Up-conversion luminescence tuning in Er~(3+) -doped ceramic glass by femtosecond laser pulse at different laser powers

The up-conversion luminescence tuning of rare-earth ions is an important research topic for understanding luminescence mechanisms and promoting related applications. In this paper, we experimentally study the up-conversion luminescence tuning of Er~(3+)-doped ceramic glass excited by the unshaped, V-shaped and cosine-shaped femtosecond laser field with different laser powers. The results show that green and red up-conversion luminescence can be effectively tuned by varying the power or spectral phase of the femtosecond laser field. We further analyze the up-conversion luminescence tuning mechanism by considering different excitation processes, including single-photon absorption(SPA), two-photon absorption(TPA), excited state absorption(ESA), and energy transfer up-conversion(ETU). The relative weight of TPA in the whole excitation process can increase with the increase of the laser power, thereby enhancing the intensity ratio between green and red luminescence(I_(547)/I_(656)). However, the second ETU(ETU2) process can generate red luminescence and reduce the green and red luminescence intensity ratio I_(547)/I_(656), while the third ESA(ESA3) process can produce green luminescence and enhance its control efficiency. Moreover, the up-conversion luminescence tuning mechanism is further validated by observing the up-conversion luminescence intensity, depending on the laser power and the down-conversion luminescence spectrum under the excitation of 400-nm femtosecond laser pulse. These studies can present a clear physical picture that enables us to understand the up-conversion luminescence tuning mechanism in rare-earth ions, and can also provide an opportunity to tune up-conversion luminescence to promote its related applications.     

Up-conversion luminescence polarization control in Er~(3+)-doped NaYF_4 nanocrystals

We propose a femtosecond laser polarization modulation scheme to control the up-conversion(UC) luminescence in Er~(3+)-doped NaYF_4 nanocrystals dispersed in the silicate glass. We show that the UC luminescence can be suppressed when the laser polarization is changed from linear through elliptical to circular, and the higher repetition rate will yield the lower control efficiency. We theoretically analyze the physical control mechanism of the UC luminescence polarization modulation by considering on- and near-resonant two-photon absorption, energy transfer up-conversion, and excited state absorption, and show that the polarization control mainly comes from the contribution of near-resonant two-photon absorption. Furthermore, we propose a method to improve the polarization control efficiency of UC luminescence in rare-earth ions by applying a two-color femtosecond laser field.     

Simulating the resonance-mediated (1+2)-three-photon absorption enhancement in Pr3+ ions by a rectangle phase modulation

Enhancing the upconversion luminescence of rare earth ions is crucial for their applications in the laser sources, fiber optic communications, color displays, biolabeling, and biomedical sensors. In this paper, we theoretically study the resonance-mediated (1+2)-three-photon absorption in Pr³⁺ ions by a rectangle phase modulation. The results show that the resonance-mediated (1+2)-three-photon absorption can be effectively enhanced by properly designing the depth and width of the rectangle phase modulation, which can be attributed to the constructive interference between on-resonant and near-resonant three-photon excitation pathways. Further, the enhancement efficiency of resonance-mediated (1+2)-three-photon absorption can be affected by the pulse width (or spectral bandwidth) of femtosecond laser field, final state transition frequency, and absorption bandwidths. This research can provide a clear physical picture for understanding and controlling the multi-photon absorption in rare-earth ions, and also can provide theoretical guidance for improving the up-conversion luminescence.     

基质材料对Yb~(3+)浓度调控的上转换荧光红绿比的影响

控制Yb~(3+)掺杂浓度是一种重要的调控红绿荧光比率的方法.然而,关于不同基质中Yb~(3+)浓度对红绿上转换荧光调控的敏感度仍缺少定量的对比研究,而且调控机理尚不清晰.本文通过乙二胺四乙酸辅助的水热法,合成了形貌可控的NaYF_4微米棒、LiYF_4微米八面体和YF_3微米砖三种氟化物晶体.通过激光共聚焦显微镜系统对比研究了Yb~(3+)/Er~(3+)掺杂的三种不同基质和形貌的单颗粒氟化物微米晶体的上转换荧光行为和红绿比率对Yb~(3+)变化的敏感度.研究结果表明:NaYF_4:Er~(3+)微米棒的红绿比率对Yb~(3+)的掺杂浓度响应最为敏感,各种Yb~(3+)浓度掺杂的LiYF_4:Er~(3+)微米八面体上转换荧光被绿光主控,而不同Yb~(3+)掺杂的YF_3:Er~(3+)微米砖表现出了稳定的黄光发射.通过分析荧光发射谱和比较上下转换荧光动力学过程结合荧光强度-功率依赖关系,基于拥有不同声子能量的基质辅助的Er~(3+)离子中间态的不同消布居途径,揭示了不同基质中红绿比率对Yb~(3+)变化响应的物理机制,并提供了一种研究上转换机理的思路.     

