Ultraviolet Luminescence of Tm∶ YAG Crystal by Direct Irradiation with Femtosecond Laser

本文报道了室温下飞秒激光辐照Tm∶ YAG晶体的紫外光上转换荧光.Tm3+荧光的强度与泵浦光的功率之间的依赖关系揭示了晶体的上转换过程由三光子吸收过程所主导.研究表明上能级粒子的增加来自于Tm3+吸收一个泵浦光子跃迁到3H4能级后再吸收两个泵浦光子,然后离子跃迁至下能级产生上转换荧光.     

NaY(WO4)2∶Sm3+晶体的生长与上转换发光

用Czochralski 法生长了高光学质量、大尺寸的NaY(WO4)2∶Sm3+单晶.测量了晶体在室温下的吸收谱,对跃迁的能级进行了指认.在946nm泵浦下测量了晶体的上转换荧光发射谱.研究了NYW晶体中Sm3+上转换发光的机制.     

红外飞秒激光诱导Ce3+掺杂闪烁晶体的上转换发光研究

本文研究了红外飞秒激光照射下Ce3+ 掺杂的YAP和LSO两种闪烁晶体的上转换发光现象.实验发现在飞秒激光泵浦下,这两种晶体的荧光均来自于Ce3+离子的5d-4f跃迁.荧光强度与泵浦光功率之间的依赖关系揭示了Ce3+:YAP和Ce3+:LSO晶体的上转换过程皆由三光子吸收过程所主导.分析表明,Ce3+:YAP和Ce3+:LSO晶体中的三光子吸收是三光子同时吸收.     

稀土Tm3+/Yb3+共掺杂氟氧化物上转换可见发光

制备了稀土Tm3+/Yb3+共掺杂氟氧化物上转换发光材料(60TeO2-10AlF3-10PbF2-10NaF-2Tm2O3-8Yb2O3),在980nm红外光泵浦激发下,测量了样品的吸收谱、上转换荧光发射谱和上转换发光强度与激光泵浦功率的对数关系.观察到峰值为477nm蓝光和651nm红光可见发射,分别是稀土Tm3+的激发态1G4→3H6,1G4→3F4跃迁;在806nm附近,观察到较强的红外发射(3H4→3H6),分析了稀土Tm3+/Yb3+共掺杂氟氧化物上转换可见发射机制,证实了稀土Tm3+上转换发射是在稀土Yb3+的敏化作用下,通过能量传递(ET)和激发态吸收(ESA),实现了激发态1G4向基态3H6、激发态3F4跃迁的三光子吸收过程和激发态3H4→3H6的双光子吸收过程.     

NaY（WO4）2：Sm^3＋晶体的生长与上转换发光

用Czochralski法生长了高光学质量,大尺寸的NaY(WO4)2:Sm^3 单晶。测量了晶体在室温下的吸收谱,对跃迁的能级进行了指认。在946nm泵浦下测量了晶体的上转换荧光发射谱,了NYW晶体中Sm^3 上转换发光的机制。     

稀土掺杂钨酸钆钠激光晶体的生长及性能研究

采用提拉法生长出纯的和Nd3+、Tm3+、Ho3+、Dy3+、Pr3+掺杂的大尺寸优质NaGd(WO4)2 晶体.测定了晶体沿(001)和(100)方向的热膨胀系数.测定了晶体的折射率,得到了折射率的色散方程.测量了NaGd(WO4)2 晶体的拉曼光谱,对晶体的振动性能进行研究.对稀土离子掺杂的NaGd(WO4)2 晶体进行了一系列的光谱性质研究,并进行了Judd-Ofelt理论计算.Nd3+:NaGd(WO4)2和Tm3+:NaGd(WO4)2晶体在800 nm附近吸收峰的半高宽和吸收截面较大,有利于LD泵浦.测定了不同能级的荧光寿命,发现Nd3+:NaGd(WO4)2 晶体具有较高的荧光量子效率.采用氙灯闪光灯作为泵浦源,研究了Nd3+:NaGd(WO4)2晶体1060 nm的激光特性.     

