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.     

Highly efficient cooperative energy transfer from Ho3+ and Tm3+ ions to Ce3+ ions in crystals

A phenomenon of highly efficient cooperative energy transfer from Ho³⁺ and Tm³⁺ ions to two-particle (2Ce³⁺) cooperative acceptors in crystals of solid solutions of La_1?x Ce _x F₃ is revealed. The rates of cooperative energy transfer in Ho³⁺→2Ce³⁺, Tm³⁺→2Ce³⁺, and Tb³⁺→ 2Yb³⁺ systems are measured, as well as their dependence on the magnitude of the matrix elements of donor transition.     

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.     

Optical transitions of Eu3+ and Dy3+ ions in lead phosphate glasses

Lead phosphate glasses containing Eu(3+) and Dy(3+) have been studied. Local structure was verified using Fourier transform (FT)-IR spectroscopy. Emission bands of Eu(3+) and Dy(3+) ions in lead phosphate glasses are observed in the visible spectral range, which correspond to 5D0→7F(J) (J=0,1,2,4) and 4F(9/2)→6H(J/2) (J=15,13,11) transitions, respectively. Shorter luminescence decays from excited states of Eu(3+) and Dy(3+0 are due to the presence of PbO in phosphate glass.     

Spectroscopic characteristics of the Nd3+ ions in garnet crystals

The article deals with the research of oscillator strengths and the Ω_t (t=2,4,6) intensity parameters of Nd³⁺ doped garnet crystals. It has been found that the absorption intensity of the ⁴I_9/2→⁴G_5/2, ²G_7/2 hypersensitive transition in the Ca₃(NbGa)₅O₁₂ crystals doped with Nd³⁺ is considerably higher than the corresponding values in the following garnet crystals: Y₃Al₅O₁₂:Nd, (GdY)₃(ScAl)₅O₁₂:Nd, Gd₃(ScAl)₅O₁₂:Nd and (GdСa)₃(GaZr)₅O₁₂:Nd. It has been established also that the Ω₂ intensity parameter of the Ca₃(NbGa)₅O₁₂:Nd crystals is one order of magnitude higher compared to the same parameter for the other garnet crystals. These effects in the Ca₃(NbGa)₅O₁₂:Nd crystals are explained by the presence of the Nd³⁺ ions optical sites with a symmetry of local environment C₂, C_2v, C₁.     

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。     

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。     

Tm3+单掺杂及Tm3+, Dy3+共掺杂YP1-xVxO4荧光粉的光谱性质

采用共沉淀法制备了Tm³⁺单掺杂及Tm³⁺,Dy³⁺共掺杂的YP_1-xV_xO₄荧光粉材料。给出了样品的XRD谱,获得了样品的SEM照片,对其发射和激发光谱也进行了测量。结果发现,随着钒酸根含量的增加,样品的激发带发生红移,这样的激发带能够满足白光LED用荧光粉的激发要求。在Tm³⁺,Dy³⁺共掺杂的样品中观测到了全色的发射,并且红、绿、蓝三个发射组分的比例也可以调整。我们计算了不同样品的色坐标,发现均在白光范围内,可见该体系样品有希望成为一种全色发射的白光LED用荧光粉。     

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.     

Electron paramagnetic resonance of Dy3+ in cubic ZnSe and Tm3+ in hexagonal CdS single crystals

Electron paramagnetic resonance has been observed for Dy³⁺ in ZnSe and Tm³⁺ in CdS. For Dy³⁺ doped ZnSe, an isotropic spectrum was observed having well resolved hyperfine lines due to ¹⁶¹Dy and ¹⁶³Dy. The g value obtained was 6.577 ± 0.002 and ¹⁶¹A was 191 ± 1 × 10⁴ cm^?1 and ¹⁶³A was 265 ± 3 × 10^?4 cm^?1. The agreement of the observed g value to g(τ₆) = 6.667 and the point-charge calculations suggest that Dy³⁺ occupies an interstitial (II) site with no local charge compensation. For Tm³⁺ doped in hexagonal CdS, an axial spectrum consistent with g_⊥ = 0, g_∥ = 10.722 ± 0.007, D = 2.57 GHz (crystal field splitting) and ¹⁶⁹A = 1207 ± 5 × 10^?4cm^?1. The large g_∥ value indicates that the Tm ion exits in the trivalent state. This is in reasonable agreement with previous reports of the non-Kramer's state of Tm³⁺.     

EPR study of some rare-earth ions (Dy3+, Tb3+, and Nd3+) in YBa2Cu3O6-compound

We investigate the low temperature X-band electron paramagnetic resonance (EPR) of YBa(2)Cu(3)O(x) compounds with x congruent with 6.0 doped with Dy(3+), Tb(3+), and Nd(3). The EPR spectra of Dy(3+) and Tb(3+) have been identified. The EPR of Tb(3+) is used also to study the effect of suppression of high T(c) superconductivity by doping with Tb(3+). The EPR of Nd(3+) is probably masked by the intense resonance of Cu(2+). All experimental EPR results compare well with theoretical estimations.     

Intensity and bandwidth of multiphonon vibronic transitions of rare-earth ions in crystals

The theory of multiphonon vibronic coupling to electronic transitions is applied in analysing fluorescence spectra of Eu²⁺ in BaFCI, which consist of the 4f⁷(⁶P_7/2,) → 4f⁷(⁸S_7/2) and 4f⁶5d → 4f⁷ transitions, and the 4f⁷-4f⁶5d excitation spectrum of Ce³⁺ in YPO⁴. The 4f electrons are weakly coupled to lattice vibration modes so that only weak one- and two-phonon sidebands are observable in the 4f-4f optical transitions, whereas the electron-phonon coupling is significantly stronger for a 5d electron. Accordingly, intensive multiphonon vibronic transitions overwhelmingly dominate the 4f⁶5d → 4f⁷ spectrum. It is shown that the extended Judd-Ofelt theory for weak vibronic coupling in the framework of the M-process is equivalent to the Huang-Rhys theory for the δ-process. In the analysis of experimental data, contributions from local ligand modes and lattice acoustic modes are separated, and the coupling strength is evaluated, in terms of the Huang-Rhys parameter S, for the 4f-4f and 5d-4f vibronic transitions.