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.     

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。     

Potential Barrier of (Zn,Nb)SnO2‐Films Induced by Microwave Thermal Diffusion of Cr3+ for Low‐Voltage Varistor

The effect of Cr³⁺ on the electrical properties of SnO₂‐based films deposited by electrophoresis on Si/Pt substrate was considered. The films were sintered in a microwave oven at 1000°C/40 min and then the surface was modified with deposition of Cr³⁺ ions by electrophoresis. The diffusion of Cr³⁺ contributes to the modification of the potential barrier formed on the grain boundary improving the electrical properties due to electron acceptor species adsorption on the grain boundary. The influence on the properties of grain boundary was verified by I versus V characterization in as a function of temperature. The films showed nonlinear coefficient over 9, potential barrier height over 0.5 eV and resistivity greater than 10⁷ Ω·cm. 4 samples were prepared at same conditions and presented similar electrical behavior, showing the efficiency of technique on reproducibility to varistor properties control. Thereby the nonlinear coefficient increases while decreasing the conductivity of the system is noticed.     

Improved Blue‐Emitting AlN:Eu2+ Phosphors by Alloying with GaN

A method is designed to improve the luminescence of AlN‐based phosphors by tuning the band structure and crystal structure due to alloying with GaN. The pure (Al,Ga)N:Eu phosphors were initially prepared by gas‐phase reaction in an NH₃ atmosphere. GaN alloying was used to expand the crystal lattice of AlN due to Ga³⁺ substituting for smaller Al³⁺ ions, making dissolution of Eu²⁺ easier. The dissolution of Ga in the AlN lattice was proven by the result of the Rietveld refinement and the increase in lattice parameters with increasing Ga content. To introduce other energy states mixing with the 5d states of Eu²⁺, Ga doping was also used to tune the band structure of AlN by acting on Eu²⁺ ions. The theoretical result was analyzed using the Cambridge Sequential Total Energy Package (CASTEP). According to the calculated total and atom resolved partial density of states, it was observed that the Ga 5p states contribute a large portion to the corresponding Eu²⁺ absorption band in (Al,Ga)N:Eu phosphors. As a consequence, an enhanced emission intensity at 470 nm and a high quantum efficiency for excitation at 330 nm was obtained despite of stronger thermal quenching of the (Al,Ga)N:Eu phosphors compared with AlN:Eu.     

Synthesis and Luminescent Properties of the Li0.995−xMgxSi2−xAlxN3: Eu2+0.005 Phosphors

Li_0.995?xMg_xSi_2?xAl_xN₃: Eu²⁺_0.005 (LSN: xM) (0 ≤ x ≤ 0.04) phosphors were successfully synthesized by gas‐pressed sintering. Double substitution which is partial replacement of (LiSi)⁵⁺ with (MgAl)⁵⁺ is presented as a useful way to improve luminescence properties. With an increase in the substitution concentration, the intensity of the emission band of LSN: xM was enhanced and the peak position shows blue shift due to the decreased stokes shift. Furthermore, LSN: xM (0 ≤ x ≤ 0.04) shows narrower full width at half maximum and higher thermal stability than Li_0.995Si₂N₃: Eu²⁺_0.005.     

Synthesis of Red‐Emitting AgGd0.9Eu0.1(MoO4)2 Phosphors by Precipitation at Room Temperature

A series of Eu³⁺‐doped AgGd(MoO₄)₂ red phosphors with well‐defined shape and size were prepared via a precipitation method at room temperature. The samples were characterized by X‐ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence (PL) spectroscopy. The crystallinity, particle size, morphology, and luminescent properties of the as‐prepared products were tuned by controlling the reaction conditions such as the precipitation reagents used and the pH of the initial solution. XRD results showed that all of the synthesized samples adopted a pure tetragonal structure. The formation mechanism of AgGdMo₂O₈ was investigated in detail, and two intermediates were found to be essential. Photoluminescence properties of the as‐prepared AgGd_0.9Eu_0.1(MoO₄)₂ phosphors under diverse experimental conditions were also studied systematically, and their emission spectra showed emission characteristic of Eu³⁺.     

