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.     

Ce3+‐ and Dy3+‐Doped Oxyfluoride Borosilicate Glasses with Near White Luminescence

A series of Ce³⁺/Dy³⁺‐doped oxyfluoride borosilicate glasses prepared by melt‐quenching method are investigated for light‐emitting diodes applications. These glasses are studied via X‐ray diffraction (XRD), optical absorption, photoluminescence (PL), color coordinate, and Fourier transform infrared (FT‐IR) spectra. We find that the absorption and emission bands of Ce³⁺ ions move to the longer wavelengths with increasing Ce³⁺ concentrations and decreasing B₂O₃ and Al₂O₃ contents in the glass compositions. We also discover the emission behavior of Ce³⁺ ions is dependent on the excitation wavelengths. The glass structure variations with changing glass compositions are examined using the FT‐IR spectra. The influence of glass network structure on the luminescence of Ce³⁺/Dy³⁺ codoped glasses is studied. Furthermore, the near‐ideal white light emission (color coordinate x = 0.32, y = 0.32) from the Ce³⁺/Dy³⁺ codoped glasses excited at 350 nm UV light is realized.     

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.     

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.     

Microstructure of Eu3+‐Doped Perovskites‐Type Niobate Ceramic La3Mg2NbO9

Eu³⁺‐doped red‐emitting ceramics of Eu³⁺‐doped La₃Mg₂NbO₉ were prepared via typical solid state. X‐ray diffraction and scanning electron microscope were utilized to characterize the ceramics. The photoluminescence excitation and emission spectra, the fluorescence decay curves, and color coordinates were investigated. The concentration quenching of the samples were discussed as well. The microstructures of the ceramics were discussed according to the spectral properties of probe ions of Eu³⁺, for example, substitution sites for Eu³⁺, inhomogeneous broadening and splitting of the emission bands, nonexponential decay, ⁵D₀→⁷F₀ emission transition, distorted symmetry sites, etc. The crystal structure of La₃Mg₂NbO₉ is heavily distorted due to the mixed occupation of Mg and Nb on B sites. Eu³⁺ ions only substitute La³⁺ sites and Eu³⁺ ions (or rare‐earth ions) are arranged in the heavily disordered environments over the whole structure in La₃Mg₂NbO₉.     

Synthesis and Characterization of Eu3+‐Doped Transparent Glass–ceramics Containing Nanocrystalline SrIINbIVO3

The glass–ceramics containing a rarely achievable nanocrystalline Sr^IINb^IVO₃ phase in the 53.75SiO₂–18.25K₂O–9Bi₂O₃–9SrO–9Nb₂O₅–0.5CeO₂–0.5Eu₂O₃ (mol%) glass system were prepared by the melt‐quench technique followed by a two‐stage controlled heat treatment. The unusual oxidation state of Nb in Sr^IINb^IVO₃ crystal is 4+ and upon heat treatment of the samples at lower temperature of 500°C for several hours, the glass composition and chemical environment around Nb ions played a key role for the formation of Sr^IINb^IVO₃ in the glass–ceramics. The microstructure of the glass–ceramics was studied using TEM and FESEM. The TEM images advocate 10–40 nm crystallite size of Sr^IINb^IVO₃. FTIR study confirms that all the samples consist of SiO₄, BiO₃, BiO₆, and NbO₆ structural units. The refractive index at different wavelengths was found to vary in the range 1.7105–1.7905 and increase with increase in heat‐treatment time. The luminescence spectra of Eu³⁺‐doped glass and glass–ceramics were recorded at 465 nm excitation wavelength and the luminescence intensity is found to be increased with heat‐treatment time due to increase in crystallinity. The high intensity ratio of ⁵D₀→⁷F₂ to ⁵D₀→⁷F₁ indicates that the Eu³⁺‐doped nanocrystalline Sr^IINb^IVO₃ glass–ceramics are promising candidate materials as red‐light source.     

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.     

Synthesis and Luminescence Properties of Blue‐Emitting Phosphor Eu2+‐Doped Zinc Fluoro‐Phosphate Zn2[PO4]F

Eu²⁺‐doped zinc fluoro‐phosphate Zn₂[PO₄]F was synthesized by the conventional high‐temperature solid‐state reaction. The phase formation was confirmed by X‐ray powder diffraction measurements and the structure refinement. The photoluminescence excitation and emission spectra, and the decay curves were measured. The natures of the Eu²⁺ emission in inorganic hosts, e.g., the emission and excitation properties, the chromaticity coordinates, the Stokes shifts, the absolute quantum efficiency, and the luminescence thermal stability were reported. Under the excitation of near‐UV light, Eu²⁺‐doped Zn₂[PO₄]F presents a narrow blue‐emitting band centered at 423 nm. The thermal stability of the blue luminescence was evaluated by the luminescence intensities as a function of temperature. The phosphor shows an excellent thermal stability on temperature quenching effects.     

