Investigation on Yb3+∕Er3+∕Tm3+ tri-doped phosphate glass ceramic for white-light-emitting diode

Yb3+∕Er3+∕Tm3+ tri-doped phosphate glass ceramics were prepared by a high-temperature melting method and thermal treatment technology. Upconversion (UC) emissions of the Yb3+∕Er3+∕Tm3+ tri-doped phosphate glass ceramic samples were studied under 975 nm excitation. The glass ceramic samples can simultaneously generate blue, green, and red emissions. The multicolor emission obtained was tuned to white light by adjusting the Er3+ ion concentration. The emission color of the sample doped with 8 mol.% Er3+ ion is white to the naked eye, and CIE coordinates (x=0.316, y=0.354) of the sample are close to the standard equal energy white-light illumination (x=0.333, y=0.333). The material will be useful in developing the white-light-emitting diode.     

真空紫外光激发下Tb~(3+)激活的稀土正硼酸盐的发光

报导了Tb3+、Ce3+激活的稀土正硼酸盐的真空紫外光谱。分析了Ce3+的4f75d能级随基质结构、基质阳离子的变化,讨论了温度、Tb3＋离子的浓度对发光的影响以及Ce3＋－Tb3＋间的能量传递.     

新型白光LED用SrMg_2(PO_4)_2单-基质荧光粉

本文通过高温固相法合成了紫外光LED用SrMg2(PO4)2为基质Eu2+,Tb3+和Mn2+为激活剂的白色荧光粉。采用XRD对荧光粉的结构和相纯度进行分析,Eu2+、Tb3+及Mn2+的加入对其结构没有明显的影响,且无杂相生成;当用Ca部分取代Sr时Eu2+和Mn2+的发射带分别发生红移和蓝移且二者之间存在着明显的能量传递;当引入共激活剂Tb3+时对其荧光光谱进行了详细研究,发现Eu2+和Tb3+,Eu2+和Mn2+之间存在部分的能量传递,通过调整它们的相对掺杂浓度可以得到发白光的荧光粉。     

Single-composition trichromatic white-emitting Ca4Y6(SiO4)6O: Ce3+/Mn2+/Tb3+ phosphor: luminescence and energy transfer

A series of Ca(4)Y(6)(SiO(4))(6)O (CYS): Ce(3+)/Mn(2+)/Tb(3+) oxyapatite phosphors were prepared via high-temperature solid-state reaction. Under UV excitation, there exist dual energy transfers (ET), i.e., Ce(3+)→Mn(2+) and Ce(3+)→Tb(3+) in the CYS: Ce(3+), Mn(2+), Tb(3+) system and their emitting colors can be adjusted from blue to orange-red via ET of Ce(3+)→Mn(2+) and from blue to green via ET of Ce(3+)→Tb(3+), respectively. Moreover, a wide-range-tunable white light emission with high quantum yields (13%-30%) were obtained by precisely controlling the contents of Ce(3+), Mn(2+) and Tb(3+) ions. On the other hand, the CL properties of CYS: Ce(3+), Mn(2+), Tb(3+) phosphors have been investigated in detail. The studied results indicate that the as-prepared CYS: Ce(3+), Mn(2+), Tb(3+) phosphors have good CL intensity and CIE color coordinate stability with a color-tunable emission crossing the whole white light region under low-voltage electron beam excitation. In general, the white light with varied hues has been obtained in Ce(3+), Mn(2+), and Tb(3+)-triactivated CYS phosphors by utilizing the principle of energy transfer and properly designed activator contents under UV (284, 358 nm) and low-voltage (1-5 kV) electron beam excitation, which make them as a potential single-composition trichromatic white-emitting phosphor.     

Gd3+-Tb3+能量转移与Tb3+自敏化效应对重金属锗酸盐玻璃发光性能的影响

研究了一组Tb^3 掺杂重金属锗酸盐玻璃的发光特性。玻璃样品的X射线激发发射光谱结果显示,玻璃基质中由Gd^3 离子向发光中心Tb^3 的能量转移机制以及在一定浓度范围内Tb^3 之间的交叉弛豫过程对玻璃的发光性能有重要影响。前者表现在Gd^3 紫外发射光的减弱及Tb^3 绿发射光的增强,后者则显示Tb^3 在一定浓度范围内所特有的自敏化效应,使其蓝发射光减弱、绿发射光增强。第3种稀土离子La^3 的引入对发光中心Tb^3 离子具有分离效应,使Tb^3 之间的交叉弛豫概率降低,蓝发射光增强。     

