硼酸镁中Ce^3＋,Gd^3＋对Dy^3＋发光的敏化作用

本文研究了铈、钆、镝激活硼酸镁的激发光谱、发射光谱、发光寿命和能量传递过程。     

Near-infrared quantum cutting in transparent nanostructured glass ceramics

Quantum cutting downconversion involving the emission of two near-infrared photons for each blue photon absorbed is realized in transparent glass ceramics with embedded Pr3+/Yb3+: beta-YF3 nanocrystals. On excitation of Pr3+ ions with a visible photon at 482 nm, Yb3+ ions emit two near-infrared photons at 976 nm through an efficient cooperative energy transfer from Pr3+ to Yb3+, with optimal quantum efficiency close to 200%. The development of the near-infrared quantum cutting transparent glass ceramic could open a route to enhance the energy efficiency of the silicon solar cell by converting one blue solar photon to two near-infrared ones.     

ZBLAN玻璃中Nd~(3+),Tm~(3+),Yb~(3+)的上转换发光特性

采用高温固相法制备了Nd,Tm和Yb掺杂的ZBLAN玻璃上转换材料.Tm3+,Yb3+的摩尔浓度分别固定为0.01%,0.3%,Nd3+摩尔浓度变化范围为0.1%～2%.在室温下,测试了样品在300～1 000nm间的吸收光谱.在798 nm近红外光激发下,测试了样品的上转换光谱.实验发现,样品在798 nm红外光激发下发出了较强的多波段(红,蓝和绿)的可见光.由上转换可见光各波段的发射谱线,给出了能级跃迁机制.蓝光主要来源于Tm3+的激发态1G4到基态3H6的跃迁,绿光来源于Nd3+的2H7/2到基态4I9/2的跃迁,红光来源于Nd3+的2H11/2到基态4i9/2的跃迁.研究发现,在Nd3+,Tm3+,Yb3+:ZBLAN玻璃样品中存在激发态吸收,能最转移和交叉弛豫等上转换过程.其发光机理是Nd3+,TM3+和Yb3+离子之间的能量转移.根据Nd3+摩尔浓度不同其上转换发光强度不同,分析了掺入稀土的浓度对上转换发光效率的影响.当Nd3+浓度为1.5%(摩尔分数)时上转换发光最强,大于1.5%后发光开始减弱.     

Power scaling method for 2-microm diode-cladding-pumped Tm(3+)-doped silica fiber lasers that uses Yb(3+) codoping

Unidirectional dual-wavelength pumping at 805 and 975 nm of a Tm(3+)-doped silica double-clad fiber laser that has been codoped with Yb(3+) is demonstrated. With equal 2-wt. % concentrations of the Tm(3+) and Yb(3+) ions, slope efficiencies of 49% (57%) and 35% (40%) with respect to the launched (absorbed) pump power of the 805- and 975-nm pump wavelengths, respectively, were obtained. Efficient Yb(3+) --> Tm(3+) energy transfer and efficient cross relaxation combined with minimal upconversion losses were thus operating. At the maximum output power of 18 W, the fiber laser operated at a center wavelength of 2050 nm.     

Sensitized thulium ultraviolet upconversion luminescence in Tm3+/Yb3+/Nd3+ triply doped nanoglass ceramics

Intense four- and five-photon ultraviolet upconversion processes through sensitization of Tm3+ ions in transparent SiO2-Al2O3-NaF-YF3 glass ceramics triply doped with Tm3+/Yb3+/Nd3+ under 796 nm excitation were investigated. Judd-Ofelt analyses evidenced the incorporation of rare-earth ions into the precipitated beta-YF3 nanocrystals. In contrast with the triply doped one, no ultraviolet upconversion luminescence was observed in the Tm3+/Nd3+ codoped glass ceramic, indicating that Yb3+ acts as bridging ions to enhance the energy transfer efficiency between Nd3+ and Tm3+. Based on the pumping power dependence of luminescence, upconversion mechanisms were proposed.     

Ultraviolet upconversion fluorescence from 6D(J) of Gd3+ induced by 980 nm excitation

Ultraviolet upconversion emissions of 246.2 and 252.8 nm from (6)D(J) levels of Gd(3+) ions were observed in GdF(3): 10% Yb(3+), 0.7% Tm(3+) nanocrystals under 980 nm excitation from a laser diode. The (6)D(J) levels of Gd(3+) ions can be efficiently populated by energy transfer processes of Yb-->Tm-->Gd and Yb-->Gd. A six-photon upconversion process was confirmed by the dependence of 252.8 nm emission intensity on the pumping power. The upconversion mechanism in the six-photon process was discussed based on excited state absorption of Gd(3+) ions, cross relaxation energy transfer between two excited Gd(3+) ions, and energy transfer between Gd(3+) and Yb(3+) or Tm(3+) ions.     

