Y0.795-xGdxYb0.2Tm0.005F3纳米晶合成及 Tm3+和Gd3+的上转换发光

利用水热法合成了氟化物Y_0.795-xGd_xYb_0.2Tm_0.005F₃ (x=0.0,0.1,0.2,0.5,0.8)纳米晶。研究了退火后系列样品的上转换发光性质以及激发态辐射跃迁寿命。在980 nm激发下,Y_0.795-xGd_xYb_0.2Tm_0.005F₃纳米微晶样品中观察到了Tm³⁺的蓝光上转换发射及紫色、紫外发射增强现象,同时还观察到Gd³⁺的⁶D_9/2、⁶I_J、⁶P_5/2及⁶P_7/2到基态⁸S_7/2的发射。实验结果表明:样品半个波长量级的颗粒尺寸是Tm³⁺紫外上转换增强以及Tm³⁺到Gd³⁺发生有效能量传递的重要因素。     

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.     

Yb3+/Ho3+/Tm3+共掺碲酸盐玻璃的上转换白光发射及其机理研究

采用高温熔融法分别制备了Yb3+/Ho3+,Yb3+/Tm3+和Yb3+/Ho3+/Tm3+共掺的碲酸盐玻璃。在980nm红外激光激发下,Yb3+/Ho3+/Tm3+共掺的玻璃样品显示了强的蓝光、绿光和红光发射,分别对应于Tm3+的1 G4→3 H6跃迁、Ho3+的5 F4(5 S2)→5I 8跃迁以及Ho3+的5 F5→5I 8和Tm3+的1 G4→3 F4跃迁。通过对比发现,Yb3+/Ho3+/Tm3+共掺样品中的红、绿光积分发射强度比值(3.95)明显大于Yb3+/Ho3+共掺样品(1.69),这是由于Ho3+和Tm3+间存在交叉弛豫过程3 H4(Tm3+)+5I 6(Ho3+)→3 F4(Tm3+)+5 F5(Ho3+)和3 F4(Tm3+)+5I 8(Ho3+)→3 H6(Tm3+)+5I 7(Ho3+)所致。在激发功率密度为8.2 W.cm-2时,Yb3+/Ho3+/Tm3+共掺样品的上转换发光色坐标值为x=0.345,y=0.338,非常接近于等能白光(x=0.333,y=0.333)。     

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+).     

Sr3Gd(PO4)3:Tm3+的真空紫外光谱特性

研究了Sr3Gd(PO4)3 : Tm3 和GdPO4 : Tm3 样品的结构特性、光谱特性.GdPO4 : Tm3 为单斜晶系,基质掺入铥离子后结构没有明显变化.GdPO4:Tm3 在164和210 nm附近有强烈的吸收峰.位于164 nm附近的强烈的吸收峰是归因于基质的吸收引起,210 nm附近的吸收峰则归因于Gd 的8S7/2-6GJ的能级跃迁.在164 nm真空紫外光激发下,样品于453及363 nm处有较强的发射峰,发射主峰位于453nm,属于Tm3 的1D2→3H4(22,123 cm-1)跃迁的典型发射.由于阳离子质量的不同,Sr3Gd(PO4)3:Tm3 在166 nm附近的激发峰高于GdPO4: Tm3 的同位置的激发峰,其在363 nm处的发射有明显减弱,而在453 nm处的蓝色发射有显著的增强.     

氟化物中Yb3+对Ho3+, Tm3+的直接敏化上转换作用

采用双掺杂(Yb^3 ／Ho^3 )和多掺杂(Ho^3 ／Yb^3 ／Tm^3 )方式,研究了氟化物中Yb^3 对Ho^3 ,Tm^3 的直接敏化上转换作用,并对它们在980nm激光激发下的上转换光谱特性进行了比较,对它们的上转换机理作了详细的讨论分析。观测到两处很强的上转换发光,分别是Yb^3 ／Ho^3 共掺杂体系中^5F4^5S2(Ho^3 )→^5Is(Ho^3 )的荧光跃迁和Ho^3 ／Yb^3 ／Tm^3 共掺杂体系中^3H4(Tm^3 )→H6(Tm^3 )的荧光跃迁。还发现由于添加了Tm^3 ,减弱了Yb^3 ／Ho^3 共掺杂体系中Ho^3 在可见光范围的上转换发光强度。     

