La(BO_3,PO_4):Ce,Tb,Gd的发光研究

以 BPO4和稀土氧化物为原料制备了铈、铽、钆共掺杂的硼磷酸镧绿色荧光粉,研究了基质中 Gd3＋、 Ce3＋、 Tb3＋的发光特性及它们之间的相互作用。在该基质中存在 Ce3＋→ Gd3＋、Gd3＋→ Tb3＋、 Ce3＋→ Tb3＋的能量传递;当钆加入到铈、铽共掺杂的硼磷酸镧基质中会导致铈离子的发射减弱,铽离子 5D4→ 7FJ的发射显著增强,而 5D3→ 7FJ的发射没有明显变化,故有利于提高荧光粉的发光强度和绿色发射纯度。用硼磷酸钆作基质比用硼磷酸镧更能提高荧光粉的发光强度、发光纯度以及发光色坐标 x的值,所以 La(BO3,PO4):Ce,Tb,Gd和 Gd(BO3,PO4):Ce,Tb均是理想的绿色发射材料。     

CeO_2对Tb~(3+)掺杂硅酸盐玻璃发光和耐辐照性能的影响

采用高温熔制工艺制备出Tb3+掺杂硅酸盐玻璃,研究了CeO2对Tb3+掺杂硅酸盐玻璃发光和耐辐照性能的影响。结果表明,Ce3+的激发带与Tb3+的激发带部分重叠,使激发Tb3+离子发光的能量减少,Tb3+离子在550nm的发光被淬灭;激发停止后,Ce3+/Ce4+减少了由陷阱中逃逸出的空穴和电子的直接复合而传递给Tb3+的激发能量,Tb3+发光余辉缩短。通过铈离子价态变化:Ce4++eCe3+,CeO2引入可以减少辐照对基础玻璃和Tb3+的损伤。综合考虑发光和辐照稳定性,Tb3+掺杂硅酸盐玻璃中CeO2的引入量应控制在0.4%～0.8%(质量分数)。     

(La，Ce，Tb)(PO4，BO3)绿粉的合成及发光研究

首次用磷酸硼和稀土氧化物为主要原料制备铈、铽共激活的硼磷酸盐绿色荧光粉,并对Ce3+-Tb3+的能量传递进行了研究,发现在该基质中Ce3+、Tb3+间的能量传递为电多极子相互作用的共振传递,能量传递效率可高达90％。还研究了助熔剂对荧光粉粒度和发光特性的影响,实验结果表明,加了助熔剂后所得样品的颗粒明显变大,在254nm紫外激发下Tb3+发射大大zk强,光的纯度也得到改善。对不同基质荧光粉的研究发现,用硼磷酸盐绿粉比用硼酸盐和磷酸盐绿粉更适合做三基色粉配料。     

(La,Ce,Tb)(PO_4,BO_3)绿粉的合成及发光研究

首次用磷酸硼和稀土氧化物为主要原料制备铈、铽共激活的硼磷酸盐绿色荧光粉 ,并对Ce3+-Tb3+的能量传递进行了研究 ,发现在该基质中Ce3+、Tb3+间的能量传递为电多极子相互作用的共振传递 ,能量传递效率可高达 90 %。还研究了助熔剂对荧光粉粒度和发光特性的影响 ,实验结果表明 ,加了助熔剂后所得样品的颗粒明显变大 ,在 2 54nm紫外激发下Tb3+发射大大增强 ,光的纯度也得到改善。对不同基质荧光粉的研究发现 ,用硼磷酸盐绿粉比用硼酸盐和磷酸盐绿粉更适合做三基色粉配料。     