Tm3+和Ho3+双掺氟锗酸盐玻璃的中红外发光性质质

用高温熔融法制备了Tm3+和Ho3+离子双掺的65GeO2-12AlF3-10BaF2-8Li2O-5La2O3氟锗酸盐玻璃,应用Judd-Ofelt理论,获得了Ho3+离子的强度参量（Ω2,Ω4,Ω6）,自发辐射跃迁几率Ar,辐射寿命τ等光谱参量。根据McCumber理论,计算了玻璃中Tm3+和Ho3+离子的吸收截面σa、受激发射截面σe和增益光谱G(λ)。在808nm激光二极管激发下,研究分析了Tm3+离子的交叉弛豫过程和Tm3+敏化Ho3+离子的2.0µm的红外发射光谱。结果表明,一定浓度Ho3+的共掺提高了Tm3+（3F4）→Ho3+（5I7）之间的能量转移效率,增强了~2.0µm的红外发光。     

Pb~(2+)掺杂导致的CaF_2中Yb~(3+)离子三聚体合作发光猝灭

利用978 nm近红外光激发样品Ca F2∶Pb2+,Yb3+,在室温下观察到二价Pb2+离子在383 nm附近的紫外上转换发光。该发射峰对应于Pb2+离子的3P0"1A1g(1S0)跃迁。瞬态光谱测量结果表明:在这个材料体系中,Pb2+离子的激发来自于Yb3+离子三聚体的合作敏化。但是随着Pb2+离子掺杂浓度的提高,Yb3+离子三聚体遭到结构性破坏,导致其合作发光减弱。本文首次利用Pb2+离子掺杂造成Yb3+离子三聚体的结构性破坏,从而引起合作荧光猝灭,并对在Ca F2基质中因其他二价离子的掺入而造成的Yb3+三聚体合作发光猝灭给予了合理的解释。     

下转换材料β-NaYF4:Tb3+,Yb3+的水热法合成和发光性质研究

利用水热法合成了粉末发光材NaYF4:Tb3+,Yb3+分别用X射线衍射(XRD),光致发光谱(PL)和激发谱(PLE)测试了合成材料的物相结构和发光性质.研究结果表明:合成的NaYF4:Tb3+,Yb3+抖材料为六方相的品体,无立方相的.改变Tb3+和Yb3+的掺杂浓度后品格结构没有变化,说明离子Tb3+和Yb3+取...     

Evidence for visible quantum cutting via energy transfer in SrAl12O19:Pr,Cr

Evidence for visible quantum cutting involving the emission of two visible photons for each vacuum-ultraviolet (VUV) photon absorbed is demonstrated in SrAl(12)O(19):Pr,Cr using synchrotron radiation as one of the excitation sources. Upon VUV excitation of the 4f5d states of Pr(3+), quantum cutting could occur by a two-step energy transfer from Pr(3+) to Cr(3+) by cross relaxation and sequential transfer of the remaining excitation energy. A theoretical visible quantum efficiency of 147% is estimated in SrAl(12)O(19):2% Pr,5% Cr, suggesting the possibility of a VUV phosphor with visible quantum efficiency higher than 100% based on Pr(3+)-Cr(3+) pair in oxide materials.     

Optical properties of Mg~(2+),Yb~(3+),and Ho~(3+) tri-doped LiNbO_3 crystals

A series of LiNbO_3 crystals tri-doped with Mg~(2+),Yb~(3+),and Ho~(3+) are grown by the conventional Czochraski technique.The concentrations of Mg~(2+),Yb~(3+),and Ho~(3+) ions in Mg:Yb:Ho:LiNbO_3 crystals are measured by using an inductively coupled plasma atomic emission spectrometry.The x-ray diffraction is proposed to determine the lattice constant and analyze the internal structure of the crystal.The light-induced scattering of Mg:Yb:Ho:LiNbO_3 crystal is quantitatively described via the threshold effect of incident exposure energy flux.The exposure energy(E_r) is calculated to discuss the optical damage resistance ability.The exposure energy of Mg(7 mol):Yb:Ho:LiNbO3 crystal is 709.17 J/cm~2,approximately 425 times higher than that of the Mg(l mol):Yb:Ho:LiNbO_3 crystal in magnitude.The blue,red,and very intense green bands of Mg:Yb:Ho:LiNbO_3 crystal are observed under the 980-nm laser excitation to evaluate the up-conversion emission properties.The dependence of the emission intensity on pumping power indicates that the up-conversion emission is a two-photon process.The up-conversion emission mechanism is discussed in detail.This study indicates that Mg:Yb:Ho:LiNbO_3 crystal can be applied to the fabrication of new multifunctional photoluminescence devices.     