Ba5SiO4Cl6: Yb3+, Er3+, Li+荧光粉的制备及上转换发光性质研究

本文采用高温固相反应法制备了Ba₅SiO₄Cl₆: Yb³⁺, Er³⁺, Li⁺ 荧光粉, 并对其上转换发光性质及其发光机理进行了研究. 在980 nm 激光的激发下, Ba₅SiO₄Cl₆: Yb³⁺, Er³⁺ 荧光粉呈现较强的红色(662 nm) 和较弱的绿色(550 nm) 的上转换发光, 红色和绿色的上转换发光分别对应于Er³⁺ 离子的⁴S_3/2/²H_11/2→⁴I_15/2 和⁴F_9/2→⁴I_15/2 跃迁, 且随着掺杂的Er³⁺ 和Yb³⁺ 离子浓度增加, 样品的上转换发光强度增加, 这是因为Yb³⁺ 离子和Er³⁺ 离子之间的能量传递效率增加引起的. 在0.5—0.8 W 功率激发下,样品属于双光子发射, 而在0.9—1.2 W 功率激发下样品具有新的上转换发光机理——光子雪崩效应. 探讨了Li⁺ 掺杂对Ba₅SiO₄Cl₆: Yb³⁺, Er³⁺ 样品的上转换发光性质的影响, Li⁺ 离子的掺杂引起Ba₅SiO₄Cl₆:Yb³⁺, Er³⁺ 上转换发光强度增加, 这是由于Li⁺ 离子的掺入降低了晶体场的对称性引起的.     

Two-photon-excited luminescence in a Tb3+ -doped lithium niobate crystal pumped by a near-infrared femtosecond laser

Blue (487.6 nm), green (544.1 nm), yellow (582.1 nm), and red (623.6 nm) upconversion (UC) luminescences are achieved in a Tb(3+)-doped lithium niobate crystal when an 800 nm femtosecond laser is loosely focused onto the sample at room temperature. The relationship between UC luminescence intensity and the pump energy indicates that a two-photon excitation process is dominant in this UC luminescence phenomenon. The Tb(3+) sensitive temperature dependence of the luminescence intensity is demonstrated via an obvious reduction of luminescence intensity with durative laser irradiation.     

Two- and three-photon excitation of Gd in CaAl12O19

We have employed two-photon excitation to study the higher energy levels of Gd³⁺ ions in CaAl₁₂O₁₉ and we compare the results with those obtained using conventional UV excitation techniques. Under two-photon excitation, the luminescence intensity exhibits an unusual temporal behavior, a very long build-up followed by a decrease by orders of magnitude, ascribed to a recombination-assisted luminescence excitation mechanism assuming photo-ionization of Gd³⁺ ions and trapping of free electrons on deep traps.

We also find that the two-photon excitation spectra contain an additional broadening contribution which can be attributed to homogeneous broadening of excitation levels caused by excited state absorption into the conduction band. We believe that this may be a general phenomenon whenever participating photons produce ionization of impurity ions from metastable excited states. The phenomenon can manifest itself also in two-photon ionization spectral hole burning and in up-conversion processes (in the latter case, the homogeneous broadening can be caused by an intra-ion excited-state absorption).     