硅衬底Al2O3∶Tb3+薄膜的制备及其发光性能

采用溶胶凝胶法在硅衬底上制备了Al₂O₃∶Tb³⁺薄膜; 并采用DTA-TG、XRD、SEM、AFM及光致发光光谱对其进行了一系列表征; 分析了Al₂O₃∶Tb³⁺薄膜的发光机理, 探讨了热处理温度和Tb³⁺掺杂浓度对发光性能的影响规律. 研究结果表明, 采用溶胶凝胶法制备工艺, 制备了高发光强度的Al₂O₃∶Tb³⁺薄膜, 薄膜的最佳激发波长为240nm, Tb³⁺的最佳掺杂浓度为5mol%(Tb₂O₃/Al₂O₃=5mol%), 在240nm光激发下, 最强的发射峰出现在544nm附近; 并且制备的Al₂O₃∶Tb³⁺薄膜表面致密、平整且无裂纹产生, 表面粗糙度约为1.3nm, 有利于硅基光电子器件的制备和应用.     

Ce、Cr∶YAG微晶玻璃的制备及光谱性能研究

目前白光LED在红光波段发射较弱,导致其显色指数偏低,在白光LED用Ce∶YAG微晶玻璃中掺入Cr3+来增强红光波段的发射,从而提高显色指数。通过X射线衍射、荧光光度计、电光源参数测试对样品的晶相、光谱性能及荧光寿命进行了表征。研究了Cr3+对Ce∶YAG微晶玻璃发光性能的影响,并对其增红机理进行了初步的探讨。结果表明基质玻璃在1400℃热处理可析出纯的YAG晶相;Ce∶YAG和Ce、Cr∶YAG微晶玻璃在460nm激发下,在480～650nm产生有效发射,发射光谱中心波长位于530nm;由于Ce3+(2E)-Cr3+(4T)之间的非辐射能量传递,Ce、Cr∶YAG微晶玻璃在688、692和705nm处有红色发射峰,能有效地提高白光LED的显色性能。     

GdP_5O_(14):Eu~(3+),Sm~(3+)晶体的研究

本文报导了水热法合成 GdP_5O_(14)∶Eu~(3+),Sm~(3+)(GdPP∶Eu,Sm)晶体的工艺。观察了晶体缺陷形成的规律,分析和讨论了缺陷的成因。用 X-射线粉末衍射法测定了晶体结构及晶胞参数。研究了室温下晶体的紫外可见吸收光谱、激发光谱、荧光光谱和红外吸收光谱。总结和讨论了 Eu~(3+),Sm~(3+)离子的4f~n 组态电偶跃迁和磁偶跃迁的荧光发射规律。给出了 GdPP 晶体中 Eu~(3+),Sm~(3+)离子的能级图。对 Gd~(3+),Sm~(3+)→Eu~(3+)离子之间的能量转移进行了讨论。得到一些规律性结果。     

Er3+/Yb3+共掺氟硅酸盐玻璃陶瓷的制备及其量子剪裁发光行为

本文报道了一类组成为50SiO2-10Al2O3-20ZnF2-20SrF2-3YbF3-0.05ErF3(mol%)的氟氧化物玻璃陶瓷的制备及其量子剪裁发光行为。XRD和TEM分析结果显示,玻璃陶瓷中均匀分布有尺度10~40nm的SrF2析晶相。光谱研究表明,玻璃陶瓷在Er3+激发峰波长377nm激发下存在Er3+向Yb3+的有效能量传递,可实现包括量子剪裁效应在内的波长变换功能。随着热处理温度的升高,玻璃陶瓷的近红外977nm发光逐渐增强,荧光寿命显著增长。     

Strong photoluminescence through up and down conversion in Tm(3+)/Ho(3+):LaOF nanoparticles

Efficient up and down frequency conversions in Tm(3+) and Ho(3+) doped LaOF tetragonal nanocrystals have been investigated. Bright fluorescence emissions are obtained in co-doped Tm(3+)/Ho(3+):LaOF tetragonal nanocrystals through UV and infrared excitation. Green florescence from doped Ho(3+) ions, which can be clearly seen with bared eyes, is obtained when Tm(3+) ion is excited. Specific mechanism of the cross relaxation between doped ions is explored through spectroscopic measurements in time and frequency domains. About 90% energy transfer efficiency is obtained when the weak radiative and nonradiative relaxations are neglected.     