Hydrothermal synthesis of Yb~(3+),Tm~(3+) co-doped Gd_6MoO_(12) and its upconversion properties

Yb3+,Tm3+co-doped Gd6 Mo O12phosphors with different morphologies are prepared by the hydrothermal method.The dendrites present different morphologies(including hexagonal prisms,spindles,and spheres) after changing the p H value and edetate disodium(EDTA) usage.It is found that each of the two factors plays a crucial role in forming different morphologies.The up-conversion(UC) luminescence is studied.Under 980-nm semiconductor laser excitation,relatively strong blue emission and weak red emission are observed.Finally,the effect of pumping power on the UC luminescence properties and the level diagram mechanism of Gd6 Mo O12:Yb3+/Tm3+phosphor are also discussed.     

Ultraviolet emissions from Gd ions excited by energy transfer from Ho ions

Ultraviolet (UV) upconversion (UC) emissions of Gd³⁺ ion were investigated in Y_1.838−xGd_xYb_0.16Ho_0.002O₃ (x=0, 0.16, 0.4, 1, 1.4) bulk ceramics under 976 nm laser diode (LD) excitation. The UC emissions centered at 309 and 315 nm are assigned to the transition of ⁶P_5/2→⁸S_7/2 (Gd) and ⁶P_7/2→⁸S_7/2 (Gd). The ⁶P_J levels of Gd³⁺ ions are populated by an energy transfer (ET) process from ⁸S_7/2 (Gd)+(³P₁, ³L₈, ³M₁₀) (Ho)→⁶P_J (Gd)+⁵I₈ (Ho). A four-photon ET UC process was confirmed by the dependence of the ⁶P_7/2 level emission intensity on the pumping power. We found that the intensity of the UC emissions increased with Gd³⁺ ion concentration and peaked at 8 mol%, then starts to decrease until the Gd³⁺ ion concentration reached 70 mol%. The variation in the UV emission intensity is the result of the competition between the ET process and concentration quenching effect. Theoretical calculations based on steady-state equations validated the proposed UC mechanisms.     

氟氧化物玻璃陶瓷中高效低阈值的红色上转换发光现象

本文报道了一种Er3 + 和Tm3 + 共掺杂新的氟氧化物玻璃陶瓷材料中高效低阈值的红色上转换发光现象。材料组份为 6 5GeO2 2 5NaF 8 5BaF 0 5Tm2 O3 1Er2 O3 (mol% ) ,文中给出了样品的制备方法。在 978nmLD激发下 ,观察到了非常强的红色上转换发光。据我们所知 ,在如此低的Er3 + 和Tm3 + 掺杂浓度下实现了如此之强的红色上转换发光 ,文献中未见报道 ;更令人惊奇的是在 2 0 0mA工作电流 (此时功率为 3 5mW )LD激发下 ,激发的功率密度为 170mW·cm-2 ,其红色光仍裸眼可见。讨论了这种高效低阈值上转换发光的机理。研究了LD的工作电流与上转换发光强度的关系     

Ca9R(VO4)7 : Eu3+ 发光粉的发光特性

采用高温固相法制备了Eu³⁺离子激活的Ca₉R(VO₄)₇(R = Y, La, Gd)红色发光粉,并利用荧光光谱对发光粉的特性进行研究。激发光谱中,Ca₉Y(VO₄)₇ : Eu³⁺ , Ca₉La(VO₄)₇ : Eu³⁺和Ca₉Gd(VO₄)₇ : Eu³⁺都有两个宽的VO^3-₄激发带和Eu³⁺的特征激发峰。发射光谱中,在Ca₉Y(VO₄)₇ : Eu³⁺ 和Ca₉La(VO₄)₇ : Eu³⁺中的350~550 nm范围内出现VO^3-₄的发射带,而在Ca₉Gd(VO₄)₇ : Eu³⁺中却没有观察到VO^3-₄的发射。在这三种发光粉中,Ca₉Gd(VO₄)₇ : Eu³⁺的发光强度远远高于其它两种,这是由于Gd³⁺的存在有效地使能量通过Gd³⁺ →VO^3-₄ → Eu³⁺及Gd³⁺ → Eu³⁺的两种方式进行能量传递,从而提高了Eu³⁺发光效率。     