Tuning the Color Emission of Sr2P2O7: Tb3+, Eu3+ Phosphors Based on Energy Transfer

A series of color tunable Tb³⁺‐ and Eu³⁺‐activated Sr₂P₂O₇ phosphors were synthesized by a traditional solid‐state reaction method in air atmosphere. The crystal structure, photoluminescence (PL) properties, energy transfer, thermal stability, and luminous efficiency were investigated. A series of characteristic emission of Tb³⁺ and Eu³⁺ were observed in the PL spectra and the variation in the emission intensities of the three emission peaks at around 416 nm (blue), 545 nm (green), and 593 nm (orange‐red) induced the multicolor emission evolution by tuning the Tb³⁺/Eu³⁺ content ratio. The energy‐transfer mechanism from Tb³⁺ to Eu³⁺ ion was determined to be dipole–dipole interaction, and the energy‐transfer efficiency was about 90%. The novel phosphors have excellent thermal stability in the temperature range of 77–473 K and the Commission International De L'Eclairage 1931 chromaticity coordinates of Sr₂P₂O₇: Tb³⁺, Eu³⁺ (λ_ex = 378 nm) move toward the ideal white light coordinates.     

Precipitation Synthesis and Color‐Tailorable Luminescence of α‐Zr(HPO4)2: RE3+(RE = Eu,Tb) Nanosheet Phosphors

The rare earth (RE = Eu and Tb) ions‐doped α‐Zr(HPO₄)₂ (ZrP) nanosheet phosphors were synthesized by direct precipitation method, and their structures and photoluminescence properties were investigated. The results of X‐ray diffraction and scanning electron microscopy indicated that the systems of ZrP:RE³⁺ had similar nanosheet structure except with relatively larger interlayer spacing as compared with pure α‐ZrP. Under the excitation of UV light, the ZrP:RE³⁺ nanosheet phosphors showed red and green emission peaks corresponding to the ⁵D₀→⁷F₂ transition of Eu³⁺ and the ⁵D₄→⁷F₅ transition of Tb³⁺, respectively. After Eu³⁺ and Tb³⁺ were co‐doped in ZrP host, not only the red and green emission peaks were simultaneously observed, but also the luminescent intensity and fluorescence lifetimes of Tb³⁺ were gradually decreased with the increase in Eu³⁺‐doping concentration, which implied the energy transfer from Tb³⁺ to Eu³⁺ happened. It was deduced that the energy transfer from Tb³⁺ to Eu³⁺ occurred via exchange interaction. Through optimization to the samples, a nearly white‐light emission with the color coordinate (0.322, 0.263) was achieved under 377 nm excitation. The ZrP:RE³⁺ nanosheet phosphors may be a potential color‐tailorable candidate for fabricating optoelectronic devices such as electroluminescence panels.     

Combustion Synthesis of Ca2Si5N8: Eu2+ Phosphors and their Luminescent properties

A combustion synthesis method has been developed for synthesis of Eu²⁺‐doped Ca₂Si₅N₈ phosphor and its photoluminescence properties were investigated. Ca, Si, and Eu₂O₃ powders were used as the Ca, Si, and Eu sources. NaN₃ and NH₄Cl were found necessary to be added for the formation of the product phase and addition of Si₃N₄ was found to enhance the product yield. These powders were mixed and pressed into a compact, which was then wrapped up with an igniting agent (Mg + Fe₃O₄). The reactant compact was ignited by electrical heating under a N₂ pressure of 0.7 MPa. Effects of these experimental parameters on the product yield were investigated and a reaction mechanism was proposed. The synthesized Ca₂Si₅N₈: Eu²⁺ phosphor absorbs light in the region of 300–520 nm and shows a broad band emission in the region of 500–670 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺. Eu₂O₃ was found partially unreacted and a certain amount of oxygen is believed to be incorporated into the lattice of the product phase. The peak emission intensity (~93% of a commercially available phosphor, YAG:Ce³⁺v) and the peak emission wavelength (571–581 nm) were found to be lower and shorter, respectively, than that reported in the literature. These are considered to be mainly due to oxygen incorporation, which not only reduces nephelauxetic effect and crystal field splitting but also causes a lowering of internal quantum efficiency.     

