红色Bi4 Ge3 O12晶体在低温下的发光性能

用下降法制备了Bi₄Ge₃O₁₂晶体,发现生长出来的圆柱状晶体外侧呈现淡红色。对红色Bi₄Ge₃O₁₂晶体进行了低温(至8 K)下的近红外发射光谱及衰减寿命等测试分析。发现低温时(200 K以下)红色Bi₄Ge₃O₁₂在1 150 nm等波长处有较强的发射峰,强度随温度降低而增强,衰减时间为几百μs。     

Preparation and characterization of nanosized (Y,Bi)VO4:Eu and Y(V,P)O4:Eu red phosphors

Nanosized luminescent (Y,Bi)VO₄:Eu³⁺ and Y(V,P)O₄:Eu³⁺ were synthesized at low temperatures either by a coprecipitation method or by a hydrothermal method from aqueous solutions. The effect of Bi³⁺ ion or P⁵⁺ ion content in the lattice, annealing temperature effects on the crystal structure and the particle size, and the luminescence property of (Y,Bi)VO₄:Eu³⁺ and Y(V,P)O₄:Eu³⁺ nanoparticles were examined with a field-enhanced scanning electron microscopy, XRD, and a spectrofluorometer. The pristine YVO₄:Eu³⁺, (Y,Bi)VO₄:Eu³⁺, or Y(V,P)O₄:Eu³⁺ nanoparticles are 35-50 nm in size. The luminescence spectrum of the Eu³⁺ ion was used to probe its position in the crystal lattice. The dopant ions enter the same lattice sites in the nanocrystalline as in the corresponding bulk material, resulting similar spectral features between them. Photoluminescence intensity is weak for the pristine nanoparticles. Annealing the nanoparticles at temperatures up to 1000 °C results in the increased luminescence intensity (>80% of micrometer-sized phosphors) with the minimal particle growth and the improved particle crystallinity.     

Bismuth- and aluminum-codoped germanium oxide glasses for super-broadband optical amplification

Broadband infrared luminescence from bismuth-doped germanium oxide glasses prepared by a conventional melting-quenching technique was discovered. The absorption spectrum of the glasses covered a wide range from the visible to the near-infrared wavelength regions and consisted of five broad peaks below 370, 500, 700, 800, and 1000 nm. The fluorescence spectrum exhibited broadband characteristics (FWHM) greater than 300 nm with a maximum at 1300 nm pumped by an 808-nm laser. The fluorescence lifetime at room temperature decreased with increasing Bi2O3 concentration in the glass. Codoping of aluminum and bismuth was indispensable for the broadband infrared luminescence in GeO2:Bi, Al glass.     

太阳电池用YVO_4∶Eu~(3+)下转换材料的掺杂改性研究

为进一步提高YVO_4材料的下转换发光性能,在改进后的溶胶-凝胶法制备的YVO_4∶Eu~(3+)中,通过掺入Bi~(3+)来拓宽其在紫外波段的光谱吸收并提高其发光强度,通过掺入P~(5+)达到以PO_4~(3-)部分取代VO_4~(3-)来改善YVO_4∶Eu~(3+)的光输出稳定性及温度猝灭特性的目的。研究表明,掺入的Bi~(3+)和P~(5+)可成功取代YVO_4晶格中的Y~(3+)和V~(5+)。当Bi~(3+)掺入量较少时,样品仍然为四方晶系,Bi~(3+)较好地取代了Y~(3+)的晶格位置,形成单相的晶体结构。而在掺入少量的P~(5+)之后,YVO_4与YPO_4之间形成了均匀的固溶体。在350 nm激发光源作用下,当Bi~(3+)和P5+掺杂摩尔分数分别为0.04和0.10时,发光强度达到最大,特别是YV0.90P0.10O4∶0.05Eu~(3+)在619 nm处的发光强度要比YVO_4∶0.05Eu~(3+)的发光强度增大1.9倍。     

高色纯度白光LED用蓝光材料Gd2MgTiO6∶Bi^3+的合成及性能

采用高温固相法合成了一系列蓝光荧光粉Gd2-xMgTiO6∶xBi3+(0.0025≤x≤0.015),并对样品的表面形貌、晶体结构、发光性能和热稳定性进行了探究。SEM测试结果显示,样品Gd2MgTiO6∶Bi3+的粒径分布范围大,颗粒尺寸在1~5μm范围。XRD测试表明,Bi3+成功掺杂进入基质Gd2MgTiO6中且无杂相产生。荧光光谱测试结果表明,在375 nm波长激发下,蓝光荧光粉Gd2MgTiO6∶Bi3+于385~500 nm波长范围内呈现出属于Bi3+的1S0→3P1能级跃迁的窄带发射峰,且发射强度最大处位于418 nm,这有利于避免光的重吸收现象。不同掺杂浓度下样品的发射光谱研究表明,最佳Bi3+掺杂浓度为x=0.0075。此外,发光强度最佳的蓝光样品Gd1.9925MgTiO6∶0.0075Bi3+的CIE坐标为(0.1629,0.0364),位于蓝光区域,色纯度高达96.42%,平均荧光寿命高达11.29 ms。样品的热稳定性高于文献报道的同类样品。这些均说明该样品是一种发光性能和热稳定性能良好的W-LEDs用蓝光组分。     