Er3+掺杂的锗铋酸玻璃光谱性质的研究

制备了一种新型掺Er3 锗铋酸盐玻璃。分析了吸收光谱和上转换荧光光谱,并应用Judd-Ofelt理论计算了锗铋酸盐玻璃的3个强度参量tΩ(t=2,4,6),分别为Ω2=3.35×10-20cm2,Ω4=1.34×10-20cm2以及Ω6=0.67×10-20cm2。研究了在两种不同的激发光下(980和808 nm)锗铋酸盐玻璃的发光机制。根据McCumber理论,分析了在1.55μm光通讯窗口的光谱性质,计算了能级4I13/2→4I15/2跃迁的受激发射截面,结果显示掺Er3 锗铋酸盐玻璃具有较宽的荧光半高宽和较大的受激发射截面。因此有希望成为高效的上转换发光材料和1.55μm光通讯材料。     

α-TeO2∶Tm3+,Ho3+,Yb3+纳米材料的红绿蓝色上转换发光（英文）

利用简单的水热合成法成功制备出α-TeO2∶Ho3+,Yb3+、α-TeO2∶Tm3+,Yb3+和α-TeO2∶Tm3+,Ho3+,Yb3+纳米材料,用980 nm的近红外光作为激发光源测定了样品的室温上转换发射光谱。结果表明:样品α-TeO2∶Ho3+,Yb3+分别发射绿光(545 nm)和红光(651 nm),分别对应于Ho3+离子的5S2→5I8和5F5→5I8能级跃迁。随着Yb3+的摩尔分数从5%增加到15%,样品在545 nm处的绿光强度明显变大,发光颜色由黄光向绿光转变。样品α-TeO2∶Tm3+,Yb3+在476 nm处发射出蓝光,对应于Tm3+离子的1G4→3H6能级跃迁,两个弱红光峰(651,675 nm)分别对应于Tm3+离子的1G4→3F4和3F2→3H6能级跃迁。随着Yb3+离子浓度的提高,蓝光与红光的相对强度也在显著提高。基于可调控性蓝光、绿光和红光的产生,α-TeO2∶Tm3+,Ho3+,Yb3+纳米材料能产生不同颜色的光,包括白光。     

YLiF4: Er3+, Tm3+, Yb3+中Tm3+浓度对上转换发光的影响

利用水热法合成了YLiF4: Er3 , Tm3 , Yb3 , 其中Er3 和Yb3 的浓度保持固定不变, 分别为1 mol%和1.5 mol%, Tm3 浓度变化范围是2 mol%～8 mol%. 在这种共掺杂体系中, 同时观察到了Er3 , Tm3 和Yb3 的吸收, 且Tm3 的吸收随着其浓度的增强而增强. 在980 nm光的激发下, 当Tm3 浓度很小时, 这种材料的上转换发光为白光. 其中蓝光主要来源于Tm3 的激发态1G4到基态3H6的跃迁, 绿光来源于Er3 的4S3/2和2H11/2到基态4I15/2的跃迁, 红光既来源于Tm3 的1G4→3F4的跃迁, 也来源于Er3 的4F9/2→4I15/2的跃迁. 并且这种上转换发光强度随着Tm3 浓度的增强而降低, 但对应不同能级跃迁的发光强度降低的幅度不同, 这是因为Er3 和Tm3 之间的相互作用.     

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.     

Nanocrystalline RE2O3:Tm3+ (RE: Gd3+, Y3+) Blue Phosphors Synthesized via the Combustion Method

This work reports on the preparation of a luminescent blue-emitting rare earth (RE) Tm-doped oxide phosphor. Nanocrystalline RE2O3:Tm3+ particles were prepared via the combustion method using citric acid, glycine, or urea as fuels. Samples were doped with different percentages of the activator Tm3+. The post-annealing treatment was performed in air for all the samples, at temperatures ranging from 800 to 1100 degrees C, for 4 h. The samples were characterized by X-ray diffraction (XRD), photoluminescence spectroscopy (PL) and scanning electron and transmission microscopies (SEM and TEM) in order to determine the best synthetic procedure. The post-annealed powders showed blue emission with maximum at 452 nm characteristics for Tm3+ transition 1D2 --> 3H4 (under UV excitation at 360 nm). Samples, presented a tri-dimensional porous structure (50-200 nm) formed of spheroid particles with a diameter between 20 and 60 nm. The best luminescent material was obtained when urea was used to prepare nanoparticles of Gd2O3 doped with 0.5% Tm3+, and 1100 degrees C was used as the post-annealing temperature.     