White‐Emitting Tuning and Energy Transfer in Eu2+/Mn2+‐Substituted Apatite‐Type Fluorophosphate Phosphors

Herein, a series of Eu²⁺&Mn²⁺substituted fluorophosphates Ca₆Gd₂Na₂(PO₄)₆F₂ phosphor with apatite structure have been synthesized and investigated by the powder X‐ray diffraction, photoluminescence spectra, fluorescence decay curves, thermal quenching, and chromaticity properties. Particularly, both Eu²⁺ and Mn²⁺ emissions at the two different lattice sites 4f and 6h in Ca₆Gd₂Na₂(PO₄)₆F₂ matrix have been identified and discussed. The dual energy transfer of Eu²⁺→Mn²⁺ and Gd³⁺→Mn²⁺ in Ca₆Gd₂Na₂(PO₄)₆F₂:Eu²⁺,Mn²⁺ samples have been validated and confirmed by the photoluminescence spectra. The dependence of color‐tunable on the activator concentration of Mn²⁺ was investigated to realize white light emission. By varying the doping concentration of the Mn²⁺ ion, a series of tunable colors including pure white light and candle light are obtained under the excitation of 350 nm. Moreover, the fluorescence decay curves have been fitted and analyzed using the Inokuti–Hirayama theoretical model to estimate the Eu–Mn interaction mechanism. We also investigated temperature‐dependent photoluminescence quenching characteristics according to the Arrhenius equation. Preliminary studies on the properties of the phosphor indicated that the obtained phosphors might have potential application as a single‐component white‐emitting phosphor for UV‐based white LEDs.     

Long Afterglow SrAl2O4:Eu2+,Dy3+ Phosphors as Luminescent Down‐Shifting Layer for Crystalline Silicon Solar Cells

SrAl₂O₄:Eu²⁺,Dy³⁺ phosphors can convert near ultraviolet light with lower sensitivity to the solar cell to yellow‐green light at which the solar cell has higher sensitivity and exhibit the excellent luminescent property of long persistence. Therefore, in this study, the authors firstly synthesized the fine SrAl₂O₄:Eu²⁺,Dy³⁺ phosphors and then produced SrAl₂O₄:Eu²⁺,Dy³⁺/SiO₂ composite films as spectral shifters to understand the effects of SrAl₂O₄:Eu²⁺,Dy³⁺ phosphor on photoelectric conversion efficiencies of a crystalline silicon photovoltaic module. Under one sun illumination, the composite film containing an appropriate amount of SrAl₂O₄:Eu²⁺,Dy³⁺ phosphor enhances the photoelectric conversion efficiency of the cell through spectral down‐shifting as compared to the bare glass substrate, and the maximum achieves 11.12%. In contrast, the commercial SrAl₂O₄:Eu²⁺,Dy³⁺ phosphor composite film is not effective for improving the photoelectric conversion efficiency because of the relatively lower visible light transmittance of film caused by the large aggregates. After one sun illumination for 1 min, the light source was turned off, and the cell containing the synthesized SrAl₂O₄:Eu²⁺,Dy³⁺ phosphor still shows an efficiency of 1.16% in the dark due to the irradiation by the long persistent light from SrAl₂O₄:Eu²⁺,Dy³⁺, which provides a possibility to fulfill the operation of solar cells even in the dark.     