新型黄绿色发光材料Sr2MgSi3O9:Ce3+,Tb3+的合成及光谱分析

采用凝胶-燃烧法在活性炭弱还原气氛下成功合成了新型荧光粉Sr2MgSi3O9 :Tb3+、Sr2MgSi3O9:Ce3+,Tb3+,用X射线粉末衍射仪(XRD)、扫描电镜(SEM)、荧光分光光度计等对合成产物进行了分析和表征.结果表明,所合成的发光材料与Sr2MgSi2O7具有相似的晶体结构,同属四方晶系.样品一次颗粒近似球形,粒径在100nm左右.Sr2MgSi3O9:Tb3+的激发光谱为一位于249nm的宽带,发射光谱主要由473、491、547、585nm等一系列发射峰组成,其中473nm(5D3→<7F3)为主发射峰,547nm(5D4→7F5)为次发射峰;样品Sr1.955MgSi3O9:Tb3+0.04,Ce3+0.005的激发光谱由峰值分别位于249和335nm的双激发带组成,其中后者为主激发带.在335nm激发下,其发射光谱由两部分组成,其中400nm附近的带状发射对应于Ce3+的发射,而491、547、588nm处的发射峰归属为Tb3+的5+D4→7FJ(J=6,5,4)跃迁发射,最强峰位于547nm,对应Tb3+的5D4→7F5跃迁.此外,探讨了Ce3+掺杂量对样品发光亮度的影响,发现Ce3+可以把能量传递给Tb3+,对Tb3+起到敏化作用.     

Sm3+/Ce3+/Tb3+共掺CaO-B2O3-SiO2发光玻璃的制备及发光性能研究

采用高温熔融法制备了Sm3+/Ce3+/Tb3+共掺杂的CaO-B2O3-SiO2发光玻璃材料,并用荧光分光光度计和CIE色度坐标对其发光性能进行了研究。发射光谱表明,在374nm激发下,Sm3+/Ce3+/Tb3+共掺杂CaO-B2O3-SiO2发光玻璃的发射光谱中同时观测到了红橙光、蓝光和绿光的发射带,这些发射带的混合实现了白光发射。此外,在Sm2O3和Tb4O7含量不变的情况下,随着CeO2含量的减小,Sm3+/Ce3+/Tb3+共掺杂发光玻璃的发光颜色在白光区逐渐由蓝光区附近过渡到黄光区附近。     

Ca_8MgY(PO_4)_7:Re~(3+)(Re~(3+)=Eu~(3+),Ce~(3+),Tb~(3+))发光材料的合成及发光性能研究

采用固相法成功合成了具有β-Ca3(PO4)2结构的发光材料Ca8MgY(PO4)7∶Re3+(Re3+=Eu3+,Ce3+,Tb3+)。XRD、FT-IR及TG-DSC的测试结果表明,该发光材料的最佳烧结温度为1 200℃。PL测试结果表明,在252nm紫外光激发下,Ca8MgY(PO4)7∶Eu3+呈现Eu3+的特征发射,其中以位于612nm红光发射为主(5D0-7F2),Eu3+的最佳掺杂浓度为5.0%(摩尔分数)。在295nm紫外光激发下,Ce3+激活的Ca8MgY(PO4)7由峰值位于363nm的带状5d1-4f1发射为主,Ce3+的最佳掺杂浓度为1.0%(摩尔分数)。在228nm紫外光激发下,低掺杂浓度的Ca8MgY(PO4)7∶Tb3+以位于5D3-7FJ的蓝光发射为主,高掺杂浓度的Ca8MgY(PO4)7∶Tb3+以5D4-7FJ绿光发射为主,这是由于Tb3+的交叉弛豫造成的。Tb3+的最佳掺杂浓度为7.0%(摩尔分数)。     

Sr2Al2SiO7体系荧光粉掺杂Eu2＋和Ce3＋的光谱性能及能量传递研究

采用高温固相法合成了Sr2Al2SiO7∶Re（Re=Eu2＋,Ce3＋）荧光粉,研究了Eu2＋和Ce3＋在该基质中的发光特性,以及Eu2＋、Ce3＋共掺时的能量传递现象。研究表明Sr2Al2SiO7∶Eu2＋激发光谱呈宽带激发,最大发射峰位于513nm,Eu2＋最佳掺杂浓度为5%（摩尔分数）。Sr2Al2SiO7∶Ce3＋有两个激发峰,分别位于300和337nm,发射峰位于406nm,当Ce3＋浓度达到2%（摩尔分数）时发射强度最大。Eu2＋和Ce3＋在该体系共掺时存在Ce3＋到Eu2＋的有效能量传递,有利于提高体系的发光效率。     