SiN_x:Tb~(3+)薄膜中Tb~(3+)与银表面等离激元耦合

本文采用PECVD方法在石英衬底上生长不同剂量比的氮化硅薄膜SiNx,并利用离子注入方法在SiNx中注入Tb3+离子。然后通过在SiNx薄膜表面沉积银岛膜,研究了银表面等离激元和SiNx:Tb3+发光的相互作用。研究发现,银岛膜的存在降低了SiNx:Tb3+发光荧光寿命,而且SiNx:Tb3+发光荧光寿命随着银岛膜厚度的增加而减小。而氮化硅薄膜中的硅纳米晶也会影响Tb3+的光模密度,并对SiNx:Tb3+发光荧光寿命产生影响。     

Effect of structure, particle size and relative concentration of Eu(3+) and Tb(3+) ions on the luminescence properties of Eu(3+) co-doped Y(2)O(3):Tb nanoparticles

Eu(3+) co-doped Y(2)O(3):Tb nanoparticles were prepared by the combustion method and characterized for their structural and luminescence properties as a function of annealing temperatures and relative concentration of Eu(3+) and Tb(3+) ions. For Y(2)O(3):Eu,Tb nanoparticles annealed at 600 and 1200?°C, variation in the relative intensity of excitation transitions between the (7)F(6) ground state and low spin and high spin 4f(7)5d(1) excited states of Tb(3+) is explained due to the combined effect of distortion around Y(3+)/Tb(3+) in YO(6)/TbO(6) polyhedra and the size of the nanoparticles. Increase in relative intensity of the 285?nm peak (spin-allowed transition denoted as peak B) with respect to the 310?nm peak (spin-forbidden transition denoted as peak A) with decrease of Tb(3+) concentration in the Y(2)O(3):Eu,Tb nanoparticles heated at 1200?°C is explained based on two competing effects, namely energy transfer from Tb(3+) to Eu(3+) ions and quenching among the Tb(3+) ions. Back energy transfer from Tb(3+) to Eu(3+) in these nanoparticles is found to be very poor.     

Spectroscopic properties of Eu3+/Nd3+ co-doped phosphate glasses and opaque glass–ceramics

This paper reports the fabrication and characterization of Eu³⁺/Nd³⁺ co-doped phosphate (PNE) glasses and glass–ceramics as a function of Eu³⁺ concentration. The precursor glasses were prepared by the conventional melt quenching technique and the opaque glass–ceramics were obtained by heating the precursor glasses at 450 °C for 30 h. The structural and optical properties of the glass and glass–ceramics were analyzed by means of X-ray diffraction, Raman spectroscopy, UV–VIS–IR absorption spectroscopy, photoluminescence spectra and lifetimes. The amorphous and crystalline structures of the precursor glass and opaque glass–ceramic were confirmed by X-ray diffraction respectively. The Raman spectra showed that the maximum phonon energy decreased from 1317 cm⁻¹ to 1277 cm⁻¹ with the thermal treatment. The luminescence spectra of the glass and glass–ceramic samples were studied under 396 nm and 806 nm excitation. The emission intensity of the bands observed in opaque glass–ceramic is stronger than that of the precursor glass. The luminescence spectra show strong dependence on the Eu³⁺ ion concentration in the Nd³⁺ ion photoluminescence (PL) intensity, which suggest the presence of energy transfer (ET) and cross-relaxation (CR) processes. The lifetimes of the ⁴F_3/2 state of Nd³⁺ ion in Eu³⁺/Nd³⁺ co-doped phosphate glasses and glass–ceramics under 806 nm excitation were measured. It was observed that the lifetimes of the ⁴F_3/2 level of Nd³⁺ of both glasses and glass–ceramics decrease with the increasing Eu³⁺ concentration. However in the case of opaque glass–ceramics the lifetimes decrease only 16%.     

Structure and optical properties of Dy3+/Tm3+ co-doped oxyfluoride glass ceramics containing β-NaGdF4 nanocrystals

Dy³⁺/Tm³⁺ co-doped oxyfluoride glass ceramics containing hexagonal β-NaGdF₄ nanocrystals were prepared by the melt-quenching method and subsequent heat-treatment procedure. During the crystallization process, the structural evolution of glass network was systematically investigated using XRD, TEM and FTIR spectra. Experimental results provided new evidences that a silica-enriched layer around the precipitated fluoride nanocrystals was formed during the crystallization process. Strong white light emission was obtained in the oxyfluoride glass ceramics by modifying the relative concentration ratio of Tm³⁺ and Dy³⁺ ions.     

Tb3+-Yb3+共掺氟氧化物微晶玻璃的发光特性及其外量子效率的评价

本研究制备了Tb3+-Yb3+共掺杂含CaF2纳米晶相的氟氧化物透明微晶玻璃,并通过XRD验证了CaF2纳米晶的形成。基于Tb3+对Yb3+的协同能量传递,通过激发Tb3+∶5D4能级可观察到由Yb3+∶2F5/2→2F7/2跃迁引起的950~1100nm近红外发射。利用积分球测试系统评价了Yb3+在玻璃及微晶玻璃体系中的外量子效率,数据表明经过热处理后Yb3+的外量子效率有明显的增加,这是由于在微晶玻璃体系中掺杂的Tb3+离子和Yb3+离子富集在具有低声子能量的CaF2晶相从而获得了更有效的能量传递而引起的。同时利用Tb3+荧光寿命计算获得了材料的内量子效率,其值远大于外量子效率,这是由计算过程中的诸多近似所导致。     