Tm3+/Ho3+掺杂的Gd3Ga5O12～2.0μm波段红外激光晶体的生长和性能研究

采用提拉法生长了最大尺寸为φ25mm×(30～40)mm优质透明的Tm3+:GGG、Yb3+/Tm3+:GGG、Cr3+/Tm3+:GGG、Tm3+/Ho3+:GGG和Cr3+/Tm3+/Ho3+:GGG共五种晶体.在室温下测试了这些晶体的吸收光谱、荧光光谱及荧光衰减曲线等,详细研究了光谱性能,对部分晶体进行了Judd-Ofelt理论计算,得到强度参数等重要的光谱参数.计算了～2.0μm附近荧光峰值波长处相应的能级跃迁的发射截面、量子效率等.研究表明:Yb3+和Cr3+的掺入分别使得Tm:GGG晶体在980nm附近和451 nm、628 nm附近的吸收大大增强,有利于商业激光二极管和闪光灯泵浦.在Tm激活的Tm3+:GGG、Yb3+/Tm3+:GGG、Cr3+/Tm3+:GGG晶体中,～2.0μm波段附近发射强度和发射截面值最大的峰值对应的波长为2000nm;而在Ho激活的Tm3+/Ho3+:GGG和Cr3+/Tm3+/Ho3+:GGG晶体中,发射强度和发射截面最大的峰值对应的波长为2080 nm.用氙灯抽运键合的尺寸为φ5mm×45mm Cr3+/Tm3+/Ho3+:Gd3+ Ga5 O12晶体,在2.086～2.102μm波段实现了平均功率为170 mw的激光输出.     

大尺寸优质激光晶体Nd3+/Yb3+∶NaY(WO4)2的生长和性能研究

采用提拉法生长了尺寸为φ25 mm×100 mm的大尺寸Nd3+与Yb3+掺杂的NaY(WO4)2晶体.对晶体的生长习性进行了讨论,利用XRD对晶体进行了相分析.测试了晶体的热膨胀特性,得到了主轴方向的热膨胀系数,测得沿c轴的膨胀系数大约为a轴的两倍.在室温下测试了Yb3掺杂的NaY( WO4)2晶体的吸收谱、荧光光谱和相关能级的荧光衰减,用标准与改进的J-O理论分析了吸收光谱与荧光光谱.结果表明,Yb3+掺杂的NaY( WO4)2晶体有着较好的光谱性能参数.采用氙灯泵浦Nd3+掺杂的NaY( WO4)2,实现了1.06 μm波段786 mJ的激光输出,同时在LD泵浦下,采用LBO晶体倍频,实现了87 mW的激光输出,基频光光转换效率为25;,斜率效率为7.98;.     

Er3+,Yb3+:YAl3(BO3)4晶体的光谱性质研究

采用助熔剂法生长了Er3+,Yb3+共掺的YAl3(BO3)4晶体,测量了晶体的室温吸收谱.由此吸收谱,根据JuddOfelt理论计算了Er3+在Er3+,Yb3+:YAl3(BO3)4晶体中的强度参数、自发辐射几率、积分发射截面等参数.强度参数为Ω2=2.44×10-20cm2、Ω4=2.00×10-20cm2、Ω6=6.10×10-20cm2.研究了晶体的荧光特性,并在976nm激光泵浦下得到了上转换绿色荧光.     

稀土掺杂钨酸镧钠激光晶体的生长及其性能研究

采用提拉法生长出了纯的和Nd3+、Tm3+、Dy3+、Ho3+、Pr3+离子掺杂的大尺寸优质的NaLa(WO4)2晶体.TG/DTA实验表明NaLa(WO4)2晶体在1251℃同成分熔化,热膨胀实验结果显示该晶体沿(100)和(001)方向的热膨胀系数分别为1.23×10-5K-1和2.49×10-5K-1.在室温下测量了该晶体的红外和拉曼光谱,对晶体的振动性质进行了研究.对稀土离子掺杂的NaLa(WO4)2晶体进行了光谱性质的研究.N3+:NaLa(WO4)2和Tm3+:NaLa(WO4)2晶体800 nm附近的吸收峰半高宽和吸收截面较大,有利于用LD泵浦.采用小型的氙灯泵浦,研究了Nd3+:NaLa(WO4)2晶体的激光特性.当氙灯输入能量为1.28 J时,获得14.77mJ的激光输出能量,光光转换效率为1.15;.     

Optical and Luminescence Properties of YAlO3 ‐Tm Crystals

The results on optical absorption, photoluminescence and thermoluminescence of YAP‐Tm crystals of 1 at.% and 4 at.% of Tm are presented as well as influence of UV‐, γ‐radiation and thermal treatments on optical and luminescence properties of the crystals. The blue‐green luminescence of defect centers was observed in YAP‐Tm crystals at Ar⁺‐laser excitation. The possibility of energy transfer processes between defect centers and Tm³⁺ ions was shown.     