试验优化设计Er3+/Yb3+共掺BaGd2ZnO5荧光粉及其上转换发光性质

为得到绿光和红光最大发光强度的Er³⁺/Yb³⁺共掺BaGd₂ZnO₅上转换材料荧光粉, 首先采用试验优化设计中的均匀设计初步寻找Er³⁺/Yb³⁺合理的掺杂浓度; 其次通过二次通用旋转组合设计进一步优化实验, 建立起Er³⁺/Yb³⁺掺杂浓度与绿光和红光发光强度的回归方程; 最后通过遗传算法计算出方程的最优解, 即绿光和红光最大发光强度时对应的Er³⁺/Yb³⁺掺杂浓度. 利用传统的高温固相法分别制备出最优样品. 采用X 射线衍射对得到荧光粉的晶体结构进行了分析, 证明了所有产物均为纯相BaGd₂ZnO₅. 采用980 nm抽运激光作为激发源, 在同样的条件下测量了样品的上转换荧光发射光谱, 从中可见样品有较强的红光发射和绿光发射, 发光中心位于662, 551和527 nm, 分别对应于⁴F_9/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2 及²H_11/2→⁴I_15/2能级跃迁. 研究了绿光和红光最优样品的上转换发光强度与激光器工作电流之间的关系, 通过分析发现红色和绿色上转换发光均为双光子过程. 由归一化的绿色上转换发射光谱可以看出, 激光器工作电流导致的样品温度变化可以忽略不计. 由于能级²H_11/2和⁴S_3/2之间存在热平衡, 并满足玻尔兹曼分布, 由此探讨了绿光最优样品上转换发射光谱中的绿色发射与温度的关系, 计算出²H_11/2和⁴S_3/2之间的能级差为ΔE=926.11 cm^-1. 研究了绿光最优样品的温度效应, 随着温度的升高, 发射强度逐渐变小, 出现了温度猝灭现象. 并计算了样品的激活能, 分别为总体激活能ΔE_总=0.45 eV, 绿光激活能ΔE_绿=0.45 eV, 红光激活能ΔE_红=0.46 eV.     

Simulating resonance-mediated two-photon absorption enhancement in rare-earth ions by a rectangle phase modulation

Improving the up-conversion luminescence efficiency of rare-earth ions via the multi-photon absorption process is crucial in several related application areas. In this work, we theoretically propose a feasible scheme to enhance the resonance-mediated two-photon absorption in Er~(3+) ions by shaping the femtosecond laser field with a rectangle phase modulation. Our theoretical results show that the resonance-mediated two-photon absorption can be decomposed into the on-resonant and near-resonant parts, and the on-resonant part mainly comes from the contribution of laser central frequency components, while the near-resonant part mainly results from the excitation of low and high laser frequency components.So, the rectangle phase modulation can induce a constructive interference between the two parts by properly designing the modulation depth and width, and finally realizes the resonance-mediated two-photon absorption enhancement. Moreover, our results also show that the enhancement efficiency of resonance-mediated two-photon absorption depends on the laser pulse width(or laser spectral bandwidth), final state transition frequency, and intermediate and final state absorption bandwidths. The enhancement efficiency modulation can be attributed to the relative weight manipulation of on-resonant and near-resonant two-photon absorption in the whole excitation process. This study presents a clear physical insight for the quantum control of resonance-mediated two-photon absorption in the rare-earth ions, and there will be an important significance for improving the up-conversion luminescence efficiency of rare-earthions.     

温度对飞秒激光脉冲在NaCl溶液中成丝产生的超连续谱的影响

利用飞秒激光脉冲在NaCl溶液中成丝,研究了溶液温度对飞秒激光成丝过程中产生的超连续谱的影响.发现在激光脉冲能量较低时,溶液温度对超连续谱的影响几乎可以忽略;而在激光脉冲能量较高时,随着NaCl溶液温度的升高,超连续谱呈现出被压缩的趋势.此外,在激光脉冲能量较高的情况下, NaCl中会产生大量的气泡.通过分析,得出了飞秒激光在溶液中成丝产生的气泡是影响超连续谱发射的主要因素.     

Lu_(2)O_(3)∶Er^(3+)/Yb^(3+)荧光材料的上转换发光及其温度传感特性EI北大核心CSCD

采用CO_(2)激光区熔法制备了Lu_(2)O_(3)∶0.5%Er^(3+)/x%Yb^(3+)(x=1,3,5)上转换荧光材料。X射线衍射结果表明,所制备的Lu_(2)O_(3)∶Er^(3+)/Yb^(3+)荧光材料具有纯Lu_(2)O_(3)晶相。在980 nm激光激发下,样品发出明亮的上转换荧光。光谱测试结果表明,样品上转换荧光强度和荧光中绿光与红光比例随Yb^(3+)离子浓度改变,当Er^(3+)和Yb^(3+)离子浓度分别为0.5%和3%时,样品上转换荧光强度最强。通过荧光强度比(FIR)技术研究了样品Lu_(2)O_(3)∶0.5%Er^(3+)/3%Yb^(3+)在298~873 K温度范围内上转换荧光温度传感特性,在532.8 K时最大绝对灵敏度为0.0060 K^(-1),在298 K时最大相对灵敏度为0.0090 K^(-1)。结果表明,Lu_(2)O_(3)∶Er^(3+)/Yb^(3+)荧光材料非常适合用于宽温度范围荧光温度传感。     