Structural and luminescence properties of Ho(3+)/Yb(3+)-doped Lu3Ga5O12 nano-garnets for phosphor applications

Lu3Ga5O12 nano-garnet powders doped with Ho(3+)/Yb(3+) ions have been prepared using a citrate sol-gel technique. The structural and morphological properties have been investigated by X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy. The materials are found to exist in single phase of cubic garnet structure with an average particle size of around 45 nm. The Ho(3+)/Yb(3+)-doped Lu3Ga5O12 nano-garnet powders give rise to an intense green and weak red emission of Ho3+ ions under 457.5 nm direct excitation. Moreover, when the Yb3+ ions are excited at 950 nm a very bright green luminescence of the Ho3+ ions is observed by the naked eyes even for such low laser power as 10 mW and the intensity of the red emission have been increased compared to that found under direct excitation of the Ho3+ ions. The power dependency and dynamics of the infrared-to-visible upconverted luminescence confirm the existence of different two-photon energy transfer processes. All these results have been compared with those obtained for other garnets doped with similar lanthanide ions which suggest that the Lu3Ga5O12 nano-garnets are potential materials for light emitting devices.     

Controllable morphology and high photoluminescence of (Y, Gd)(V, P) O4:Eu3+ nanophosphors synthesized by two-step reactions

Multi-ion doped YVO(4):Eu(3+) nanophosphors with high photoluminescence intensity were successfully prepared by a two-step reaction process for the first time, including YVO(4):Eu(3+) seeds synthesized by hydrothermal reaction and co-doping P(5+) and Gd(3+) in a sol-gel process. X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and photoluminescence spectroscopy were adopted to detect the structure, grain size, morphology and optical properties of the nanophosphors, respectively. Owning to the template-induced effect of the seeds, the morphology and size of the nanophosphors could be controlled by adjusting the molar ratios between the seeds and doping ions. The size of these nanophosphors increased as P(5+) and Gd(3+) co-doped. However, most of the samples kept approximately spherical morphology and narrow size distribution. The composition-optimized (Y, Gd)(V, P)O(4):Eu(3+) nanophosphors with spherical morphology in the 80-100 nm range exhibit better red emission and superior color saturation under vacuum ultraviolet excitation compared with that of the commercial phosphor (Y, Gd)BO(3):Eu(3+).     

White luminescence by up-conversion from thin film made with Ln(3+)-doped NaYF4 nanoparticles

White light-emitting thin films containing Ln(3+)-doped NaYF4 nanoparticles were prepared by a simple spin-coating method. White light was generated by two different lanthanide ions, Er3+ (red and green) and Tm3+ (blue), by upconversion process under the excitation of a 980-nm laser diode. The ratio of the intensity of the three main emissions was tuned by controlling the concentration of the nanoparticles in the thin film and the concentration of the lanthanide ions in the nanoparticles. The color coordinates corresponding to emissions of different nanoparticle concentrations and with the different pump powers were investigated. When the pump power was fixed at 900 mW, the thin film with a concentration ratio of 2.5:1 emitted pure white light with coordinates of (0.333, 0.339).     

Dy3+-doped nano-glass ceramics comprising NaAlSiO4 and NaY9Si6O26 nanocrystals for white light generation

The radiative emission properties of the Dy³⁺ ions in oxyfluoride glasses and glass ceramics have been investigated for the generation of white light. The X-ray diffraction pattern of the glass ceramics reveals the presence of NaAlSiO₄ nanocrystals along with secondary phase of NaY₉Si₆O₂₆ in the glass matrix after a suitable thermal treatment of the pristine glasses. Intense white light emission has been observed when the samples are excited with 350 nm light. Yellow to blue emission intensity ratios and chromaticity color coordinates have been determined from the visible luminescence spectra. All color coordinates are found to lie in the white region of the chromaticity color diagram proposing the suitability of the present studied materials for color display devices.     

YAG:Yb~(3+),Tm~(3+)纳米晶粉体的制备及其蓝色上转换发光

以稀土氧化物、硝酸铝为原料,采用溶胶-凝胶法合成了Yb3+、Tm3+共掺的钇铝石榴石(Y3Al5O12,YAG)纳米晶粉体。采用X射线衍射(XRD)确定了1200℃煅烧后的晶体粉为纯YAG结构,无杂质相,晶体尺寸约为90nm;该粉体在波长为980nm的半导体激光器激发下发射出中心波长为487nm的蓝色上转换荧光,对应于Tm3+离子的1G4→3H6的跃迁。发光强度和激发功率关系的研究揭示了其为双光子过程,Tm3+的激发态吸收及Tm3+、Yb3+间的交叉驰豫型能量传递和是该上转换发光的主要机制。