescent properties were systemically investigated by XRD, HRTEM, and a series of spectroscopy methods. The temperature‐dependent up‐conversion spectra prove that ²H_11/2 and ⁴S_3/2 levels of Er³⁺ are thermally coupled energy levels (TCEL). Consequently, the ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 emissions of Er³⁺ in Sr₂YbF₇:Er³⁺ glass‐ceramics can be used as optical thermometry based on fluorescence intensity ratio (FIR) technique. Combined with low phonon energy and high thermal stability, Er³⁺ ions in Sr₂YbF₇ glass‐ceramics present broad operating temperature range (300–500 K), large energy gap of TCEL (786 cm^?1) and high theoretical maximum value of relative sensitivity (62.14 × 10^?4 K^?1 at 560 K), which suggests that Sr₂YbF₇:Er³⁺ glass‐ceramics may be excellent candidates for optical temperature sensors.     

Eu2+‐Doped Yellow‐Emitting CsBaB3O6 Glass‐Ceramic Prepared by Melt Quenching and Re‐Crystallization Method

Eu³⁺‐doped cesium barium borate glass with the composition of Cs₂O·2BaO·3B₂O₃ was prepared by the conventional melt quenching method. The glass‐ceramic sample was obtained from the re‐crystallization of the as‐made glass to change the amorphous glass into a crystalline host. This reduces the Eu³⁺ in glass to Eu²⁺ ions resulting in a yellow‐emitting phosphor of Eu²⁺‐activated CsBaB₃O₆. The samples were investigated by the XRD patterns and SEM micrograph, the optical absorption, the photoluminescence spectra, and decay curves. The as‐made glass has only Eu³⁺ centers. Under the excitation of blue or near‐UV light, Eu²⁺‐doped CsBaB₃O₆ presents yellow‐emitting color from the allowed inter‐configurational 4f–5d transition in the Eu²⁺ ions. The maximum absolute luminescence quantum efficiencies of Eu²⁺‐doped CsBaB₃O₆ phosphor was measured to be 47% excited at 430 nm light at 300 K. By taking into account the efficient excitation in blue wavelength region, this new phosphor could be a potential yellow‐emitting phosphor for an application in white light‐emitting diodes fabricated with blue chips.     

Difference in the Nature of Eu3+ Environment in Eu3+‐Doped BaTiO3 and BaSnO3

BaTiO₃ and BaSnO₃ samples doped with Eu³⁺ ions were prepared using glycine‐nitrate gel combustion method. Relative intensities and line shapes of magnetic dipole allowed ⁵D₀ → ⁷F₁ and electric dipole allowed ⁵D₀ → ⁷F₂ transitions of Eu³⁺ from the hosts, BaTiO₃ and BaSnO₃, are significantly different. Based on detailed structural investigations, it is confirmed that synthesizedBaTiO₃ sample is tetragonal with no center of symmetry around Ba²⁺ ions. Unlike this BaSnO₃ is cubic with centrosymmetric Ba²⁺ site. From X‐ray diffraction and experimentally obtained Judd–Ofelt parameters (Ω₂ and Ω₄ values), it is confirmed that in BaTiO₃ there is a decrease in the average Ba–O and Ba–Ba distances compared with that in BaSnO₃. This leads to higher Eu–O bond polarizability and adds to the distortion in its environment around Eu³⁺ in BaTiO₃:Eu compared with BaSnO₃:Eu. This is responsible for the observed difference in the luminescence properties.     

Luminescence and Quantum Efficiencies of Eu3+‐Doped Vanadate Garnets

Nondoped and 5.0 mol% Eu³⁺‐doped vanadate garnets Ca₅Mg₄(VO₄)₆, NaCa₂Mg₂[VO₄]₃, KCa₂Mg₂[VO₄]₃, and NaSr₂Mg₂[VO₄]₃ were synthesized by solid‐state reactions. The formation of single‐phase compound with garnet structure is confirmed by X‐ray diffraction. The photoluminescence (PL) and PL excitation (PLE) spectra are investigated together with color coordinates. The luminescence process is discussed on the charge‐transfer transitions in [VO₄]^3? ions and the crystal structure. The PL quantum efficiencies (QE) are measured for nondoped and Eu³⁺‐doped samples. The Eu³⁺‐doped samples have higher QEs than the corresponding nondoped ones although the energy transfer occurs from [VO₄]^3? to Eu³⁺. Broad emission band due to [VO₄]^3? with intense sharp lines due to Eu³⁺, which gives white color, is observed in Eu³⁺‐doped NaCa₂Mg₂[VO₄]₃ and NaSr₂Mg₂[VO₄]₃ under excitation with UV light. These materials are suggested to be useful for lighting under the excitation with near‐UV LED.     

