Ultraviolet and visible upconversion luminescence of Tm(0.1)Yb(5):FOV oxyfluoride nanophase vitroceramics

The ultraviolet upconversion luminescence of Tm³⁺ ions sensitized by Yb³⁺ ions in oxyfluoride nanophase vitroceramics when excited by a 975 nm diode laser was studied. An ultraviolet upconversion luminescence line positioned at 363.6 nm was found. It was attributed to the fluorescence transition of ¹D₂→³H₆ of Tm³⁺ ion. Several visible upconversion luminescence lines at 450.7 nm, (477.0 nm, 462.5 nm), 648.5 nm, (680.5 nm, 699.5 nm) and (777.2 nm, 800.7 nm) were also found, which result respectively from the fluorescence transitions of ¹D₂→³F₄, ¹G₄→³H₆, ¹G₄→³F₄, ³F₃→³H₆ and ³H₄→³H₆ of Tm³⁺ ion. The careful measurement and analysis of the variation of upconversion luminescence intensity F as a function of the 975 nm pumping laser power P prove that the upconversion luminescence of ¹D₂ state is partly a five-photon upconversion luminescence, and the upconversion luminescence of ¹G₄ state and ³H₄ state are respectively the three-photon and two-photon upconversion luminescence. The theoretical analysis suggested that the upconversion mechanism of the 363.6 nm ¹D₂→³H₆ upconversion luminescence is partly the cross energy transfer of {³H₄(Tm³⁺), ³F₄(Tm³⁺), ¹G₄(Tm³⁺)→¹D₂(Tm³⁺)} and {¹G₄(Tm³⁺)→³F₄(Tm³⁺), ³H₄(Tm³⁺)→¹D₂(Tm³⁺)} between Tm³⁺ ions. In addition, the upconversion luminescence of ¹G₄ and ³H₄ state results respectively from the sequential energy transfer {²F_5/2(Yb³⁺)→²F_7/2(Yb³⁺), ³H₄(Tm³⁺)→¹G₄(Tm³⁺)} and {²F_5/2(Yb³⁺) →²F_7/2(Yb³⁺), ³F₄(Tm³⁺)→³F₂(Tm³⁺)} from Yb³⁺ ions to Tm³⁺ ions. Supported by the National Natural Science Foundation of China (Grant No. 10674019)     

Synthesis and spectroscopy of sodium-gadolinium tungstate NaGd(WO4)2 crystals activated by Tm3+ ions

Single crystals of disordered double sodium-gadolinium tungstate NaGd(WO₄)₂ doped with Tm ions were grown by the Czochralski method. The polarized absorption and emission spectra of these crystals with different activator concentrations and the decay kinetics of the ³ H ₄ and ³ F ₄ excited states of Tm³⁺ ions at 300 K were investigated. The absorption and emission cross sections of the expected laser transition ³ F ₄ ? ³ H ₆ in the Tm³⁺ ion were determined and the amplification spectra of the active laser medium NaGd(WO₄)₂:Tm at different levels of inverse population of the upper laser level ³ F ₄ of the Tm³⁺ ion were constructed. The prospects for using these crystals as active media in 2-μm solid-state lasers are discussed.     

Concentration-dependent luminescence of Tb ions in high calcium aluminosilicate glasses

This study deals with the results on the concentration-dependent fluorescence properties of Tb³⁺-doped calcium aluminosilicate (CAS) glasses of composition (100−x)(58SiO₂–23CaO–5Al₂O₃–4MgO–10NaF in mol%)-x Tb₂O₃ (x=0, 0.25, 0.5, 1, 2, 4, 8, 16, 24, 32, 40 in wt%). The FTIR reflectance spectra suggested the role of dopant ions as network modifiers in the glass network. The fluorescence spectra of low Tb³⁺-doped glasses have revealed prominent blue and green emissions from ⁵D₃ and ⁵D₄ excited levels to ⁷F_j ground state multiplet, respectively. The glass with 2 wt% of Tb₂O₃ has exhibited maximum intensity of blue emission from ⁵D₃ level, while green emission from ⁵D₄ level has increased linearly up to 24 wt% and showed reduction in the rate of increase for higher Tb₂O₃ concentrations. The concentration quenching of blue emission (⁵D₃→⁷F_j) is attributed mainly to the resonant energy transfer (RET) assisted cross-relaxation (CR) among the excited and nearest neighbour unexcited Tb³⁺ ions in the glass matrix. The decline in rate of increase of green emission (⁵D₄→⁷F_j) at higher concentrations has been explained due to a possible occurrence of cooperative energy transfers leading to 4f⁸→4f⁷5d transition interactions. The blue and green emission decay kinetics have been recorded to compute the excited level (⁵D₃ and ⁵D₄) lifetimes, which confirmed the Tb³⁺ concentration quenching of the blue emission in these glasses.     