近紫外激发单基质白光荧光粉NaLaMgWO6∶Dy^3+/Bi^3+的制备及能量传递

采用高温固相法制备了一系列单基质荧光粉NaLa1-x-yMgWO6∶xDy3+/yBi3+(x=0.01,0.02,0.04,0.06;y=0.01,0.02,0.04,0.06)。通过对Dy3+/Bi3+双掺杂浓度进行优化,Bi3+离子的掺杂不仅可以有效增强荧光粉的发光强度,还实现了发光颜色的可调。通过对系列NaLaMgWO6∶xDy3+/0.02Bi3+样品的荧光衰减曲线的分析可知,Dy3+离子浓度从1%增加到6%,Bi3+离子的荧光寿命逐渐减少,从而有力地证明了NaLaMgWO6∶Bi3+/Dy3+荧光粉中存在Bi3+→Dy3+的能量传递过程。另外,通过电多极相互作用公式计算可知,Bi3+→Dy3+能量传递过程为偶极-偶极的相互作用,最优Bi3+/Dy3+掺杂样品的能量传递效率达到42.67%。在紫外光的有效激发下,通过改变Dy3+离子掺杂浓度,NaLaMgWO6∶Bi3+/Dy3+荧光粉可以实现白光发射。研究证明NaLaMgWO6∶Bi3+/Dy3+荧光粉是一种具有潜在应用前景的白光发光材料。     

Luminescence properties of K1/2Bi1/2TiO3:Pr3+ and Na1/2Bi1/2TiO3:Pr3+

The luminescence properties of K(1/2)Bi(1/2)TiO(3):Pr(3+) and Na(1/2)Bi(1/2)TiO(3):Pr(3+) powders are investigated in the temperature range 10-600 K. The experimental data are interpreted on the basis of metal-to-metal charge transfer processes and by considering Bi(3+)-to-Pr(3+) sensitization effects.     

硅酸锶掺Eu^3^＋的高压合成及发光特性

首次采用高压高温方法合成了Sr_2SiO_4:Eu~(3+)Bi~(3+)和SrSiO_3:Eu~(3+)Bi~(3+)发光材料,研究了合成压力、合成温度对发光特性的影响。与常压合成产物相比较,发光谱线发生了红移;谱线半宽度显著增大;发光强度和量子发光效率下降。X射线衍射分析得出,SrSiO_3:Eu~(3+)Bi~(3+)发生了结构相变,Sr_2SiO_4:Eu~(3+)Bi~(3+)结构未变但晶格参数发生了变化,且主衍射峰强度发生了反转。分析表明,发光特性的变化是压致晶场、库仑及自旋～轨道相互作用的变化引起的。     

掺铋BaF2晶体的制备及其近红外发光研究

通过温度梯度法制备了Bi₂O₃:BaF₂以及BiF₃:BaF₂晶体.在Bi₂O₃:BaF₂晶体中观察到了发光峰位于961 nm,半高宽202 nm的超宽带红外发光.在BiF₃:BaF₂晶体中检测到Bi²⁺和Bi³⁺可见区的发光,但是没有观察到红外发光.通过γ射线辐照实现了BiF₃:BaF₂晶体的近红外发光, 发光峰位于1135 nm,半高宽192 nm.讨论了Bi₂O₃和BiF₃掺杂BaF₂晶体的红外发光的机理. 关键词： 近红外发光 铋 氟化钡晶体 γ辐照     

Luminescence of Bismuth‐Activated Ceramics of Yttrium and Scandium Oxides

The luminescence spectra of Y₂O₃:Bi and Sc₂O₃:Bi ceramics have been investigated. The spectra have been resolved into elementary components by the Alentsev–Fock method. It has been established that the luminescence is attributed to emission centers of three types, two of which are due to the replacement of Y³⁺ (or Sc³⁺) by Bi³⁺ at the nodes of the crystal lattice of Y₂O₃ (or Sc₂O₃) with the point symmetry C ₂ and C _3i . The emission center Bi³⁺ in the position C_3i leads to the appearance of blue luminescence with maxima at 3.03 eV for Y₂O₃:Bi and at 3.05 eV for Sc₂O₃:Bi; this luminescence is attributed to the transition ³ P ₁–¹ S ₀. The emission center Bi³⁺ in the position C ₂ initiates green luminescence (which is also related to the ³ P ₁–¹ S ₀ transition in Bi³⁺) with a maximum in the region of 2.40 eV in Y₂O₃:Bi and in the region of 2.46 eV in Sc₂O₃:Bi. The red luminescence band with maxima at 1.85 eV in Y₂O₃:Bi and at 1.95 eV in Sc₂O₃:Bi is related to the presence of structural defects.     