Synthesis and Characterization of Oxyanion‐Doped Cobalt Containing Perovskites

In this paper, we report the incorporation of borate, silicate and phosphate into La_0.6Sr_0.4Co_0.8Fe_0.2O_3–δ (LSCF) and Sr_0.9Y_0.1CoO_3–δ (SYC) cathode materials for solid oxide fuel cells (SOFCs). In the former, an increase in the electronic conductivity was observed, which can be correlated with electron doping due to the oxyanion doping favoring the introduction of oxide ion vacancies. The highest conductivity was observed for La_0.6Sr_0.4Co_0.76Fe_0.19B_0.05O_3–δ, 1190 S cm^–1 at 700 °C, in comparison with 431 S cm^–1 for undoped La_0.6Sr_0.4Co_0.8Fe_0.2O_3–δ at the same temperature. For Sr_0.9Y_0.1CoO_3–δ series the conductivity suffers a decrease on doping, attributed to any effect of electron doping being outweighed by the effect of partial disruption of the electronic conduction pathways by the oxyanion. Composites of these cathode materials with 50% CGO10 were examined on dense CGO10 pellets and the area‐specific resistances (ASR) in symmetrical cells were determined. The ASR values, at 800 °C, were 0.20, 0.08 and 0.11 Ω cm² for La_0.6Sr_0.4Co_0.8Fe_0.2O_3–δ, La_0.6Sr_0.4Co_0.76Fe_0.19B_0.05O_3–δ and La_0.6Sr_0.4Co_0.78Fe_0.195Si_0.025O_3–δ, respectively. For the SYC materials, the oxyanion‐doped compositions also showed an improvement in the ASR values with respect to the parent compounds, despite the lower electronic conductivity in these cases. This observation may be due to an increase in ionic conductivity due to oxyanion incorporation leading to the formation of oxide ion vacancies. In addition, the stability of these systems towards CO₂ was studied. For La_0.6Sr_0.4Co_0.8(1–x)Fe_0.2(1–x)M_xO_3–δ series, all compositions showed no evidence for reactivity with CO₂ between RT and 1000 °C. On the other hand, for the Sr_0.9Y_0.1Co_1–xM_xO_3–δ series, some reactivity was observed, although the CO₂ stability was shown to be improved on oxyanion doping. Thus, these results show that oxyanion doping can have a beneficial effect on the performance of perovskite cobaltite cathode materials.     

Synthesis and Structural Probing of Eu3+ Doped BaYF5 Nano-Crystals in Transparent Oxyfluoride Glass-Ceramics

Transparent oxyfluoride glass-ceramics containing Eu: BaYF₅ nano-crystals in the newly developed SiO₂–K₂CO₃–BaF₂–YF₃–Sb₂O₃ glass system are synthesized by melt quenching method followed by optimized ceramization process. The X-ray diffraction, transmission electron microscopy, and field emission scanning electron microscopy confirmed the precipitation of tetragonal BaYF₅ nano-crystals in glass matrix. The coexistence of Eu²⁺ and Eu³⁺ ions in both glass and glass-ceramics are ascertained from their emission and excitation spectra. The in situ formation of divalent europium (Eu²⁺) along with Eu³⁺ during high temperature synthesis under ambient atmosphere is explained through optical basicity model. The Eu³⁺ emission from upper excitation states (⁵D₃₋₁) and reduced asymmetry ratio (R = I_ED/I_MD) in glass-ceramics have established the dopant ion incorporation into fluoride nano-crystalline environment. The observed luminescence properties of Eu:BaYF₅ are compared with that of Eu:BaYF₅ nanocrystals containing transparent glass-ceramics and their marked differences are discussed.     

Optical Property of Dy3+‐and Ce3+‐Doped Si–B–Na–Sr Glasses

Novel Dy³⁺ and Ce³⁺ doped Si–B–Na–Sr (SBNS) glasses were synthesized by melt‐quenching technique. Excited by 327 nm, the 0.5Dy³⁺‐and 0.5Ce³⁺‐doped SBNS exhibits white emission with Commission Internationale de L'Eclairage coordinates of (0.308, 0.280). Basic optical characterizations have been performed by measuring the absorption and emission spectra and calculating Judd–Ofelt intensity parameters, radiative probability, luminescence branching ratio, cross sections, and effective bandwidth. The Judd–Ofelt parameters Ω₂, Ω₄, and Ω₆ indicate a high asymmetrical environment and covalent environment in the optical glass. The emission color of Ce³⁺ and Dy³⁺ codoped transparent glass can be tuned from blue to white through energy transfer from Ce³⁺ to Dy³⁺ ions. The resulting glass may have potential application in white‐light‐emitting source.     

Effect of Gd Content on Luminescence Properties of Eu3+‐Doped La2−xGdxZr2O7 Transparent Ceramics

3 at.% Eu³⁺‐doped La_2?xGd_xZr₂O₇ (x = 0–2.0) transparent ceramics were fabricated by vacuum sintering. The effect of Gd content on crystal structure, in‐line transmittance, and luminescence property of the ceramics were investigated. The ceramics are all cubic pyrochlore structure with high transparency. The cut‐off edge of the transmittance curve of the ceramics varied with Gd content and was also affected by the annealing process. The luminescence intensity became stronger for the ceramics annealed in air. As Gd content increased, the energy band structure as well as the luminescence behavior of the ceramics was changed; in addition, the symmetry of the crystal lattice reduced, resulting in the shift of the strongest luminescence peak from 585 nm to around 630 nm.