Eu~(3+)掺杂的红色荧光粉制备及荧光性能研究

利用溶胶凝胶法制备了Eu3+掺杂的Y2O3荧光粉。考察了Y2O3:Eu3+的制备条件,进行了物相表征,研究了Y2O3:Eu3+的荧光性能。结果表明,在612 nm波长监测下,Y1.98O3:Eu3+0.02的激发光谱为300~550 nm,最大激发峰值位于466 nm,归属于Eu3+的7F0→5D2的跃迁。在466 nm波长激发下,Y2O3:Eu3+的发射光谱为550~700 nm,最大发射峰值位于612 nm,归属于Eu3+的5D0→7F2的跃迁主峰。Eu3+的掺杂量为x=0.02,p H=1时Y2O3:Eu3+荧光粉可以得到最强的红光荧光粉。     

Molecular‐Like Ag Clusters and Eu3+ Co‐Sensitized Efficient Broadband Spectral Modification with Enhanced Yb3+ Emission

AgNO₃/EuF₃/YbF₃ tri‐doped oxyfluoride glass was prepared by a melt‐quenching method, in which a high‐efficient broadband spectral modification can be realized due to the simultaneous energy‐transfer processes of Eu³⁺→Yb³⁺, molecular‐like Ag (ML‐Ag) clusters→Yb³⁺, and ML‐Ag clusters→Eu³⁺→Yb³⁺. The spectral measurements indicated that besides the F‐center brought by the fluorides, the formation of the ML‐Ag clusters and the evolution of silver species within the glass matrix were also closely related to the introduction of Eu³⁺ and Yb³⁺ ions and which in return greatly affected the luminescence properties of these rare‐earth ions. As the UV‐visible irradiation in the wavelength region of 250–600 nm can be efficiently converted into near‐infrared emission around 1000 nm in the AgNO₃/EuF₃/YbF₃ tri‐doped glass, which thus has promising application in enhancing the photovoltaic conversion efficiency of the silicon solar cell.     

White Light Emission from Sr2LiSiO4F:Sm3+,Tb3+ Phosphors Under Near‐UV Light Excitation

The Tb³⁺/Sm³⁺ codoped Sr₂LiSiO₄F white emitting phosphors were synthesized by a solid‐state reaction technique at high temperature. The X‐ray diffraction patterns, photoluminescence properties, and decay behaviors have been investigated. The Tb³⁺ emissions (blue and green) and Sm³⁺ emissions (orange) are both observed in the codoped samples Sr₂LiSiO₄F: 0.05Sm³⁺, xTb³⁺ by near‐UV light (370 nm) exciting. The white emission has been obtained by adjusting Tb³⁺ doping concentration at 5% (x = 0.05). These luminescent powders are expected to be a potential candidate as white emitting phosphor for near‐ultraviolet InGaN‐based white light‐emitting diodes.     

草酸沉淀法制备Y2O3：Eu^3＋粉体粒度控制

利用草酸沉淀法制备Y2O3：Eu^3 粉体。通过研究草酸沉淀过程中温度、酸度、浓度及前驱体煅烧温度等条件对粒度的影响，获得控制最终产物粒度的各种手段，进而得到分散性能良好、不结团、高光效、流明特性稳定的微米级Y2O3：Eu^3 荧光粉，以满足荧光粉生产的需要。     

草酸沉淀法制备Y2O3∶Eu3+粉体粒度控制

利用草酸沉淀法制备Y203∶Eu3+粉体.通过研究草酸沉淀过程中温度、酸度、浓度及前驱体煅烧温度等条件对粒度的影响,获得控制最终产物粒度的各种手段,进而得到分散性能良好、不结团、高光效、流明特性稳定的微米级Y203:Eu3+荧光粉,以满足荧光粉生产的需要.     

白光LED用钨酸盐红色荧光粉的制备及发光特性

采用高温固相法制备了NaY(WO_4)_2:xEu~(3+)(x=10%,15%,19%,21%,25%)红色荧光粉,并对此荧光粉的结构及发光性能进行了研究。研究结果表明,样品在用λ_(ex)=393 nm激发时,在λ=617 nm处得到了发光光谱。XRD结果表明,Eu~(3+)掺杂浓度达到25%(摩尔分数)时,仍然能够形成纯相的NaY(WO_4)_2:Eu~(3+)多晶粉末。随着Eu~(3+)浓度的增大,Na(WO_4)_2:Eu~(3+)光发射强度逐渐增大,当Eu~(3+)浓度为19%时,发光强度达到最大,随后出现浓度猝灭。     