Eu3+在硼酸盐玻璃中的发光以及Bi3+对Eu3+的敏化作用

本文研究了单掺和双掺(Eu3+,Bi3+,Fu3++Bi3+)约二十余种不同成份的硼酸盐玻璃,探讨了玻璃成份对Eu3+发光性质的影响和Bi3+对Eu3+的敏化作用.     

GaP:(Bi,N)晶体中束缚激子的辐射复合及能量转移

本文研究了在4.2K—147K温度范围内GaP:(Bi,N)晶体的光致发光光谱的精细结构,积分强度及其随温度的变化,并将它们与GaP:Bi,GaP:N光谱进行比较。首次发现在GaP:(Bi,N)晶体中激发能量从孤立N中心和NNi对(i≥3)中心到Bi中心的转移,增大了Bi束缚激子态的浓度,使Bi发射带增强。     

Origin of broadband near-infrared luminescence in bismuth-doped glasses

Interstitial negative-charged bismuth dimers, Bi(-)(2) and Bi(2-)(2), are suggested as a model of broadband IR luminescence centers in bismuth-doped glasses. The model is based on quantum-chemical calculations of equilibrium configurations, absorption, luminescence, and luminescence excitation spectra of the dimers in an alumosilicate network and is supported by IR luminescence observed for the first time, to our knowledge, in bismuth-doped polycrystalline magnesium cordierite.     

Eu3+激活的硼钒酸钇的光致发光

找出了合成Eu3+激活的硼钒酸钇铕发光粉的适宜条件和发光最佳化学组分,它是(Y0.94Eu0.06)(V0.69B0.31)O3.7.对其发光光谱的温度依赖关系的研究指出,发光最佳温度在350℃左右.发光的这种温度依赖关系与基质和Eu3+对能量的吸收,以及基质向Eu3+能量传递效率的提高有关.此外,试验结果还表明,在365nm激发下,少显Gd2O3、Zn2GeO4·GeO2:Mn2+等添加剂的加入提高了样品的发光亮度.     

Luminescence centers in thin films of yttrium oxide and yttrium-aluminum garnet activated with bismuth

Luminescence spectra and photoluminescence excitation spectra of Y₂O₃:Bi and Y₃Al₅O₁₂:Bi thin films were investigated. Luminescence was stimulated by the emission from two types of centers that were associated with the substitution of Bi³⁺ for Y³⁺ in sites of the crystal lattice of Y₂O₃ (Y₃Al₅O₁₂) with point symmetries C₂ and C_3i (D₂ and C_3i). The emission of Bi³⁺ in the site with point symmetry C_3i causes blue luminescence in both Y₂O₃:Bi and Y₃Al₅O₁₂:Bi films with maxima at 3.03 eV and 3.15 eV, respectively, that is related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry C₂ gives green luminescence in Y₂O₃:Bi with the maximum at 2.40 eV that is also related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry D₂ leads to ultraviolet luminescence in Y₃Al₅O₁₂:Bi with the maximum at 3.75 eV that corresponds to the ³P₁-¹S₀ transition. The red luminescence band with the maximum at 1.85 eV in Y₂O₃:Bi is due to the presence of structural defects. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 202–207, March–April, 2008.     

Luminescence spectroscopy of the Bi single and dimer centers in Y3Al5O12:Bi single crystalline films

Luminescence of the Bi³⁺ single and dimer centers in UV and visible ranges is studied in YAG:Bi (0.13 and 0.27 at% of Bi, respectively) single crystalline films (SCFs), grown by liquid phase epitaxy from a Bi₂O₃ flux. The cathodoluminescence spectra, photoluminescence decays, and time-resolved spectra are measured under the excitation by accelerated electrons and synchrotron radiation with energies of 3.7 and 12 eV, respectively. The energy level structure of the Bi³⁺ single and dimer centers was determined. The UV luminescence of YAG:Bi SCF in the bands that peaked at 4.045 and 3.995 eV at 300 K is caused by radiative transitions of Bi³⁺ single and dimer centers, respectively. The excitation spectra of UV luminescence of Bi³⁺ single and dimer centers consist of two dominant bands, peaked at 4.7/4.315 and 5.7/6.15 eV, related to the ¹S₀→³P₁ (A band) and ¹S₀→ ¹P₁ (C-band) transitions of Bi³⁺ ions, respectively. The excitation bands that peaked at 7.0 and 7.09 eV are ascribed to excitons bound with the Bi³⁺ single and dimer centers, respectively. The visible luminescence of YAG:Bi SCF presents superposition of several wide emission bands peaking within the 3.125-2.57 eV range and is ascribed to different types of excitons localized around the Bi³⁺ single and dimer centers. Apart from the above mentioned A and C bands the excitation spectra of visible luminescence contain wide bands at 5.25, 5.93, and 6.85 eV ascribed to the O²⁻→Bi³⁺ and Bi³⁺→Bi⁴⁺ + e charge transfer transition (CTT) in Bi³⁺ single and dimer centers. The observed significant differences in the decay kinetics of visible luminescence under excitation in A and C bands of Bi³⁺ ions, CTT bands, and in the exciton and interband transitions confirm the radiative decay of different types of excitons localized around Bi³⁺ ions in the single and dimer centers.     

