Infrared energy transfer in Tm3+:LiNbO3

The infrared optical properties of LiNbO₃ crystals doped with variable thulium concentrations have been studied. In particular, the infrared emissions that appear after direct pumping to the ³H₄ multiplet (795 nm) have been analyzed. The emission spectra, as well as the lifetimes, show that an efficient energy transfer between ³F₄ and ³H₄ levels takes place. The concentration dependence of the lifetimes has been studied and the transfer probability has been characterized.     

Modelling of Tm3+-doped LiNbO3 Waveguide Lasers

In this work, CW laser operation of Tm³⁺-doped LiNbO₃ channel waveguides has been modelled. The model is based on time dependent laser rate equations coupled with the laser signal and pump photon flux equations. Steady state solutions for the population densities, pump and signal powers are obtained by using finite difference discretization of the active volume. The effects of spectroscopic parameters such as concentration dependent cross-relaxation and excess waveguide loss have been analyzed. We demonstrate good agreement with experimental data previously reported in Zn-diffused LiNbO₃:Tm³⁺ channel waveguide lasers. It is shown also that laser performance can be substantially improved by optimizing the cavity length.     

Polarized emission and absorption cross-section calculation in LiNbO3:Tm3+

Absorption and emission cross-sections are essential spectroscopic parameters that determine the performance of rare-earth solid state lasers and amplifiers. A precise characterization of such parameters is of great interest in order to proceed with the necessary optimization stage which will assure the development of photonic devices with high efficiency. In particular, in order to model Tm³⁺ infrared lasers under 800 nm pumping, the absorption and emission cross-sections associated with optical transitions involving the ³H₄ and ³F₄ manifolds are needed. In this work, the classical McCumber theory is applied to evaluate the polarized absorption and emission cross-sections of Tm³⁺ ions in LiNbO₃.     

Excitation energy transfer between Er3+ and Tm3+ in LiNbO3

Conclusions Nonradiative energy transfer between similar and different rare-earth ions in LiNbO₃ has been evidenced for the first time. The contribution of nonradiative energy transfer to the decay of the¹G₄ and³H₄ levels of thulium and the⁴S_3/2 and⁴I_13/2 levels of erbium is significant for activator concentrations of the order of several thousand ppm in LiNbO₃. The excitation of higher-lying levels of both activators is transferred faster in codoped crystal to the lowest luminescent levels, from which the luminescence in the 1–2-μm spectral region occurs. This accelerated relaxation is advantageous for broadband optical pumping since the contribution of radiative transitions competing with the³F₄−³H₆ laser transition of thulium is reduced. On the other hand, it appears that erbium ions will influence adversely the efficiency of a laser-diode-pumped LiNbO₃∶Er, Tm laser operating near 1.8 μm since the part of the³H₄ excitation transferred to erbium ions is emitted from the long-lived⁴I_11/2 level of Er³⁺. Furthermore, the⁴I_13/2 excitation is not transferred fully to thulium ions and is lost in⁴I_13/2−⁴I_15/2 emission. Lithium niobate singly doped with thulium is more promising since the cross-relaxation process that transfers the excitation from the³H₄ level to the³F₄ level appears to be efficient in this host. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 5, pp. 125–133, September–October, 1995.     

镱铥共掺杂的氟化镧纳米粒子的亮蓝色上转换发光

采用反胶束法合成镱铥共掺杂的氟化镧纳米粒子.这种反胶束是由微乳液作为合成媒介,这些分散的纳米粒子在化学成分、尺寸分布上是可控的.产物形貌经场发射扫描电镜和透射电镜表征.固态样品分散在乙醇中,在未经超声处理时,样品表现为玉米棒样的聚集.棒的平均直径和长度分别为110,575nm.我们认为这种大量纳米粒子聚集成良好超结构是由于溶剂挥发,分子交叉链接或者表面活性剂分子附着于纳米粒子特殊晶面造成的.当样品经过超声处理后,由于超声振动破坏了上述因素,玉米棒形貌的聚集体转为大量纳米粒子.单个粒子的高分辨电镜显示出该纳米粒子的单晶结构.并且晶面间距约为0.366nm,与纯氟化镧六角相[002]晶面相一致.样品在300℃退火30min后的透射电镜照片显示纳米粒子的平均直径大约为35nm,这与XRD结果相吻合.并且,这些纳米粒子表现出了良好的单分散性,并且在978nm二极管激发下,纳米粒子呈现出亮蓝色上转换发光,这种上转换荧光粉在光电子或生物检测中有潜在的应用前景.     