Efficient tunable laser operation of diode- pumped Yb,Tm:KY(WO4)2 around 1.9 μm

A new laser medium – Yb,Tm:KY(WO₄)₂ – for diode pumped solid state laser applications operating around 1.9 to 2.0 μm has been investigated and the main laser characteristics are presented. Diode pumping at 981 nm and around 805 nm was realised. For 981-nm pumping, the excitation occurs into Yb³⁺ ions followed by an energy transfer to Tm³⁺ions. A slope efficiency of 19% was realised. For pumping around 805 nm, the excitation occurs directly into the Tm³⁺ ions. Here a maximum slope efficiency of 52%, an optical efficiency of 40%, and output powers of more than 1 W were realised. Using a birefringent quartz plate as an intracavity tuning element, the tunability of the Yb,Tm:KY(WO₄)₂ laser in the spectral range of 1.85–2.0 μm has been demonstrated. The possibility of laser operation in a microchip cavity configuration for this material has also been shown. Received: 12 March 2002 / Revised version: 20 May 2002 / Published online: 25 September 2002 RID="*" ID="*"Corresponding author. Fax: +49-531/592-4116, E-mail: stefan.kueck@ptb.de     

Photophysics of the Lanthanide Complexes with Conjugated Carboxylic Acids by Low Temperature Fluorescent Spectroscopy

In the context, some lanthanide (Eu³⁺, Tb³⁺ and Sm³⁺) complexes with conjugated carboxylic acids (pyridine-carboxylic acids derivatives) have been synthesized and characterized. The low temperature fluorescent spectra for these complexes have been measured at nitrogen atmosphere (77 K), indicating that the central Ln³⁺ ions locate in an equivalent coordination environment with low symmetry for most of these lanthanide complexes belonging to dimeric or polymeric structure. Therefore, the electronic dipole transition (supersensitive transition) (⁵D₀ → ⁷F₂ for Eu³⁺, ⁵D₄ → ⁷F₆ for Tb³⁺, ⁴G_5/2 → ⁶H_9/2 for Sm³⁺) and magnetic dipole transition (⁵D₀ → ⁷F₁ for Eu³⁺, ⁵D₄ → ⁷F₅ for Tb³⁺, ⁴G_5/2 → ⁶H_5/2 for Sm³⁺) show the regular change in the corresponding split number of fluorescent spectra, which can be realized to predict the fine structure of lanthanide complexes.     

The 1S0 emission from the minor site of Pr3+ in (Ba,La)F2:Pr

In this paper we present and discuss results of detailed spectroscopy studies of Pr³⁺ luminescence from the (Ba,La)F₂:0.2 m%Pr crystals under UV and VUV synchrotron excitation.We have measured time resolved emissions from the minor site Pr³⁺ in (Ba,La)F₂:Pr at 10 and 300 K. The spectra clearly show the ¹S₀ emission from the Pr³⁺ ions in some low symmetry Pr-sites (we designate them La-sites) previously identified in higher concentration (0.3 m%Pr and more) crystals. However most of emission from the Pr activated (Ba,La)F₂ crystals originates in Pr³⁺ ions in other sites which produce an efficient d-f emission. As demonstrated by excitation spectra, the emission from some of these sites (denoted as Ba-sites) closely resembles the d-f emission from BaF₂.The La-site, time resolved and long delay emission spectra are dominated by hypersensitive transitions from the ¹S₀ and ³P₀ levels to lower energy levels of the 4f² configurations. Only these transitions contribute to the photon cascade emission desired for some mercury free phosphor applications.     

Multiphoton ultraviolet and visible upconversion luminescence of TmYb co-doped oxyfluoride glass