ZnS晶体中浅电子陷阱对光电子衰减过程的影响

本文采用微波吸收法,测量了ZnS:Mn,Cu:I,Br粉末材料受到超短激光脉冲激发后,其光生电子和浅束缚电子的衰减过程.发现制备过程中Mn2+、Cu1、I-、Br-的掺杂量对光生导带电子的衰减过程有明显的影响.光生电子寿命是I-、Br-形成的浅施主能级和Cu+受主能级、Mn2+发光中心共同作用的结果.本文还测量了材料的热释光曲线,Cu+受主能级、Mn2+发光中心会影响热释光强度,证实I-、Br-形成电子陷阱对光生电子和浅陷阱中的电子寿命有延长作用,而Mn2+发光中心会起到缩短寿命的作用.     

Simulation of the optical properties of Tm:ZBLAN glass

The optical properties of Tm:ZBLAN glass have been simulated. The simulated optical spectra agreed substantially with the observed spectra. The population of the energy levels of the Tm³⁺ ion under dual-wavelength excitation for upconversion emission and amplification was evaluated by solving the rate equation with the simulated transition probabilities and spectral shapes of the transitions of which the initial levels were from the ³H₆ to ³P₂ levels. The large population of the ¹G₄ level, which is the upper level for 480 nm laser oscillation, was estimated for the conditions of laser oscillation at room temperature. We also proposed new combinations of the excitation wavelengths for the amplification of the 1470 nm signal.     

Surface plasmon excited infrared-to-visible upconversion in Er-doped transparent glass ceramics

The surface plasmon (SP) excited infrared-to-visible upconversion luminescence has been studied in the oxyfluoride glass ceramics containing Er³⁺-doped fluoride nano-crystals. Upconversion luminescence was observed at glass ceramics. Quantum yield of upconversion luminescence increased with increasing heat-treatment temperature. The transparent glass ceramics heat-treated at 700 °C was covered with a 50 nm gold film, and then attached to an SF10 prism with index-matching oil to make an attenuated total reflection (ATR) illumination. The intense upconversion luminescence bands at 540 and 660 nm were observed at the SP resonance angle by using p-polarized laser beam. The apparent dependences of the upconversion efficiency on laser polarization and on incident angle demonstrated the SP excited upconversion of Er³⁺.     

NaMn3 F10∶Yb/（Er,Tm,Ho）纳米颗粒的制备及光谱研究

由于具有毒性低、稳定性好、发光强度高等优点,稀土上转换纳米颗粒在细胞成像和标记方面具有十分广泛的应用前景。本文采用了常规的热分解法,制备了粒径均一、均匀分散的NaMn3 F10∶Yb/( Er,Tm,Ho)上转换纳米颗粒。研究表明,制备的纳米颗粒的粒径都在10 nm以下。 NaMn3 F10∶Yb/Er和NaMn3 F10∶Yb/Tm纳米颗粒在980 nm连续激光的激发下分别发射660 nm和800 nm的单色光,这主要归因于Mn2+离子4 T1能级可以作为中间过渡能级,将Er3+离子2 H11/2能级和4 S3/2能级上的光电子通过非辐射的方式转移到2 F9/2能级上,降低2 H11/2能级和4 S3/2能级上的光电子数同时增加2 F9/2能级上的光电子数,使2 F9/2与4 I15/2基态能级产生较大的粒子数反转,以产生较强的波长为660 nm光辐射。通过对NaYF4∶Yb3+20;,Er3+2;纳米颗粒中掺杂Mn2+离子的研究发现,随着Mn2+离子掺杂浓度的提高,该纳米颗粒的发光颜色从绿色逐渐向红色转变,光谱中红绿光的强度比逐渐升高,在Mn掺杂浓度为58;时即可得到纯红光发射的上转换纳米颗粒。     

Optical properties of Er3+-singly doped and Er3+/Yb3+-codoped novel oxyfluoride glasses

Novel oxyfluoride glasses SiO₂–Al₂O₃–Na₂O–ZnF₂ doped with Er³⁺ and Er³⁺/Yb³⁺ were fabricated. The optical properties of the synthesized glasses were experimentally and theoretically investigated in detail. The experimental and calculated oscillator strengths of Er³⁺ were determined by measurement of the absorption spectrum of Er³⁺-singly doped glass. According to the Judd–Ofelt theory, the experimental intensity parameters were calculated, from which the radiative transition probabilities, fluorescence branching ratios and radiative lifetimes were obtained. The fluorescence lifetime and quantum efficiency for the near-infrared emission of Er³⁺-singly doped glass were determined to be 3.0 ms, and 42%, respectively. Visible upconversion luminescence was observed under 980 nm diode laser excitation. The dependence of the upconversion emission intensity upon the excitation power was examined, and the upconversion mechanisms are discussed.     