Monitoring the t → m Martensitic Phase Transformation by Photoluminescence Emission in Eu3+‐Doped Zirconia Powders

In this work, we demonstrate that the martensitic t → m phase transformation of ZrO₂ powder stabilized with Eu³⁺ and Eu³⁺/Y³⁺ ions, can be effectively monitored by photoluminescence (PL) spectroscopy. As the luminescent properties of Eu³⁺ from within a host lattice are strongly influenced by the coordination geometry of the ion, we used the emission spectrum to monitor structural changes of ZrO₂. We synthesized Eu³⁺‐doped and Eu³⁺/Y³⁺‐codoped samples via the coprecipitation method, followed by calcination. We promoted the martensitic transformation by applying mechanical compression cycles with an increasing pressure, and deduced the consequential structural changes from the relative intensities of the ⁵D₀ → ⁷F₂ hypersensitive transitions, centered, respectively, at 606 and 613 nm whether the Eu³⁺ is in the eightfold coordinated site of the tetragonal phase or in the sevenfold coordinated site of the monoclinic phase. We suggest that the unique emission profile for Eu³⁺ ions in different symmetry sites can be exploited as a simple analytical tool for remote testing of mechanical components that are already mounted and in use. The structural changes observed by PL spectroscopy were corroborated by X‐ray powder diffraction (XRPD), with the phase compositions and volume fractions being determined by Rietveld analysis.     

Cathodoluminescence Properties of Blue Emitting Eu2+‐Doped AlN‐Polytypoids for Field‐Emission Displays

Eu²⁺‐doped AlN‐polytypoids (8H, 15R, 12H, and 21R) were successfully synthesized by nitrogen‐gas‐pressure sintering. The phosphors show intense blue emissions under the electron beam excitation. All the polytypoid phosphors exhibit relatively a smaller degradation in luminance and a higher thermal stability in comparison to the oxide counterparts. Among the polytypoids, 12H has no luminance saturation, and shows a brightness of 40 cd/m² at 3 kV and 100 μA. These results indicate that Eu²⁺‐doped AlN‐polytypoids could also be used as blue phosphors for FEDs.     

Structure and Luminescence of New Red‐Emitting Materials‐Eu3+‐Doped Triple Orthovanadates NaALa(VO4)2 (A = Ca,Sr, Ba)

The new red‐emitting phosphors of Eu³⁺‐doped triple orthovanadates NaALa(VO₄)₂ (A = Ca, Sr, Ba) were prepared by the high‐temperature solid‐state reaction. The formation of single phase compound with isostructural structure of Ba₃(VO₄)₂ was verified through X‐ray diffraction (XRD) studies. The photoluminescence excitation and emission spectra, the fluorescence decay curves and the dependence of luminescence intensity on doping level were investigated. The phosphor can be efficiently excited by near UV and blue light to realize an intense red luminescence (613 nm) corresponding to the electric dipole transition ⁵D₀→⁷F₂ of Eu³⁺ ions. Their potential applications as red‐emitting phosphors for solid‐state lighting were evaluated in comparison with the Eu³⁺‐doped lanthanum orthovanadate LaVO₄ and other reported references. The luminescence was discussed in detail on the base of the crystal structures. The luminescence thermal stability on temperature was investigated and the thermal activated energy was calculated. The phosphors can be suggested to be a potential red‐emitting phosphor for the application on white LEDs under irradiation of near‐UV or blue chips.     

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.     

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.     

Photoluminescence Properties of Heavily Eu3+‐Doped BaCa2In6O12 Phosphor for White‐Light‐Emitting Diodes

Heavily Eu³⁺‐doped BaCa₂In₆O₁₂ phosphors were prepared by conventional solid‐state reaction, and its structural properties were investigated by means of Rietveld refinement method using an X‐ray source. XRD patterns confirm the hexagonal phase of BaCa₂In₆O₁₂: Eu³⁺ phosphors. The obtained spectrum data indicate that the emission spectra of Ba_1?xEu_xCa₂In₆O₁₂ samples excited at 393 nm exhibit a series of shaped peaks assigned to the ⁵D_0,1,2,3 →⁷F_J (J = 0,1,2,3,4) transitions. Luminescence from the higher excited states, such as ⁵D₁, ⁵D₂, and ⁵D₃, were also observed even though the Eu³⁺ concentration was up to x = 0.4. More importantly, the Ba_1?xEu_xCa₂In₆O₁₂ phosphor still emits white luminescence, when the Eu³⁺ ion concentration is up to x = 0.07 before concentration quenching is observed, which shows that the phosphor is a promising single‐phase phosphor for near ultraviolet (NUV) light‐emitting diodes (LED). Furthermore, the temperature's impact on white luminescent properties was studied. Finally, a white‐light‐emitting diodes (W‐LEDs) fabricated with the Ba_0.95Eu_0.05Ca₂In₆O₁₂ phosphor incorporated with an encapsulant in ultraviolet LEDs (λ_max = 395 nm) is discussed.     