不同波长激发下YLiF4：Er3+,Tm3+,Yb3+的发光

水热法合成了YLiF₄:Er³⁺,Tm³⁺,Yb³⁺,其中Er³⁺、Yb³⁺和Tm³⁺的摩尔分数分别为1%、1.5%和2%。当用355nm光激发时,其发光为蓝色,峰值位于450nm,对应于Tm³⁺的¹D₂→³F₄跃迁。用378nm激发时,发光为绿色,主要发光峰位于552nm。980nm光激发时,发光为白色,发光峰分别位于665(651),552(543),484,450nm处,并在648nm处还观察到了一个发光峰,其中最强的发射为红光。YLiF₄:Er³⁺,Tm³⁺,Yb³⁺的蓝光来源于Tm³⁺的激发态¹G₄到基态³H₆的跃迁,绿光来源于Er³⁺的⁴S_3/2和²H_11/2到基态⁴I_15/2的跃迁,红光既来源于Tm³⁺的¹G₄→³F₄的跃迁,也来源于Er³⁺的⁴F_9/2→⁴I_15/2的跃迁。在上转换发光中,还探测到了紫外光359nm的发射。监测665nm得到的激发光谱不同于监测552nm的激发光谱,在665nm的激发光谱中出现了对应Tm³⁺的¹G₄能级的峰。在双对数曲线中,蓝光484nm、绿光552nm和红光665nm的斜率分别为2.25、2.28和2.21,紫外光359nm的斜率为2.85。因此在980nm激发下,蓝光484nm、绿光552nm和红光665nm都是双光子过程,紫外光359nm的发射是三光子过程。     

Upconversion white-light emission in Ho3+/Yb3+/Tm3+ codoped LiNbO3 polycrystals

Ho³⁺/Yb³⁺/Tm³⁺ codoped LiNbO₃ polycrystals exhibiting upconversion white-light under 980 nm excitation have been successfully fabricated by the high temperature solid-state reaction method. CIE coordinate of the Ho³⁺/Yb³⁺/Tm³⁺/LiNbO₃ polycrystal is (0.34, 0.35), which is very close to the standard equal energy white-light illuminate (0.33, 0.33). Efficient green, red, and blue upconversion emissions have been observed. The luminescent decay dynamics are studied, and rate equations for the blue, green, and red emissions are set up to analyze the upconversion luminescence mechanism. The present results demonstrate that the competition between the linear decay and the upconversion process for the depletion of the intermediate excited states plays an important role in upconversion mechanism. The LiNbO₃ with upconversion white-light will be a promising luminous material.     

Eu3+掺杂LiNbO3晶体的变温发射光谱特征

在488nFn波长光的激发下，研究了用坩埚下降法生长的掺杂Eu^3 离子的下部与上部LiNbO3晶体从77到600K的变温发射光谱特征。实验结果表明，对于生长后期的上部晶体，随着温度的升高，其发光强度总体增强；然而对于生长初期的下部晶体，随着温度的升高，其发光强度首先增强，到540K时达最大值，然后随着温度的升高，其发光强度反而下降。用热激活效应、声子辅助吸收效应与热猝灭效应解释了晶体上部与下部的发光特征。     

Tm3+离子掺杂氟铝酸盐玻璃红外及上转换光谱性质

制备了Tm^3 掺杂氟铝酸盐玻璃，以实测的吸收光谱使用Judd-Ofelt理论详细计算了Tm^3 在氟铝酸盐玻璃中的光谱参数，在此基础上研究了Tm^3 离子掺杂氟铝酸盐玻璃的上转换光谱性质和红外光谱性质。研究表明：在800nm激光二级管激发下，1.45μm（^3F4→^3H4)荧光浓度猝灭要明显强于1.77μm（^3H4→^3H6)荧光；在655nm激发下上转换荧光主要是由单个Tm^3 离子的步进二光子吸收过程所致。     

