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.     

High-power diode-cladding-pumped Tm<Superscript>3+</Superscript>, Ho<Superscript>3+</Superscript>-doped silica fibre laser

The fundamental characteristics of a continuous-wave high-power diode-pumped Tm³⁺, Ho³⁺-doped double-clad silica fibre laser are presented. A maximum output power of 5.2 W was measured and was generated at a slope efficiency of 42 (44)% with respect to the launched (absorbed) pump power. At the optimum length of 7 m (_effL=2.9, where _eff is the effective absorption coefficient of the fibre and L is the fibre length), the fibre laser output was measured to have a centre wavelength of 2105 nm and a line width of 20 nm. The centre wavelength of the emission was tunable over a 32-nm extent when 0.68<_effL<3.28 or for a 6.2-m change in L. PACS 42.55.Wd; 42.55.Xi; 42.60.Lh; 42.60.Pk     

铒离子浓度对掺Er3+碲酸盐玻璃的Judd-Ofelt理论参数的影响

制备了四种不同铒离子掺杂浓度的碲酸盐玻璃,通过测定吸收光谱计算了吸收谱线的振子强度,根据Judd-Ofelt理论计算了不同浓度下Er3 离子发光光谱的强度参数Ωi(i=2,4,6),计算了自发辐射电偶和磁偶跃迁概率、辐射寿命、荧光分支比等参数,讨论了Er3 离子浓度变化对以上这些参数的影响.测试了Er3 :4I13/2→4I15/2跃迁对应的荧光光谱和Er3 :4I13/2能级荧光寿命.最后应用McCumber理论计算了玻璃中Er3 :4I13/2→415/2跃迁对应的受激发射截面大小.结果表明:振子强度基本上随Er3 离子浓度的增大而增强;随着Er3 离子浓度的增加,自发辐射跃迁概率A基本呈现出递增的趋势,但荧光分支比β却只有很小的变化;Er3 :4I13/2→4I15/2的发射截面随Er3 离子浓度的增大而改变很小,有效线宽都在50 nm左右.     

掺饵碲酸盐玻璃的光谱性质和能量传递

测试了掺Er碲酸盐玻璃在974nmLD泵浦下的吸收光谱、荧光光谱和上转换光谱，应用McCumber理论计算了Er^3 的受激发射截面，分析了碲酸盐玻璃中Er^3 离子的上转换发 光机制，研究了Yb^3 离子对Er^3 离子上转换发光强度的影响以及两者之间的能量传递特性。     

The comparative analysis and optimization of the free-running Tm<Superscript>3+</Superscript>:YAP and Tm<Superscript>3+</Superscript>:YAG microlasers

The thulium microlasers based on yttrium-aluminium perovskite and yttrium-aluminium garnet crystals are considered as coherent light sources at the wavelength near 2 μm. The comparative analysis of these lasers is carried out by means of the lasers’ parameters optimization for each value of the pumping power taking into consideration the cross-relaxation and up-conversion processes as well as heating of the active medium. The optimal values of the active medium length, activator concentration and the output mirror reflectivity are determined both for Tm:YAP- and Tm:YAG-laser. The pulse generation of Tm:YAP- and Tm:YAG-lasers is also considered, the parameters of this regime are determined. The comparison shows the suitability of Tm:YAP laser crystal both for cw and pulse generation. The up-conversion influence on the laser characteristics is also analyzed. PACS 42.60.Gd     

793 nm抽运下的掺Tm3+碲酸盐玻璃的发光特性

研究了掺Tm^3 碲酸盐玻璃在793nm钛宝石激光器抽运下的发光特性,结果发现除常规的^3H4→^3H6的811nm荧光外,还存在很强的^1G4→H5的785nm二光子转换荧光以及较弱的710nm和677nm三光子上转换荧光。     

Stable and Efficient Pulsed Mid-Infrared Laser Generation from an Er<Superscript>3+</Superscript>-Doped ZBLAN Fiber Laser

We demonstrate a stable and efficient passively Q-switched 2.8 μm Er³⁺-doped ZBLAN fiber laser with a broadband semiconductor saturable absorber mirror. Enabled by the broadband optical modulator, the stable Q-switched fiber laser can deliver a maximum average power over 700 mW with corresponding per-pulse energy of 8.19 μJ and a pulse width of 1.3 μs at a repetition rate of 88.6 kHz under an incident pump power of 3.8 W. In addition, the slope efficiency can reach 22.5%. To the best of our knowledge, this is the highest reported slope efficiency for the passively Q-switched Er³⁺-doped ZBLAN fiber laser.     

