High-temperature VUV spectroscopy of KYF4 crystals doped with Nd3+, Er3+ and Tm3+ ions

Thermal quenching of 5d-4f luminescence from Nd³⁺, Er³⁺ and Tm³⁺ ions doped into KYF₄ crystals has been investigated in the temperature range up to ∼750 K where this luminescence is completely quenched. The obtained temperatures of thermal quenching (T_q) are ∼270, 495, 450 K for Nd³⁺, Er³⁺, Tm³⁺, respectively. At high temperatures, thermal quenching of 5d-4f luminescence from Nd³⁺ and Er³⁺ is accompanied by the appearance of 4f-4f luminescence from the lower-energy 4f levels. It has been shown that the dominating mechanism of thermal quenching for Nd³⁺ and Er³⁺ ions is thermally stimulated non-radiative transitions (intersystem crossing) from the 5d states to lower-energy 4f levels, namely ²G(2)_9/2 and ²F(2)_7/2, respectively, whereas for the Tm³⁺ ion, thermally stimulated ionization of 5d electrons to the conduction band states is responsible for thermal quenching of 5d-4f luminescence. The energy gap between the lowest Tm³⁺ 5d level and the bottom of the KYF₄ conduction band has been estimated to be 0.66 eV.     

Time-resolved spectra of excited-state absorption in Er3+ doped YAlO3

A pump- and probe-beam technique is used for measuring time-resolved excited-state absorption (ESA) and stimulated-emission (SE) spectra of Er³⁺ doped YAlO₃. The Er^{3+ 4} I _15/2 ⁴ F _7/2 transition of the sample is excited at 488 nm by an excimer laser pumped dye laser. The ESA and SE of broadband xenon flashlamp light is monitored between 300 and 860 nm by an optical multichannel analyzer (OMA). The analysis of the experimental results provides information on the effective cross sections _ESA and _SE originating from several levels and on the populations of these levels. To our knowledge this represents the first detailed investigation of time-resolved ESA and SE over a broad spectral range in rare-earth doped materials.     

EPR of Er3+, Nd3+, and Ce3+ ions in YAlO3 single crystals

EPR spectra of the Er³⁺, Nd³⁺, and Ce³⁺ ions substituting for the Y³⁺ ion in the YAlO₃ yttrium orthoaluminate lattice are studied. The EPR spectra of these rare-earth ions are described by a spin Hamiltonian of rhombic symmetry with an effective spin S=1/2. The principal values of the g tensors were determined from an analysis of the angular dependences of the EPR spectra. The orientation of the local magnetic axes of paramagnetic centers relative to the YAlO₃ crystallographic directions are shown to depend on the actual rare-earth species. The EPR spectra exhibit a hyperfine structure due to the ¹⁶⁷Er, ¹⁴³Nd, and ¹⁴⁵Nd odd isotopes, which permitted unambiguous identification of these spectra. The hyperfine coupling constants for the odd erbium and neodymium isotopes are determined.     

Thermal Behavior of the Fluorescence Lines of Ho3+ in Cr,Tm,Ho:YAG

The fluorescence spectra of Cr,Tm,Ho∶YAG crystal have been detected at the temperature from 65 to 295 K with interval of 10 K.The width and the shift of Ho3+ lines at 4959.6 cm-1 (at 65 K) have been investigated and interpreted in terms of the interactions between lattice vibration (phonons) and ions.The results showed that the line broadening with the temperature was mainly due to the Raman scattering of phonons,and the line shift with temperature was mainly due to the emission and absorption of virtual phonons.     

Submillimeter electron-nuclear excitation spectra in CsCdBr3:Ln3+ (Ln=Tm, Ho) crystals

The ESR spectra of single and pair impurity centers of thulium and holmium ions in CsCdBr₃:Tm³⁺ and CsCdBr₃:Ho³⁺ crystals are measured in the frequency range 160-400 GHz. Analysis of the characteristic features of the hyperfine structure of the ESR lines and analysis of the variations in the spectra as a function of the temperature and external magnetic field shows that the Ln³⁺ ions substitute for Cd²⁺ ions and predominantly form symmetric pair centers of the type Ln³⁺-(vacancy at a neighboring Cd²⁺ site)-Ln³⁺. The ESR spectra of CsCdBr₃: Ln³⁺ crystals are used to make a positive identification of the optical spectra of selective laser excitation. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 7, 535–540 (10 April 1997)     