绿色荧光粉Zn_2Ca(PO_4)_2:Tb~(3+)的制备及发光性能研究

采用高温固相法合成了绿色荧光粉Zn2Ca(PO4)2:Tb3+,测定了该荧光粉的XRD图谱、激发光谱及发射光谱。XRD图谱表明在高温还原气氛下合成了纯相的荧光粉Zn2Ca(PO4)2:Tb3+。该荧光粉的激发谱位于340～400nm。在紫外激发下主要发射峰位于490、544、584、622nm,对应于Tb3+的5D4→7F6、5D4→7F5、5D4→7F4、5D4→7F3的特征发射。考察了Tb3+的掺杂浓度对样品发光效率的影响,分析了Tb3+的544nm发射的自身浓度猝灭机理并探讨了敏化剂Ce3+离子的加入对荧光粉发光的影响。此绿色荧光粉Zn2Ca(PO4)2:Tb3+是一种很有潜力的适于UVLED管芯激发的发光粉。     

KBaPO4:Tb3+材料制备及其发光特性

采用高温固相法合成了KBaPO4:Tb3+绿色发光荧光粉,并研究了材料的发光性质.KBaPO4:Tb3+材料呈多峰发射,发射峰位于437、490、545、586和622 nm,分别对应Tb3+的5D3→7F4和5D4→7FJ=6,5,4,3跃迁发射,主峰为545 nm;监测545 nm发射峰,所得激发光谱由4f 7-5d1的宽带吸收(200～330 nm)和4f-4f电子吸收(330～400 nm)组成,主峰为380 nm.研究了Tb3+掺杂浓度,电荷补偿剂Li+、Na+、K+和Cl-,及敏化剂Ce3+对KBaPO4:Tb3+材料发射强度的影响.结果显示,调节激活剂浓度、添加电荷补偿剂或敏化剂均可在很大程度上提高材料的发射强度.上述结果表明KBaPO4:Tb3+材料是一种很好的近紫外光激发型高效绿色发光荧光粉.     

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.     

Tunable luminescence and energy transfer properties of Sr₃AlO₄F:RE³+ (RE = Tm/Tb, Eu, Ce) phosphors

Sr(3)AlO(4)F:RE(3+) (RE = Tm/Tb, Eu, Ce) phosphors were prepared by the conventional solid-state reaction. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), photoluminescence (PL) spectra, as well as lifetimes were utilized to characterize samples. Under the excitation of UV light, Sr(3)AlO(4)F:Tm(3+), Sr(3)AlO(4)F:Tb(3+), and Sr(3)AlO(4)F:Eu(3+) exhibit the characteristic emissions of Tm(3+) ((1)D(2)→(3)F(4), blue), Tb(3+) ((5)D(4)→(7)F(5), green), and Eu(3+) ((5)D(0)→(7)F(2), red), respectively. By adjusting the doping concentration of Eu(3+) ions in Sr(3)AlO(4)F:0.10Tm(3+), 0.10Tb(3+), zEu(3+), a white emission in a single composition was obtained under the excitation of 360 nm, in which an energy transfer from Tb(3+) to Eu(3+) was observed. For Sr(3)AlO(4)F:Ce(3+),Tb(3+) samples, the energy transfer from Ce(3+) to Tb(3+) is efficient and demonstrated to be a resonant type via a dipole-quadrupole interaction by comparing the experimental data and theoretical calculation. Furthermore, the critical distance of the Ce(3+) and Tb(3+) ions has also been calculated to be 9.05 ?. The corresponding luminescence and energy transfer mechanisms have been proposed in detail. These phosphors might be promising for use in near-UV LEDs.     

Investigations of Ce3+ co-doped SbPO4:Tb3+ nano-ribbons and nanoparticles by vibrational and photoluminescence spectroscopy

Nano-ribbons and very small nanoparticles (size 2-5 nm) of SbPO4 doped with lanthanide ions (Ce3+ and Tb3+) are prepared at a relatively low temperature of 120 degrees C based on a solution method. Detailed vibrational and luminescence studies on these samples establish that these lanthanide ions are incorporated at Sb3+ site of the SbPO4 lattice. The excitation spectrum corresponding to the Tb3+ emission and the excited state lifetime of the 5D4 level of Tb3+ ions in the sample confirm the energy transfer from Ce3+ to Tb3+ ions in the SbPO4 host. The extent of energy transfer from Ce3+ to Tb3+ in these samples is found to be around 60%. Dispersion of these nanomaterials in silica matrix effectively shields the lanthanide ions at the surface of the nano-ribbons/nanoparticles from the stabilizing ligands resulting in the reduction in the vibronic quenching of the excited state. Our results show significant reduction in the surface contribution in the decay curve corresponding to the 5D4 level of the Tb3+ ions after incorporating the nano-ribbons/nanoparticles in silica. These nanomaterials incorporated in silica matrix can have potential applications in bio-assays and bio-imaging.     