Green,blue, red,near-infrared up-conversion luminescence of Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>/Tm<Superscript>3+</Superscript> co-doped YVO<Subscript>4</Subscript> nanoparticles

YVO₄:Yb³⁺,Er³⁺; YVO₄:Yb³⁺,Tm³⁺; and YVO₄:Yb³⁺,Er³⁺,Tm³⁺ were all synthesized via sol-gel method with a subsequent thermal treatment. Specifically, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ phosphors were prepared with different annealing temperatures to study the influence of temperature. The transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffractometer (XRD), and photoluminescent (PL) spectrofluorometer were used to investigate the morphology, crystal structure, and up-conversion luminescent properties of all samples. In summary, all samples were granular-like nanoparticles and well crystallized with the same tetragonal phase as YVO₄. Under the irradiation at 980 nm, YVO₄:Yb³⁺,Er³⁺ phosphors can generate green emission at 525 and 553 nm and red emission at 657 nm, while YVO₄:Yb³⁺,Tm³⁺ phosphors can generate blue emission at 476 nm, red emission at 648 nm, and near-infrared emission at 800 nm. Notably, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ samples can exhibit green emission, blue emission, red emission, and near-infrared emission at the same time, which might endow the as-prepared samples with potential applications in many fields, such as luminous paint, infrared detection, and biological label.     

Observation and interpretation of the Tm<Superscript> 3+</Superscript> free ion spectrum

The emission spectrum of thulium produced by a vacuum spark source was observed in the wavelength range from 700 to 2320 ? on the 10.7 m normal-incidence vacuum ultraviolet spectrograph at the Paris-Meudon observatory. In the unknown spectrum of Tm IV, more than 760 lines have been identified for the first time as transitions between 157 levels of 4f¹¹5d, 33 levels of 4f¹¹6p, 9 levels of 4f¹¹6s and 10 levels of the 4f¹² ground configuration. A parametric interpretation of the levels has been carried out using the Cowan codes. Configuration interaction effects are discussed, in particular with the core-excited configurations 5p⁵4f¹³ and 5p⁵4f¹²5d. Radial Slater parameters derived from 4f¹² levels are larger than those pertaining to trivalent Tm ions in compounds. A selection of 105 prominent lines is given.     

The upconversion luminescence and magnetism in Yb<Superscript>3+</Superscript>/Ho<Superscript>3+</Superscript> co-doped LaF<Subscript>3</Subscript> nanocrystals for potential bimodal imaging

Biocompatible upconversion nanoparticles with multifunctional properties can serve as potential nanoprobes for multimodal imaging. Herein, we report an upconversion nanocrystal based on lanthanum fluoride which is developed to address the imaging modalities, upconversion luminescence imaging and magnetic resonance imaging (MRI). Lanthanide ions (Yb³⁺ and Ho³⁺) doped LaF₃ nanocrystals (LaF₃ Yb³⁺/Ho³⁺) are fabricated through a rapid microwave-assisted synthesis. The hexagonal phase LaF₃ nanocrystals exhibit nearly spherical morphology with average diameter of 9.8 nm. The inductively coupled plasma mass spectrometry (ICP-MS) analysis estimated the doping concentration of Yb³⁺ and Ho³⁺ as 3.99 and 0.41%, respectively. The nanocrystals show upconversion luminescence when irradiated with near-infrared (NIR) photons of wavelength 980 nm. The emission spectrum consists of bands centred at 542, 645 and 658 nm. The stronger green emission at 542 nm and the weak red emissions at 645 and 658 nm are assigned to ⁵S₂ → ⁵I₈ and ⁵F₅ → ⁵I₈ transitions of Ho³⁺, respectively. The pump power dependence of luminescence intensity confirmed the two-photon upconversion process. The nanocrystals exhibit paramagnetism due to the presence of lanthanide ion dopant Ho³⁺ and the magnetization is 19.81 emu/g at room temperature. The nanocrystals exhibit a longitudinal relaxivity (r ₁) of 0.12 s^?1 mM^?1 and transverse relaxivity (r ₂) of 28.18 s^?1 mM^?1, which makes the system suitable for developing T2 MRI contrast agents based on holmium. The LaF₃ Yb³⁺/Ho³⁺ nanocrystals are surface modified by PEGylation to improve biocompatibility and enhance further functionalisation. The PEGylated nanocrystals are found to be non-toxic up to 50 μg/mL for 48 h of incubation, which is confirmed by the MTT assay as well as morphological studies in HeLa cells. The upconversion luminescence and magnetism together with biocompatibility enables the adaptability of the present system as a nanoprobe for potential bimodal imaging.     