Absorption and photoluminescence of YAG:Er3+, YAG:Ce3+, and YAG:Er3++Ce3+ crystals

We have studied absorption and luminescence spectra of yttrium-aluminum garnets doped with Er³⁺ and Ce³⁺ ions, as well as co-doped with Er³⁺+Ce³⁺ impurity ions. Luminescence of studied crystals was excited by cw laser radiation at the wavelengths 457 and 980 nm. We revealed obvious display of the energy transfer processes occurring in the impurity subsystem of a YAG: Er³⁺+Ce³⁺ crystal.     

5d-4f luminescence of Nd3+, Gd3+, Er3+, Tm3+, and Ho3+ ions in crystals of alkaline earth fluorides

The vacuum ultraviolet emission spectra of alkaline-earth fluoride (CaF₂, SrF₂, BaF₂) crystals with rare earth impurity ions (Nd, Gd, Er, Tm, Ho) have been investigated. The main luminescence bands are described well by the transitions from the lowest excited 5d state to different 4f levels of rare earth ions.     

Hypersensitive transitions of Tm3+, Ho3+ and Dy3+ rare-earth ions in garnet crystals

In this work, spectroscopic characteristics (oscillator strengths, intensity parameters) of intermanifold f–f transitions of Tm^{3 +}, Ho³⁺and Dy³⁺ions in garnet crystals are investigated. It has been found that the intensity change of the hypersensitive intermanifold f–f transitions of rare-earth ions in garnet crystals is determined by the characteristics of their local environment.     

YPO4∶Ho3+,Yb3+,Tm3+微纳米管的合成及上转换白光发射

水热法合成了均匀管状Tm3+,Ho3+和Yb3+三掺的YPO4微纳米管,在波长为980nm的近红外光激发下能够发射出红绿蓝三条可见光谱带以及中心波长位于795nm的近红外发射带,从而实现上转换白光发射。通过TEM,XRD和荧光光谱等表征手段对合成的Tm3+,Ho3+和Yb3+三掺YPO4微纳米管进行了结构和性能分析,结果表明,合成的YPO4微纳米管为纯净六方相,水热反应温度对荧光材料的发射光谱有较明显的影响,然而对材料物相的影响却不大。在相同反应温度下,随着掺杂稀土离子浓度的升高,相应发射峰的强度并不是单调的增强,而是由于浓度猝灭和交叉弛豫等因素呈现非单调性的变化。探讨了可能的上转换发射机制。这种上转换发射强度可调控荧光材料在三维固体显示、上转换荧光照明以及荧光探测等领域有潜在的应用。     

Thermal Behavior of the Fluorescence Lines of Ho3+ in Cr,Tm,Ho:YAG

The fluorescence spectra of Cr,Tm,Ho:YAG crystal have been detected at the temperature from 65 to 295 K with interval of 10 K. The width and the shift of Ho3+ lines at 4959.6 cm-1 (at 65 K) have been investigated and interpreted in terms of the interactions between lattice vibration (phonons) and ions. The results showed that the line broadening with the temperature was mainly due to the Raman scattering of phonons,and the line shift with temperature was mainly due to the emission and absorption of virtual phonons.     

Crystal growth and optical properties of Cr3+, Er3+, RE3+: Gd3Ga5O12 (RE=Tm,Ho, Eu) for mid-IR laser applications

In this paper we report on the optical properties of triply Cr³⁺, Er³⁺, and RE³⁺ (RE=Tm, Ho, Eu) doped Gd₃Ga₅O₁₂ crystals that were grown by the Czochralski method. Optical absorption, near-infrared (NIR), and mid-infrared (mid-IR) fluorescence spectra were characterized for the fabricated crystals and corresponding luminescence decay measurements under 654 nm excitation were also carried out. Based on the analysis of energy transfer process between Er and RE (RE=Tm, Ho, Eu) ions, the energy transfer efficiency (ETE) values were evaluated, correspondingly. From the spectral data of all the studied crystals, it is observed that the co-doped Cr³⁺ ion highly increases the absorption pump power and the three kinds of co-doped RE³⁺ ions depopulate the Er:⁴I_13/2 energy level effectively. The spectral analysis shows that titled rare earth doped crystals are promising materials for ～3.0 μm mid-IR laser applications and among them Cr,Er,Eu:GGG is relatively more suitable due to its excellent optical properties compared with others.     