Eu‐Doped β‐SiAlON Phosphors: Template‐Assistant Low Temperature Synthesis,Dual Band Emission,and High‐Thermal Stability

A hard template route has been successfully developed for synthesis of β‐SiAlON:Eu phosphors at low temperatures. The synthesis utilizes mesoporous silica (SBA‐15) skeleton as an active Si source, combined with the carbothermal reduction and nitridation method. It has been shown that the additional driving force from high surface area and porosity of SBA‐15 enables β‐SiAlON:Eu (with compositions of Si_6?zAl_z?xO_z+xN_8?z?x: xEu, x = 0.010–0.200 and z = 1.000) phosphors to be formed as a dominant phase at low temperature of 1400°C. The resultant β‐SiAlON:Eu phosphor powders exhibit a typical rod‐like morphology and a well dispersed state. By tailoring the Eu²⁺ concentration in the phosphors, a continuous change in emission band can be realized, that is a blue emission dominated for low Eu²⁺ concentrations and a green emission dominated for high Eu²⁺ doping concentrations. Furthermore, the resultant phosphors exhibit a small thermal quenching up to high temperature of 250°C. Therefore, the developed method is beneficial to synthesize LED phosphors of oxynitride systems at lower temperatures.     

Synthesis of Eu3+‐doped BaBi2Ta2O9 based glass‐ceramic nanocomposites: Optical and dielectric properties

In this paper we report for the first time synthesis of Eu³⁺‐doped transparent glass‐ceramics (TGC) with BaBi₂Ta₂O₉ (BBT) as the major crystal phase using the glass system SiO₂–K₂O–BaO–Bi₂O₃–Ta₂O₅ by melt quenching technique followed by controlled crystallization through ceramming heat treatment. DSC studies were conducted in order to determine a novel heat‐treatment protocol to attain transparent GCs by controlling crystal growth. The structural properties of the BBT GCs have been investigated using XRD, FE‐SEM, TEM and FTIR reflectance spectroscopy. Optical band gap energies of the glass‐ceramic samples were found to decrease with respect to the precursor glass. An increased intensity of emission along with increase in the average lifetime of Eu³⁺ was observed due to incorporation of Eu³⁺ ions into the low‐phonon energy BBT crystal site. The local field asymmetric ratios of all the samples were observed greater than unity. The dielectric constant (ε_r), dielectric loss, and dissipation factor values of both the base glass and ceramized samples were found to decrease with increase in frequency.     

白光LED用红色发光材料CaLa_2(MoO_4)_4:Eu~(3+)的微波辅助溶胶–凝胶法合成及发光特性

以柠檬酸为络合剂,采用微波辅助溶胶–凝胶法制备了CaLa2(MoO4)4:Eu3+红色荧光粉。研究了前驱体的热分解历程,分析表征了样品的结构、形貌和发光性能。探讨了焙烧温度、Eu3+掺杂量、柠檬酸与乙二醇摩尔比和硼酸用量等对样品发光性能的影响。结果表明:前驱体经700~900℃焙烧均能得到目标产物CaLa2–x(MoO4)4:x Eu3+,样品具有白钨矿结构,属于四方晶系。样品的激发光谱在250~350 nm处有一宽吸收带,对应于Mo–O,Eu–O电荷迁移带;在395和464 nm处存在很强的吸收峰,归属于Eu3+的4f–4f跃迁。发射光谱主峰位于616 nm处,归属于Eu3+的5D0→7F2电偶极跃迁发射。前驱体经800℃焙烧所得样品发光强度最大,且发光强度随着Eu3+掺杂量的增加而增大,在x=0.2~1.0范围内未出现猝灭现象。体系中加入适量乙二醇,可以起到细化晶粒、提高粉体分散性的作用,但浓度过高则会降低样品的发光强度;助熔剂硼酸的用量对样品发光强度影响较大,当用量为3%时,样品的发光性能较好。