Ultraviolet upconversion fluorescence in rare-earth-ion-doped Y2O3 induced by infrared diode laser excitation

Room-temperature ultraviolet emission of Tm(3+) ions at 298 ((1)I(6)-->(3)H(6)), 364 ((1)D(2)-->(3)H(6)), and 391 nm ((1)I(6)-->(3)H(5)) was obtained in Y(2)O(3):Yb(3+)-Tm(3+) by continuous-wave diode laser excitation of 980 nm. Power dependence analysis demonstrates that five- and six-photon upconversion processes populate the (1)D(2) and (1)I(6) states, respectively. We believe that the (1)D(2) population originates from the cross relaxation (1)G(4)+(3)F(4)-->(3)H(4)+(1)D(2) of the Tm(3+) ions, while subsequent energy transfer from Yb(3+) to Tm(3+) excites the (1)D(2) state to the upper (1)I(6) state. High multiphoton-induced ultraviolet emission is also expected for other trivalent rare-earth ions similar to Tm(3+).     

氟氧化物纳米相玻璃陶瓷Tb(0.7)Yb(5)∶FOV的合作下转换发光

报道了氟氧化物纳米相玻璃陶瓷Tb(0.7)Yb(5)∶FOV的红外量子剪裁研究,测量了从可见到红外的荧光发光光谱、激发谱、和荧光寿命,分析了{1([5 D4→7 F6](Tb3+),2([2 F7/2→2 F5/2] (Yb3+)}的红外量子剪裁现象,发现了487.0nm光激发5 D4能级和378.0nm光激发(5 D...     

Tm3+/Yb3+共掺杂玻璃和玻璃陶瓷中蓝色 上转换发光中的能量传递过程

利用高温固相法制备了Tm³⁺/Yb³⁺共掺杂的氟氧化物玻璃和玻璃陶瓷材料,在980 nm的激光激发下,样品发射出明亮的蓝色上转换荧光。通过对玻璃和玻璃陶瓷样品的对比,发现Tm³⁺离子和Yb³⁺离子之间存在着Tm³⁺(³H₄)→Yb³⁺(²F_5/2)的反向能量传输通道,并且与晶场有较强的依赖关系。分析了在玻璃和玻璃陶瓷中蓝色上转换发光过程,随着敏化剂Yb³⁺浓度的增加,在玻璃中正向和反向能量传递的竞争作用使得Tm³⁺离子在Yb³⁺离子的最佳浓度时上转换发光最强;而在玻璃陶瓷中, Tm³⁺离子的上转换发光始终随着Yb³⁺离子的浓度增加而增强。     

铒离子在氟氧化物玻璃陶瓷中的上转换发光特性研究

用转移函数方法分析了Er^3 在铒镱共掺杂的氟氧化物玻璃陶瓷中的上转换发光过程,Er^3 绿色辐射的上转换发光强度与泵浦激光功率的非平方关系是由于Er^3 和Yb^3 之间的强交叉驰豫过程引起的,讨论了在稀土离子共掺杂的氟氧化物玻璃陶瓷中提高Er^3 的上转换发光强度的几种方法。     

溶胶-凝胶法制备Bi3+,Yb3+单掺和共掺Gd2O3荧光粉及其荧光性能

利用溶胶-凝胶法制备了Bi³⁺、Yb³⁺单掺和共掺的Gd₂O₃荧光粉。研究了Gd_2-x-yO₃: Bi_x³⁺,Yb_y³⁺的制备条件并表征了Gd_2-x-yO₃: Bi_x³⁺,Yb_y³⁺的荧光性能。 由于Gd₂O₃: Bi³⁺,Yb³⁺中Bi³⁺对Yb³⁺的能量传递,Gd₂O₃: Bi³⁺,Yb³⁺在Bi³⁺的特征激发峰338 nm激发时,可以产生Yb³⁺的900~1 100 nm近红外特征发射和Bi³⁺的400~700 nm特征发射的两个波段光谱。所制备的Gd₂O₃: Bi³⁺,Yb³⁺荧光材料可将太阳光谱中硅太阳能电池吸收较弱的300~400 nm光转换成有较强吸收的500~700 nm 和1 000 nm附近的近红外光子,提高硅太阳能电池的光伏效率。     