Polyol-mediated synthesis and photoluminescent properties of Ce3+ and/or Tb3+-doped LaPO4 nanoparticles

Rare-earth ion (Ce3+, Tb3+) doped LaPO4 nanoparticles were prepared by the polyol method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), UV-vis absorption spectroscopy, photoluminescence (PL) spectroscopy, and lifetimes. The results of XRD indicate that the as-prepared nanoparticles are well-crystallized at 160 degrees C and assigned to the monoclinic monazite structure of the LaPO4 phase. The obtained LaPO4:Ce3+, Tb3+ nanoparticles are spherical with narrow size distribution and average size of 20 nm. The doped rare-earth ions show their characteristic emission in LaPO4 nanoparticles, i.e., Ce3+ 5d-4f and Tb3+ 5D4-7FJ (J = 6-3) transitions, respectively. The optimum doping concentration for Tb3+ in La(0.8-x)Ce0.2TbxPO4 nanoparticles is determined to be 15 mol% (x = 0.15). The luminescence decay curves of Ce3+ in LaPO4:Ce3+ and LaPO4:Ce3+, Tb3+ nanoparticles present a single-exponential behavior, and the lifetimes (tau) of Ce3+ decrease with increasing Tb3+ concentrations (at the constant Ce3+ concentration) in LaPO4:Ce3+, Tb3+ nanoparticles due to the energy transfer from Ce3+ to Tb3+. The energy-transfer efficiency from Ce3+ to Tb3+ was calculated, which depends on the doping concentrations of Tb3+ if the concentration of Ce3+ is fixed.     

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。     

Luminescence and energy transfer characteristics of Ce3+- and Tb3+-codoped nanoporous 12CaO 7Al2O3 phosphors

The novel green-emitting phosphors of 12CaO 7Al2O3:Ce3+ , Tb3+ (C12A7:Ce3+, Tb3+) were synthesized by a solid-state reaction. Upon the excitation of Ce3+ at 350 nm, the C12A7:Ce3+, Tb3+ phosphor shows intense green emissions located at 543 nm assigning to 5D4-7F5 transitions of Tb3+ ions, and weak blue emissions centered at 434 nm due to the transitions of Ce3+ 5d-4f. The photoluminescence (PL) intensity of Ce3+ decrease with increasing Tb3+ concentration, indicating the effective energy transfer (ET) occurred from Ce3+ to Tb3+ in C12A7:Ce3+, Tb3+. The ET efficiency between Ce3+ and Tb3+ in the optimum composition reaches to 99%. Based on Dexter's ET theory, we have demonstrated that the efficient ET is a resonant type via dipole-dipole mechanism with an energy transfer critical distance of 4.02 A. Our results suggested that C12A7:Ce3+, Tb3+ phosphor would be a promising green-emitting phosphor for UV-converting white light-emitting diodes.     

White Light Emission Characteristics of Tb~(3+)/Sm~(3+) Co-Doped Glass Ceramics Containing YPO_4 Nanocrystals

The Tb~(3+)/Sm~(3+) single-doped and co-doped glasses and glass ceramics containing YPO_4 nanocrystals have been synthesized by melt quenching method. The structural and luminescent properties of these glass specimens were investigated. Under 375 nm wavelength excitation, the emission spectra combined with blue, green and red bands were observed, which achieved the white light emission. Moreover, the energy transfer between Tb~(3+) and Sm~(3+)ions was validated by decay lifetime measurement and energy level diagram.The color coordinates(x = 0.333, y = 0.333), correlated color temperature(5595 K) and the color rendering index(Ra = 80.5) indicated that the glass ceramics were considered to be good lighting source. Hence,the YPO_(4-) based Tb~(3+)/Sm~(3+) co-doped glass ceramics can act as potential matrix materials for white lightemitting diodes under ultraviolet excitation.