Spectroscopic indications of the possible optical cooling effect in fluoride crystals activated by Yb<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> ions

The results of spectral kinetic studies of several fluoride crystals activated by Yb³⁺ and Tm³⁺ ions are presented, and their possible application as cooling elements of optical refrigerators is discussed. Optimum excitation conditions for the laser cooling effect in these crystals are found. The cooling efficiency is established to depend on the degree of order in the active medium.     

Molecular self-organization of Ho<Superscript>3+</Superscript> impurity ions in synthetic forsterite

The structure of paramagnetic centers formed by impurity Ho³⁺ ions in synthetic forsterite is studied by submillimeter EPR spectroscopy in the frequency range 65–200 GHz. It is found that Ho³⁺ enters into the Mg²⁺ sublattice in the form of single ions and dimer centers. The concentration of dimer centers considerably exceeds the concentration of single ions, which points to the molecular self-organization of Ho³⁺ impurity ions into dimers during the growing of the crystals from melt. Possible structures of the dimer center are discussed. The parameters of the effective spin Hamiltonian describing the behavior of the electron-nuclear sublevels of the two lowest electronic levels of the Ho³⁺⁵I₈ ground multiplet are determined for a single ion and a dimer center.     

Structural Properties of Cr<Superscript>3+</Superscript>-Doped Cadmium Oxide Nanopowders

The Cr³⁺-doped cadmium oxide nanopowder is prepared at room temperature by a mild and simple solution method. The prepared powder is characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), optical, electron paramagnetic resonance (EPR) and Fourier transform infrared (FT-IR) techniques. The XRD powder pattern reveals the lattice structure and cell parameters are evaluated. The SEM image shows the stone-like morphology of the nanopowder. The optical absorption spectrum indicates the distorted octahedral site symmetry of Cr³⁺ ions. The crystal field Dq and interelectronic repulsion parameters B and C are evaluated. The EPR spectrum gives a resonance signal at g = 1.973 for Cr³⁺ ions. The FT-IR spectrum reveals the characteristic vibrations of cadmium oxide.     

Laser-polarimetric measurements of magnetic ac-susceptibility in LiYF<Subscript>4</Subscript>: Ho<Superscript>3+</Superscript> crystals

Laser-polarimetric technique with the shot-noise-limited polarimetric sensitivity is used to study magnetic ac-susceptibility in holmium doped LiYF₄ crystals in the range of Zeeman energies comparable with that of the hyperfine interaction in Ho³⁺ ions. Specific features of optical methods of magnetic measurements, the experimental setup, and results of measurements are discussed. Polarimetric sensitivity of the setup (～10^?8 rad) allowed us to measure the ac-susceptibility of LiYF₄ single crystals containing 0.1–0.3 mol % of impurity Ho³⁺ ions with the signal-to-noise ratio exceeding 10². The obtained field-strength and frequency dependences of the ac-susceptibility show that the resonant peaks of the susceptibility mainly result from cross-relaxation transitions between the electronic-nuclear sublevels of Ho³⁺ ions.     