Quantum cutting in CaYAlO4: Pr3+, Yb3+

The deposition of a thin layer of a quantum-cutter material on top of silicon-based solar cells seems to be a promising solution to reduce the thermalization losses. This mechanism has been reported in materials codoped with Pr3+-Yb3+, where Pr3+ can sensitize two Yb3+ ions for one absorbed blue photon. In the present Letter, we analyze precisely energy transfers between Pr3+ and Yb3+ in CaYAlO4, and we measure a quantum-cutting rate of 145%. We show that a very efficient back transfer from Yb3+ toward the (1)G4 level of Pr3+ ion leads to a strong reduction of the quantum yield.     

Tm3+/Yb3+共掺碲酸盐玻璃的近红外发光及能量传递机理

采用高温熔融法制备了组分为TeO2-ZnO-Na2O的Tm3+离子单掺和Tm3+/Yb3+共掺碲酸盐玻璃,应用Judd-Ofelt理论计算分析了玻璃样品的强度参量Ωt(t=2,4,6),自发辐射跃迁几率A,荧光分支比β和荧光辐射寿命τrad等光谱参量,测量得到了不同Yb3+离子掺杂浓度下玻璃样品的Tm3+离子上转换发光谱.结果显示,在980nm泵浦光激励下玻璃样品发射出强烈的近红外上转换荧光.对Tm3+离子上转换发光分析表明,强烈的Tm3+离子近红外上转换发光主要来自于Yb3+/Yb3+离子间的共振能量传递以及基于单声子和双声子辅助的Yb3+/Tm3+离子间的非共振能量传递过程,并进一步计算得到了声子贡献比和能量传递系数.最后,计算分析了Tm3+∶3 F4→3 H6能级间跃迁的1.8μm波段吸收截面、受激发射截面和增益系数.研究表明,Yb3+/Tm3+共掺TeO2-ZnO-Na2O玻璃可以作为近红外波段固体激光器的潜在增益基质.     

Sr_3Al_2O_6∶Tb~(3+),Yb~(3+)荧光粉的近红外量子剪裁效应

硅材料带隙与太阳光子光谱的失配导致了比较严重的光子损失,大大降低了硅太阳能电池的效率。为了减少入射光子的损失,可以利用具有近红外量子剪裁效应的光谱转换材料来提高硅太阳能电池的效率。本研究采用溶胶凝胶法制备了Sr_3Al_2O_6∶Tb~(3+),Yb~(3+)荧光粉,并研究了其近红外量子剪裁效应。实验结果表明:在320 nm的紫外光激发下,Sr_3Al_2O_6∶Tb~(3+),Yb~(3+)荧光粉发射出Tb~(3+):5D4→~7F_j的可见光;另外,由于Tb~(3+)、Yb~(3+)离子之间的合作能量传递,得到了Yb~(3+):~7F_(5/2)→7F7/2的近红外发光。荧光寿命衰减证明Tb~(3+)到Yb~(3+)之间的确存在合作能量传递,而且存在量子剪裁效应,其中,能量传递效率为35.9%,量子剪裁效率为135.9%。由于Yb~(3+)的发射光谱与硅太阳能电池的吸收匹配,Sr_3Al_2O_6∶Tb~(3+),Yb~(3+)荧光粉有可能作为潜在的光谱转换材料应用于硅太阳能电池以提高其光电转换效率。     

Visible quantum cutting via downconversion in LiGdF4 : Er, Tb upon Er 4f→4f5d excitation

Visible quantum cutting (the emission of two photons of visible light per absorbed photon) is reported for LiGdF₄ codoped with Er³⁺ and Tb³⁺. In this compound visible quantum cutting is achieved through downconversion, i.e., by making use of energy transfer between different lanthanide ions. Upon VUV excitation in the 4f¹⁰5d levels of Er³⁺, part of the excitation energy can be transferred to Gd³⁺ by cross-relaxation, yielding both Er³⁺ and Gd³⁺ in an excited state. This is followed by the emission of two visible photons: one from Er³⁺ due to the ⁴S_3/2→⁴I_15/2 transition, and, after energy transfer from Gd³⁺ to Tb³⁺, one from Tb³⁺ due to the ⁵D_J→⁷F_J transition. It is shown that this process occurs, next to other energy transfer processes from the Er³⁺ 4f¹⁰5d states to Gd³⁺ yielding only one visible photon.