Tm3+掺杂Ge-Ga-Se玻璃中红外发光特性与多声子弛豫分析

用熔融急冷法制备了系列不同Tm3+掺杂浓度的Ge30Ga5Se65玻璃样品,测试了样品折射率、拉曼光谱、吸收光谱以及800nm激光泵浦下的近红外及中红外波段荧光光谱和荧光寿命。用Judd-Ofelt理论计算了Tm3+在Ge30Ga5Se65玻璃中的强度参数Ωi(i=2,4,6)、自发辐射跃迁概率A、荧光分支比β和辐射寿命τrad等光谱参数。讨论了800nm激光泵浦下掺杂1Wt%Tm3+样品在近红外1.23,1.48和1.8μm处的发光特性及各量子效率,研究了800nm激光泵浦下的样品中红外荧光特性与掺杂浓度之间的关系,计算了常温下该基质玻璃中Tm3+:3H5→3F4跃迁对于3.8μm处的多声子弛豫速率Wmp和Ge30Ga5Se65玻璃基质中多声子弛豫常数W(0)和电子-声子结合常数α值。结果表明Ge30Ga5Se65硒基玻璃较低的声子能量可以大大降低稀土离子能级间跃迁的多声子弛豫概率,从而提高中红外荧光发光效率,因此硒基玻璃作为稀土离子的掺杂基质材料对实现中红外荧光输出是非常有利的。     

激发功率、退火温度及Tm3+浓度对Tm3+/Er3+/Yb3+三掺YF3粉末上转换发光性质的影响

用水热法合成了Tm³⁺/Er³⁺/Yb³⁺三掺杂YF₃上转换发光粉末,并对其进行了结构和形貌表征.对上转换发射谱的研究表明,在相对低激发功率下,可以观察到比较明亮的近白色发光,且随着激发功率的增大,上转换发射强度迅速增大并达到饱和状态,继续增大激发功率,出现发光猝灭现象.退火温度对上转换发射强度的影响表明,随着退火温度的升高,Tm³⁺,Er³⁺的所有特征发射峰均相对增强.上转换发射谱随Tm³⁺浓度变化关系表明,在相对低Tm³⁺掺杂浓度下,Tm³⁺-Er³⁺相互作用占优势,Tm³⁺把能量传递给Er³⁺,Er³⁺发射相对增强;在相对高掺杂浓度下,Tm³⁺-Tm³⁺之间交叉弛豫过程占优势,Er³⁺发射相对减弱.从实验结果看出,该粉末的上转换发光非常丰富,从紫外到红外均有发射,是一种潜在的白色上转换发光及三维固体显示材料.     

场发射显示器用蓝色YVO_4∶Tm~(3+)纳米荧光粉的制备及性能研究

采用溶剂热法成功地制备出了YVO4∶Tm3+纳米荧光粉,并用X射线衍射仪(XRD)、透射电子显微镜(TEM)、紫外分析仪、紫外可见(UV-Vis)吸收光谱和光致发光(PL)光谱对YVO4∶Tm3+纳米荧光粉进行测试和表征。实验结果表明,YVO4∶Tm3+纳米荧光粉可发出明亮的蓝光,色纯度和发光强度都很高,而且具有良好的热稳定性。因此,YVO4∶Tm3+纳米荧光粉是一种十分适用于场发射显示器的荧光粉。     

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.     

Spectroscopic properties and exicted-state relaxation dynamics of Er3+ in LiNbO3

Nonequivalent Er³⁺ sites in LiNbO₃ crystals have been evidenced by low-temperature optical absorption measurements. The radiative transition rates for the ⁴ S _3/2, ⁴ F _9/2, ⁴ I _9/2, ⁴ I _11/2, and ⁴ I _13/2 levels have been evaluated by the Judd-Ofelt method, and the contribution of multiphonon relaxation to the decay of excited states has been estimated. The quantum efficiency of the ⁴ I _11/2 level has been estimated to be 6% only, thus the excitation of levels lower than ⁴ S _3/2 is expected to populate efficiently the ⁴ I _13/2 level.     

Low-threshold continuous-wave Tm3+:YAlO3 laser

We describe a continuous-wave, low-threshold Tm:YAlO₃ (Tm:YAP) laser operating at 1945 nm with incident threshold pump powers in the 10–20 mW range. The z-cavity containing a 2-mm-long Tm:YAP crystal with 4 at.% Tm³⁺ concentration was end pumped by a continuous-wave Ti:sapphire laser at 795 nm. Tight focusing of the pump and the laser beams enabled low-threshold operation. The power performance of two different cavity configurations with 5-cm radius (R = 5 cm cavity) and 10-cm radius (R = 10 cm cavity) curved mirrors was tested. The best performance was obtained with the R = 10 cm configuration, where, the incident threshold pump power could be lowered to 10 mW after optimizing the polarization direction of the pump beam and by employing double pumping. Theoretical estimation of the threshold power was in good agreement with the experimental observations. The laser could be further tuned from 1842 to 1994 nm.     

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.     

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.