Comparative study of continuous wave Tm<Superscript>3+</Superscript>-doped silica and fluoride fiber lasers

We compare Tm³⁺-doped silica and fluoride fiber lasers in continuous wave operation using the same experimental setup. For incident pump powers of up to 50 W, the fluoride fiber is shown to have higher output power and efficiency compared to silica and reaches a maximum output power of 20 W at 1.94 μm. A slope efficiency of 49% (41%) and a maximum optical-to-optical efficiency of 45% (35%) at an incident pump power of 25 W (37 W) were determined for the fluoride (silica) fibers, respectively. These optical-to-optical efficiencies are the highest reported for directly diode-pumped Tm³⁺-based fiber lasers. We establish that in free-running mode, fiber lasers using fluoride glass are temporally more stable than fiber lasers using a silica host. PACS 42.55.Wd; 42.55.Xi; 42.60.Mi; 42.70.Hj     

Intensity of the <Emphasis Type="Italic">f-f</Emphasis> transitions of Nd<Superscript>3+</Superscript>, Er<Superscript>3+</Superscript>, and Tm<Superscript>3+</Superscript> rare-earth ions in calcium niobium gallium garnet crystals

This paper reports on the results of the investigation into the intensities of the f-f transitions of Nd³⁺, Er³⁺, and Tm³⁺ ions in calcium niobium gallium garnet (CNGG) crystals. The values of the oscillator strengths and line strengths obtained for hypersensitive transitions and the intensity parameters Ω _t of the rare-earth ions in the CNGG crystals are compared with the corresponding quantities for crystals of other garnets and some oxide and fluoride crystals. The assumption is made that an increase in the oscillator strengths and line strengths for the hypersensitive transitions and the intensity parameters Ω₂ of the Nd, Er, and Tm ions in the CNGG crystals as compared to those for crystals of other garnets is associated with the specific features revealed in the crystal structure of the calcium niobium gallium garnet, in particular, with the lowering of the symmetry of the positions occupied by rare-earth ions in the crystal structure.     

Lines of Ho<Superscript>3+</Superscript>-Ho<Superscript>3+</Superscript> pair centers in optical spectra of LiYF<Subscript>4</Subscript> and LiLuF<Subscript>4</Subscript> crystals

The high-resolution spectra of LiYF₄ and LiLuF₄ crystals doped with holmium are studied. It is shown that the weak satellites of some principal lines observed in the optical spectra belong to Ho³⁺-Ho³⁺ pair centers. The role played by local crystal-field distortions in the formation of the spectrum of pair centers is verified experimentally.     

Sensitizer-dependent up-conversion of Ho<Superscript>3+</Superscript> in nanocrystalline Y<Subscript>2</Subscript>O<Subscript>3</Subscript>

Ho³⁺–Yb³⁺ co-doped Y₂O₃ nanocrystals were synthesized by firing hydroxy carbonate precursors. Yb³⁺-concentration-dependent up-conversion properties of Ho³⁺ in Y₂O₃ nanocrystals have been investigated. The relative intensity of up-converted red emission increases more quickly than that of the green and the near-infrared ones with the enhancement of the concentration of Yb³⁺. It is believed that the energy process ⁵ S ₂ (⁵F₄) (Ho) + ⁵ I ₇ (Ho) →⁵ I ₆ (Ho)+⁵ F ₅ (Ho) plays an important role in the population of the ⁵ F ₅ level of Ho³⁺. The result indicates that the intensity ratio of the green emission to the red one can be tuned by changing the sensitizer concentration. PACS 78.55.-m     

Spectroscopy of NaLa(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>: Tm<Superscript>3+</Superscript> and NaGd(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>: Tm<Superscript>3+</Superscript> crystals as advanced laser materials

Single crystals of double sodium-containing lanthanum and gadolinium molybdates doped with Tm³⁺ ions were synthesized by the Czochralski method. The spectroscopic properties of these crystals were investigated from the viewpoint of their use as active media in diode-pumped lasers. The polarized spectra of absorption on the ³ H ₄ and ³ F ₄ levels and the polarized spectra of luminescence due to the ³ F ₄-³ H ₆ laser transition were recorded, and the lifetimes of the ³ H ₄ and ³ F ₄ excited states of the Tm³⁺ ions were determined. The luminescence cross sections were calculated using the Füchtbauer-Ladenburg formula. The simulation of the decay curve of the ³ H ₄ excited state according to the Golubov-Konobeev-Sakun method revealed that, in the crystals under investigation, the interaction between Tm³⁺ ions predominantly occurs through the dipole-dipole mechanism.