Frequency upconversion and its new mechanism in Tm-doped fluoroaluminate glasses

Upconversion fluorescences have been observed in the UV (363 nm) and the blue region (451 and 476 nm) in Tm³⁺-doped fluoroaluminate glass by pumping with a DCM dye laser. The two-photon absorption process of upconversion fluorescences was confirmed by the quadratic dependence of the emission intensity on incident pumping power. The excitation spectra for upconversion fluorescences show that the mechanism of upconversion is a simple ESA (excited state absorption) process. In addition to ESA, it was found that the energy transfer by cross-relaxation (³H₄, ³H₆ → ³F₄, ³F₄) is also involved in the mechanism of the 476 nm blue upconversion fluorescence which differs from that of the UV and the 451 nm blue upconversion fluorescence. The difference was confirmed by measuring both the radiative and the non-radiative decay rate of the ³H₄ level.     

Dynamics of excited state relaxation and frequency upconversion in Tm3+ and Tm3+/Tb3+ doped ZBLAN glass

The effects of activator concentration on the relaxation of the ¹I₆, ¹D₂, ¹G₄ and ³H₄ levels of Tm³⁺ were investigated by the analysis of the fluorescence decay curves in Tm³⁺ and Tm³⁺/Tb³⁺ doped ZBLAN glasses. UV and blue upconversion luminescence bands around 362 and 450 nm were observed by 655 nm laser excitation in all the samples. The upconversion mechanism was attributed to excited state absorption (ESA) by analyzing the decay profiles and the intensity dependence.     

α相和β相BiNbO4∶Eu3+的荧光性能

采用高温固相法合成出正交相和三斜相结构的BiNbO₄∶Eu³⁺样品,利用X 射线衍射(XRD)、拉曼光谱、吸收光谱和荧光光谱对样品的结构和光学性能进行了研究。结果表明:900 ℃合成样品为正交相结构α-BiNbO₄,而1 200 ℃得到三斜相结构β-BiNbO₄。吸收光谱得到α相和β相BiNbO₄的光学带隙分别为2.69 eV和2.96 eV,与第一性原理的理论结果2.640 eV和3.032 eV相吻合。Eu³⁺掺杂诱导二者的光学带隙蓝移至2.89 eV和3.05 eV,有效改变了其光响应范围。荧光光谱表明:Eu³⁺在两种结构的最强荧光峰均来自⁵D₀→⁷F₂电偶极跃迁,最强荧光峰分别位于615 nm和611 nm。Eu³⁺在β-BiNbO₄中的荧光强度更高,而且其⁵D₀→⁷F₂和⁵D₀→⁷F₁的荧光强度比值更大。与Eu³⁺相似,Er³⁺在β-BiNbO₄中具有更高的上转换荧光强度,其强度约是在α-BiNbO₄中荧光的近40倍,说明三斜结构BiNbO₄更适合做稀土离子的基质材料。     

柠檬酸燃烧法制备Gd3Ga5O12:Eu3+纳米晶及发光性质

以柠檬酸为燃烧剂,乙二醇为分散剂,采用燃烧法制备了Gd3Ga5O12∶Eu3+纳米晶.利用X射线衍射仪、扫描电镜和荧光光谱对样品的结构、形貌和发光性能进行了研究.XRD研究结果表明:合成的样品均为单一的Gd3Ga5O12晶相,纳米晶的一次性粒径分布在16～ 30nm.发射光谱和激发光谱的研究表明:主发射峰来自于Eu3+的5D0→7F1的跃迁;宽激发带主要来自于Eu-O电荷迁移带.讨论了柠檬酸和乙二醇用量对晶粒尺寸、品格常数、发射和激发强度的影响.结果表明:过量的柠檬酸和适量的乙二醇有利于晶体发育和发光强度的提高.