低强度飞秒激光激发下CdTe和CdTe/CdS核壳量子点的荧光上转换研究

利用400 nm和800 nm不同波长的低强度飞秒激光,对CdTe和CdTe/CdS核壳量子点溶胶进行激发,研究其稳态和时间分辨荧光性质.800 nm飞秒激光激发下,CdTe和CdTe/CdS核壳量子点产生上转换发光现象,上转换荧光峰与400 nm激发下的荧光峰相比蓝移最多达15 nm,而且蓝移值与荧光量子产率有关.变功率激发确认激发光功率与上转换荧光强度间满足二次方关系,时间分辨荧光的研究表明荧光动力学曲线服从双e指数衰减.提出表面态辅助的双光子吸收模型是低激发强度上转换发光的主要机理.CdTe和CdT 关键词： CdTe量子点 CdTe/CdS核壳量子点 时间分辨荧光 上转换荧光     

Simultaneous three-photon absorption induced ultraviolet upconversion in Pr:Y2SiO5 crystal by femtosecond laser irradiation

Near-infrared to ultraviolet upconversion luminescence was observed in the Pr³⁺:Y₂SiO₅ crystal with 120 fs, 800 nm infrared laser irradiation. The observed emissions at around 270 nm and 305 nm could be assigned to 5d → 4f transitions of Pr³⁺ ions. The relationship between the upconversion luminescence intensity and the pump power of the femtosecond laser reveals that the UV emission belongs to simultaneous three-photon absorption induced upconversion luminescence.     

磁控溅射制备Er~(3+)/Yb~(3+)共掺杂TiO_2薄膜的上转换发光特性

采用射频磁控溅射法制备得到Er~(3+)/Yb~(3+)TiO_2薄膜,980 nm的抽运源作用下上转换可以得到490 nm的绿光和670 nm的红光,上转换红、绿光发光强度受到烧绿石Er_xYb_(2-x)Ti_2O_7晶体的生成以及Er~(3+)/Yb~(3+)掺杂浓度的影响,实验表明,适量共掺杂Er~(3+)/Yb~(3+)可明显增强上转换发光,Er~(3+)在上转换发光中起主要作用,而引入敏化离子Yb~(3+)可以大大提高上转换发光效率,磁控溅射法制备的TiO_2薄膜声子态密度较小,从而抑制了无辐射跃迁过程,导致490nm绿光形成以及红光强度大于绿光强度。     

Measurement of infrared level lifetime by upconversion luminescence

Based on repetition frequency-dependent excited state absorption (ESA) upconversion (UC) luminescence, a method to measure the lifetime of an IR intermediate level is proposed so long as ESA UC luminescence can occur in the rare earth ions. The feasibility of this idea is demonstrated via a theoretical simulation. A Er(3+):LiNbO? crystal ESA UC luminescence under femtosecond laser excitation is used to illustrate this measurement method, and the obtained 1.5 μm lifetime of 2.31 ms is shorter than previous reported values. This method can obviate the influence of radiation trapping effect on lifetime measurement, which is crucial in the traditional pulse sampling technique.     

高浓度Er~(3+)掺杂Y_3Sc_2Ga_3O_(12)晶体的吸收光谱与晶体场模型研究

采用提拉法生长出了高浓度掺铒(35 at%)钇钪镓石榴石(Er:YSGG)激光晶体.测试了该晶体在340—1700 nm波段内的吸收光谱,对其中Er3+的实验能级进行了分析指认.用Er:YSGG的102个实验Stark能级,拟合了它的自由离子参数和晶体场参数,均方根误差(拟合精度)σ为10.34 cm-1.结果表明,参数化Stark能级的拟合结果与实验光谱符合得较好.将拟合得到的Er:YSGG实验结果与文献中已报道Er:YAG的自由离子参数和晶体场参数进行了比较.指出Er:YSGG具有较强的晶体场相互作用或许是其激光效率较高的主要原因之一.     