β-NaGd_(0.794)Yb_(0.200)Ho_(0.001)Tm_(0.005)F_4纳米颗粒的白色上转换发光

利用简单的水热合成法制备了β-NaGd0.794Yb0.200Ho0.001Tm0.005F4纳米颗粒。采用X射线粉末衍射(XRD)技术测定了样品的物相,结果显示样品为六角相。通过透射电子显微镜(TEM)和高分辨透射电子显微镜观察的结果样品为椭球和六角形状,颗粒的平均尺寸为23 nm。用980 nm半导体激光二极管为激发光源,测定了样品的室温上转换发射谱,结果表明:样品分别发射红、绿和蓝色光,其相对发射强度,从强到弱的顺序为蓝色、绿色和红色,与其对应辐射跃迁分别为Tm3+离子的1G4→3H6,Ho3+离子的5F4→5I8,5F5→5I8跃迁。样品发射的蓝、绿和红光组合而发出强的白色上转换发光,其色品坐标为(x=0.271 7,y=0.267 3)。     

波导适用型铝锗酸盐玻璃中铥离子上转换荧光光子输出与量子产率定量

制备了适用于钾钠离子交换波导的Tm~(3+)/Yb~(3+)掺杂铝锗酸盐玻璃,利用积分球配以光纤光谱仪在975nm激光泵浦下对玻璃的上转换荧光进行测试,解析出样品的绝对荧光特征参量。测试与计算结果显示,在380℃的KNO3熔盐中,Tm~(3+)/Yb~(3+)掺杂的铝锗酸盐玻璃的钾钠离子交换有效扩散系数为0.070μm~2/min,热离子交换过程易于控制。铝锗酸盐玻璃样品中,Tm~(3+)主要发出477 nm蓝光和806 nm近红外光,其中近红外光为支配性发射。绝对荧光参数和激发功率密度呈正相关,当功率密度达到1 482 W/cm2时,三光子上转换蓝光的绝对光谱功率、净发射光子数和量子产率分别为269μW、6.46×10~(14)/s和1.43×10~(-4),双光子近红外光上转换对应的3个参量分别为4 024μW、1.63×10~(16)/s和3.61×10~(-3)。基于波导适用型铝锗酸盐玻璃中Tm~(3+)上转换荧光的绝对化表征,为进一步研发光电子器件和激光材料提供了有益的数据参考。     

Enhanced green upconversion emission of Er(3+) through energy transfer by Dy(3+) under 800 nm femtosecond-laser excitation

Er(3+) green upconversion (UC) emission corresponding to the transition of (4)S(3/2) ((2)H(11/2))-->(4)I(15/2) is enhanced in a Er/Dy-codoped LiNbO(3) crystal compared with Er-doped LiNbO(3) under 800 nm femtosecond-laser excitation at room temperature. The upconversion mechanisms are proposed based on spectral, kinetic, and pump-power dependence analyses. The energy-transfer efficiency from Dy(3+)((4)F(9/2)) to Er(3+)((4)F(7/2)) is 33%, which results in the enhancement of green UC emission. This energy transfer is advantageous for the Er(3+) UC emission sensitized by Dy(3+), especially in a low-phonon-energy host matrix.     

LaOBr中Ce—Tb、Tm—Er间能量传递的光声光谱和光致发光研究

本文首次报导了发光材料中两个不同稀土离子间能量传递的光声光谱研究。测量了LaOBr:Tb,Ce和LaOBr:Er,Tm体系的光声光谱,结合它们的光致发光特性,讨论了Ce³⁺对Tb³⁺的敏化、Tm³⁺对Er³⁺的猝灭。基质中掺入两种不同稀土离子后光声光谱的变化进一步证实了它们间的能量传递都伴随着多声子过程。分析LaOBr:Er,Tm的光声光谱,对Er³⁺r的红光猝灭的机制提出了新的解释。     

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。