LiSrAlF6晶体Cr3+掺杂中心电子结构的研究

使用离散变分方法(DVM)对LiSrAlF6晶体中以Cr3+为中心的多种分子团簇的电子结构进行了计算.主要研究了镶嵌势、团簇大小、基组类型对单电子能量本征值、基态原子轨道特性的影响,给出了使计算结果趋于收敛的基本条件.     

Tm，Ho双掺杂YV04晶体中Tm对Ho敏化发光现象

摘要：报道了对Tm,Ho双掺YVO4晶体光谱性能的测量结果,包括用UV-365型分光光度计测出单掺Tm：YVO4及Ho：YVO4吸收谱以及双掺Tm：Ho：YVO4的吸收谱;用Ar离子激光器488nm,LD激光器激发测量样品荧光光谱;用J-O理论进行光谱参数计算及对能级结构进行分析;研究了在λ=805nm的激光二极管激发下Tm对Ho的敏化发光过程。发现与YAG,YLF为基质的Tm,Ho双掺材料相比,该材料中的Tm3+离子具有大而均匀的吸收宽度(～26nm),大的峰位吸收截面和积分吸收截面(～1.4×10-20cm2和274.5×10-20 cm),能量转换效率高(可达87％),且泵浦阈值低(～15mW)。表明了YVO4晶体中Tm能有效地敏化Ho,并产生2μm的发射。文中对发射强度与泵浦功率及Tm,Ho之间掺杂浓度的关系进行了初步的分析与讨论。光谱的观察结果表明：在实现LD泵浦,全固体化,小型,高效的,2μm激光振荡的探索中,Tm：Ho：YVO4晶体将是一种很有实际应用潜力的材料。     

Upconverted VUV luminescence of Nd and Er doped into LiYF4 crystals under XeF-laser excitation

The upconverted VUV (185 nm) and UV (230 and 260 nm) luminescence due to 5d-4f radiative transitions in Nd³⁺ ions doped into a LiYF₄ crystal has been obtained under excitation by 351/353 nm radiation from a XeF excimer laser. The maximum upconversion efficiency, defined as the ratio of intensity for 5d-4f luminescence to overall intensity for 5d-4f and 4f-4f luminescence from the ⁴D_3/2 Nd³⁺ level, has been estimated to be about 70% under optimal focusing conditions for XeF laser radiation. A redistribution of intensity between three main components of 5d-4f Nd³⁺ luminescence is observed under changing the excitation power density, which favors the most long-wavelength band (260 nm) at higher excitation density level. The effect is interpreted as being due to excited state absorption of radiation emitted. The upconverted VUV and UV luminescence from the high-lying ²F(2)_7/2 4f level of Er³⁺ doped into a LiYF₄ crystal has also been obtained under XeF-laser excitation the most intense line being at 280 nm from the spin-allowed transition to the ²H(2)_11/2 4f level of Er³⁺, but the efficiency of upconversion for Er³⁺ emission is low, less than 5%.     

Luminescence of YAG doped with Eu,Yb, and Mn ions under VUV excitation

Hydrothermal synthesis has been successfully used to obtain fine-crystalline powders of yttrium aluminum garnet (YAG) doped with manganese ions and codoped with cerium and manganese ions. Using the method of high-temperature solid-state synthesis, ceramic specimens of YAG that contain europium and ytterbium ions have been obtained. In synthesized YAG:Eu and YAG:Yb ceramics, no luminescence that can be attributed to 5d-4f transitions in Eu²⁺ or Yb²⁺ ions has been detected, even though the scheme of energy levels of these ions constructed with respect to YAG energy bands indicates that there is a potential possibility of the occurrence of 5d-4f luminescence for Eu²⁺ ions in YAG. At room temperature, the luminescence spectrum of hydrothermally synthesized YAG doped with manganese ions consists of two broad bands with maxima at ～600 and ～750 nm and does not contain any narrow bands in the red or IR range. Therefore, the spectrum contradicts to the properties of the luminescence of Mn²⁺, Mn³⁺, or Mn⁴⁺ ions in YAG described in the literature, even though the obtained hydrothermal specimens can contain noticeable concentrations only of Mn³⁺ ions.     

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。