单颗粒稀土微/纳晶体上转换荧光行为的光谱学探究

利用激光共聚焦显微镜系统研究了系列单颗粒NaYF_4:Yb/Er微晶的上转换荧光强度、空间分布和动力学过程.结果表明:荧光强度和动力学过程不但依赖于样品的长径比,而且依赖于样品的具体制备途径.荧光强度和红色荧光寿命随样品长径比的增大而增大,在具有相同长径比的NaYF_4:Yb/Er微米棒中,相比于调柠檬酸的量,调控pH制备的样品展示了更优异的上转换荧光特性.更有趣的是:不同样品的荧光图案展示了异向空间分布,暗示了其在编码和显示等领域的应用优势.荧光特性依赖于样品长径比和制备过程的物理机理被进一步研究和揭示:在微米晶体内,荧光强度主要依赖于样品的晶格内Na~+缺陷的数量.该研究为高效上转换荧光材料的合成积累了数据,而NaYF_4:Yb/Er微晶中红色荧光寿命对晶格缺陷更加敏感的特性也可能使其成为晶格结晶度的探针.     

He原子体系中偶极子响应的周期性量子相位调控的理论研究

基于激光诱导相位模型, 研究了周期性相位调控的He原子体系的光谱响应. 研究发现,周期性的相位调控会导致He原子吸收谱由单个孤立的洛伦兹线型转化为等间隔的“梳状”结构. “梳状”光谱的性质主要由原子系统和控制脉冲链的性质决定, 并给出了表征“梳状”光谱的理论公式. 该机理具有普遍适用性, 它可以应用到任意原子体系, 进而推广到任意波段, 并且为任意波段的脉冲整形提供了可能.     

YNbO4：Tm3+/Yb3+上转换发光特性研究

按照50Nb₂O₅-（46-x）Y₂O₃-4Yb₂O₃-xTm₂O₃（x=0.1,0.2,0.5,1,2）的配比方式,采用高温固相法制备出了掺杂Tm³⁺/Yb³⁺的YNbO₄晶体粉末。在980 nm红外光激发下,观测到波长为478,645,707 nm的上转换荧光,分别对应于Tm³⁺离子的¹G₄→³H₆、¹G₄→³F₄、³F₃→³H₆能级跃迁过程。利用上转换发射功率与980 nm激光器工作电流关系估算出跃迁过程吸收光子数目为2.72,2.69,2.01,从而确定出前两者为三光子吸收过程,最后一个对应于双光子吸收过程。运用Judd-Ofelt理论研究样品光谱特性,根据样品的吸收谱得到样品的谱线强度参数Ω_t（t=2,4,6）,进而得出理论振子强度及实验振子强度,二者均方根偏差δ_rms=1.299×10^-7。计算了Tm³⁺离子向下能级跃迁的跃迁几率、跃迁分支比等参数。最后得出结论：（1）³F₄能级寿命较长,适合作为上转换中间能级;（2）³H₅能级寿命较长,且³H₅→³H₆跃迁分支比（96.46%）接近100%,可用于产生1 216 nm激光。     

BaY_2ZnO_5:Tm~(3+)/Yb~(3+)荧光粉的试验优化设计合成及发光性质研究

为了获得BaY_2ZnO_5:Tm~(3+)/Yb~(3+)荧光粉材料的最大蓝色上转换发光强度,采用正交试验设计与二次通用旋转组合设计相结合的两步连续优化法对Tm~(3+)和Yb~(3+)掺杂浓度进行全局优化,得到该体系最强蓝光发射下的离子掺杂最佳浓度.采用高温固相反应法合成出蓝色上转换发光强度最强的BaY_2ZnO_5:Tm~(3+)/Yb~(3+)荧光粉材料,并对样品的晶体结构和上转换发光性质进行了研究.980nm红外光激发下,测量了最优样品在不同激发电流下的上转换发射光谱,由强度制约关系确定样品的蓝色上转换发光为三光子过程.测量了最优样品温度相关的上转换发射光谱,发现样品的蓝色上转换发光强度随着样品温度的升高而持续减弱,即发生了温度猝灭现象,计算得激活能约为0.602eV.