Spectral management and energy‐transfer mechanism of Eu3+‐doped β‐NaGdF4:Yb3+,Er3+ microcrystals

β‐NaGdF₄:Yb³⁺,Er³⁺ upconversion (UC) microcrystals were prepared by a facile hydrothermal process with the assistance of ethylene diamine tertraacetic acid (EDTA). The β‐NaGdF₄ UC microcrystal morphology was controlled by changing the doses of EDTA and NaF. Uniform hexagonal structure can be obtained at the 2 mmol EDTA and 9‐10 mmol NaF. The UC emissions of β‐NaGdF₄:Yb³⁺,Er³⁺ microcrystals were tuned by the variation of Eu³⁺ doping level (0%‐5%), where the red/green intensity ratio decreased with the Eu³⁺ concentration increase. It was found on the base of rate equations that with the Eu³⁺ doping, the energy back transfer process ²H_11/2/⁴S_3/2 (Er³⁺) → ⁴I_13/2 (Er³⁺) decreased. In addition, an energy‐transfer process from ⁴F_7/2 (Er³⁺) to ⁵D₁ (Eu³⁺) and a cross relaxation process of ⁷H_9/2 (Er³⁺) + ⁵D₀ (Eu³⁺) → ⁴F_7/2 (Er³⁺) + ⁵D₂ (Eu³⁺) were proposed and verified by rate equations, which dominated the energy‐transfer mechanism between Er³⁺ and Eu³⁺, resulted in the spectra tuning of β‐NaGdF₄:Yb³⁺,Er³⁺. The results suggested that the color tuning of β‐NaGdF₄:Yb³⁺,Er³⁺,Eu³⁺ UC microcrystals would have potential applications in such fields as flat‐panel displays, solid‐state lasers, and photovoltaics.     

GdF3∶Eu3+和NaGdF4∶Eu3+发光粉的可控合成与发光性质

采用聚乙烯吡咯烷酮(PVP)辅助水热法合成了GdF3∶Eu3+和NaGdF4∶Eu3+发光粉。利用X射线衍射(XRD)、扫描电子显微镜和荧光光谱对样品的结构、形貌和发光性能进行了研究。XRD分析表明:GdF3晶相到NaGdF4晶相的转换可以通过改变初始溶液pH值、PVP加入量和NaF与稀土离子(Gd3+和Eu3+)摩尔配比等合成条件实现。NaGdF4∶Eu3+发光粉的形貌受合成条件的影响。荧光光谱研究表明:GdF3∶Eu3+发光粉主发射峰位于593nm处,来自于Eu3+的5 D0→7 F1磁偶极跃迁;NaGdF4∶Eu3+发光粉主发射峰位于616nm,来自于Eu3+的5 D0→7 F2电偶极跃迁。2个样品中Gd3+与Eu3+离子之间存在较好的能量传递,而NaGdF4晶格更有利于2种离子的能量传递。     

Synthesis,Structure, and Thermally Stable Luminescence of Dy3+‐Doped Na3YSi2O7 Host Compound

Dy³⁺‐activated Na₃YSi₂O₇ phosphors have been prepared via a solid‐state reaction technique and may be used as a component of white light‐emitting diodes. X‐ray diffraction analysis demonstrates the single‐phase formation and the substitution of activator ions for Na₃YSi₂O₇:Dy³⁺ materials. The emission of Dy³⁺ in different Y³⁺ lattice sites exhibits blue (⁴F_9/2→⁶H_15/2) and yellow (⁴F_9/2→⁶H_13/2) lights, which function together to generate white light. The optimum doping concentration is 3 mol% and energy transfer between Dy³⁺ ions has been validated to be a resonant type via an electric dipole–dipole mechanism. The temperature‐dependent luminescent properties from 25°C to 400°C are studied, and the blue emission increases as a function of the temperature. This interesting phenomenon is proposed to be the result of the model in the configurational coordination diagram. The present investigation reveals the potential application for Na₃YSi₂O₇:Dy³⁺ system in solid‐state lighting.     

掺钆的铝酸锶铕镝磷光体的发光特性及晶相分析

采用高温固相法在弱还原气氛下制备了掺入Gd3+的SrAl2O4:Eu2+,Dy3+磷光体.研究了Gd3+对SrAl2O4:Eu2+,Dy3+磷光体的发光性能的影响.结果发现:引入Gd3+以后,对SrAl2O4基质的晶体结构基本上没有影响,也并未改变磷光体的发光光谱,却使磷光体的初始亮度显著提高,并使余辉时间延长.其余辉强度随时间的变化由最初的快衰减过程和随后的慢衰减过程组成,符合t-1.1的双曲线规律.并初步探讨了Gd3+的作用机制.     

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.