花状Bi2WO6∶Er3+纳米球的纯绿色上转换荧光和增强的光催化活性

用水热法合成了花状Bi₂WO₆ 和 Bi₂WO₆∶Er³⁺球型微粒样品。Bi₂WO₆∶Er³⁺微粒在980 nm光激发下发射纯绿色上转换荧光,退火温度和Er³⁺的掺杂量对Er³⁺的光谱形状没有明显的影响。Bi₂WO₆∶Er³⁺ 除了具有上述发光性质外,在可见光照射下还存在很高的光催化活性。实验证明:Bi₂WO₆ 和 Bi₂WO₆∶Er³⁺对罗丹明B的光降解效率分别达到68.9%和 95.3%,Er³⁺离子的掺杂提高了罗丹明B的吸附量以及Bi₂WO₆∶Er³⁺光催化活性。     

Bi3+和Eu3+在Ca2SiO4中的发光和能量传递

用高温固态反应合成了Ca2SiO4:Bi3+,Ca2SiO4:Eu3+和Ca2SiO4:Eu3+,Bi3+发光体。讨论了不同掺杂量和掺杂种类时Bi3+对Eu3+的5D0-7F1,5D0-7F2发射的影响规律。实验发现,Ca2SiO4:Bi3+在紫外线激发下发出明亮的蓝色光,Ca2SiO4:Eu3+,Bi3+中的Bi3+能将激发能传递给Eu3+,使Eu3+的5D0-7F1和5D0-7F2两种跃迁都大大加强,同时,Bi3+也发出鲜艳的紫色光。     

红色荧光粉Na_zCa_(1-x-2y-z)Bi_yMoO_4∶Eu_(x+y)~(3+)发光研究

采用高温固相法制备系列红色荧光粉NazCa1-x-2y-zBiyMoO4∶Eux3++y(y,z=0,x=0.24,0.26,0.30,0.34,0.38;x=0.30,y=0.01,0.02,0.03,0.04,0.05,0.06,0.07,z=0;x=0.30,y=0.04,z=0.38)。用X射线粉末衍射(XRD)法测试了所制样品晶相结构。采用荧光光谱仪对样品的发光性能进行了表征,结果表明:当Eu3+单掺杂量浓度x=0.30时,荧光粉(Ca0.70MoO4∶Eu03.+30)的发光强度最强;当Eu3+-Bi3+共掺杂量浓度y=0.03时,电荷迁移带(CTB)强度达到最强,而对于Eu3+特征发射峰,当共掺杂浓度y<0.03时,位于393 nm处的激发峰强度比464 nm强,共掺浓度y>0.03时,464 nm峰比393 nm峰强,共掺浓度为y=0.04时,393和464 nm处两峰位置强度都达到最强。作为电荷补尝剂的Na2CO3掺入上述荧光粉中后,荧光粉激发和发射强度明显地增强。结果表明,通过调节Bi3+/Eu3+掺杂比例可以改变位于近紫外光393 nm和蓝光区464 nm处激发光相对强度。     

The effect of P2O5 on the ultra broadband near-infrared luminescence from bismuth-doped SiO2-Al2O3-CaO glass

The effect of P₂O₅ on infrared luminescence properties of bismuth-doped SiO₂-Al₂O₃-CaO (SAC) glass was investigated. Under excitation of 690 and 808 nm LD, two infrared emissions from bismuth ions central at 1100 and 1300 nm were observed, respectively. The addition of P₂O₅ was not only found to lead to the increase of full width at half maximum (FWHM) of two infrared emissions, but also result in intensity variety of the infrared emissions. The intensity of the infrared emission located at 1300 nm is reduced by a factor of 2, while the luminescence at 1110 nm is increased by a factor of 5. We propose that the infrared emissions at 1100 and 1300 nm may originate from different valence Bi ion in glasses. Compared with emission at 1300 nm, the infrared emissions at 1100 nm is more possibly from the transition of lower valent Bi ion.