The ultraviolet upconversion luminescence of Tm³⁺ ions sensitized by Yb³⁺ ions in oxyfluoride glass when excited by a 975 nm diode laser was studied in this paper. One typical ultraviolet upconversion luminescence lines positioned at 362.3 nm was found. It can be attributed to the five-photon upconversion luminescence transition of ¹D₂ → ³H₆. Several visible upconversion luminescence lines at 451.1 nm, (477.9 nm, 462.5 nm), 648.7 nm, (680.5 nm, 699.5 nm) and (777.5 nm, 800.7 nm) were found also, which results from the fluorescence transitions of five-photon ¹D₂ → ³F₄, three-photon ¹G₄ → ³H₆, three-photon ¹G₄ → ³F₄, two-photon ³F₃ → ³H₆ and two-photon ³H₄ → ³H₆ of Tm³⁺ ion, respectively. The theoretical analysis suggests that the upconversion mechanism of the 362.3 nm ¹D₂ → ³H₆ upconversion luminescence is the cross energy transfer of {³H₄(Tm³⁺) → ³F₄(Tm³⁺), ¹G₄(Tm³⁺) → ¹D₂(Tm³⁺)} and {¹G₄(Tm³⁺) → ³F₄(Tm³⁺), ³H₄(Tm³⁺) → ¹D₂(Tm³⁺)} between Tm³⁺ ions. In addition, the upconversion luminescence of ¹G₄ and ³H₄ state results from the sequential energy transfer {²F_5/2(Yb³⁺) → ²F_7/2(Yb³⁺), ³H₄(Tm³⁺) → ¹G₄(Tm³⁺)} and {²F_5/2(Yb³⁺) → ²F_7/2(Yb³⁺), ³F₄(Tm³⁺) → ³F₂(Tm³⁺)} from Yb³⁺ ions to Tm³⁺ions, respectively.     

Up-conversion emission in triply-doped Ho/Yb/Tm KGd(WO4)2 single crystals

Detailed spectroscopic studies of the triply doped KGd(WO₄)₂:Ho³⁺/Yb³⁺/Tm³⁺ single crystals (which exhibit multicolor up-conversion fluorescence) are reported for the first time. The absorption spectra of crystals were measured at 10 and 300 K; the room temperature luminescence spectra were excited at 980 nm wavelength. The dependence of the intensity of luminescence on the excitation power for three different concentration of Ho³⁺, Yb³⁺ and Tm³⁺ ions was investigated. Efficient green and red up-converted luminescence of Ho³⁺ ions and weak blue up-conversion luminescence of Tm³⁺ ions were observed in spectra. The red emission of Ho³⁺ ions is more intensive than their green emission. Dependence of the up-conversion luminescence intensity on the excitation power and impurities concentration was also studied; the number of phonon needed for efficient up-conversion was determined for each case. All possible energy transfer processes between different pairs of the impurity ions' energy levels are also discussed.     

On spectroscopic properties of the KYb(WO4)2:Pr3+ crystal

Spectroscopic properties of Pr³⁺ doped KYb(WO₄)₂ single crystals were investigated. The crystal lattice parameters were determined. Energy levels of Pr³⁺ in KYb(WO₄)₂ were assigned. The absorption, emission, excitation, time-resolved emission and excitation spectra were measured at low (10 K) and at room temperature. Decay times of the praseodymium emissions are non-exponential and unusually short. Site selection spectroscopy evidences several different Pr³⁺ sites. The Judd-Ofelt intensity model was used to analyse the experimental data. The Ω λ parameters, branching ratio and electric dipole transition probabilities were determined.     

Photoluminescence and energy transfer of Tm doped LiIn (WO4)2 blue phosphors

Room temperature steady and time resolved emission spectra of LiIn_1−xTm_x(WO4)2 (where thulium concentration is 0, 0.5, 1, 5 and 10 at%) blue phosphors, under UV excitation energy have been investigated. The concentration quenching effect on the blue emission, due to the (WO₄)⁻² groups and ¹G₄→³H₆ emission transition of Tm³⁺ were studied. Two energy transfer mechanisms are shown. The first takes place between excited (WO₄)⁻² groups and the ¹G₄ energy level of Tm³⁺, and is mainly analyzed by phonon-assisted energy transfer. The second mechanism is due to an energy transfer from the excited Tm³⁺ ions to the surrounding ground state Tm³⁺ ions. The non-exponential decay curves of the ¹G₄ level observed for higher concentrations are analyzed by the Inokuti–Hirayama model. We think that the quenching effect between Tm³⁺ ions is mainly linked to the dipole–dipole interactions.     

CW laser performance of Yb and Er,Yb doped tungstates

 Room temperature cw laser action of Yb³⁺-doped KY(WO₄)₂ and KGd(WO₄)₂ crystals at 1.025 μm and Er, Yb : KY(WO₄)₂ at 1.54 μm has been demonstrated under pumping by both Ti-sapphire laser and InGaAs laser diodes. A slope efficiency of Yb-lasers up to 78% has been obtained. Received: 19 June 1996     

Tm3+离子掺杂的钨酸钇钠晶体中浓度猝灭效应的研究

测量了Tm³⁺离子不同浓度(0.5at.%, 3 at.%, 5 at.%)掺杂的NaY(WO₄)₂晶体在800nm激光二极管激发下的上转换发射光谱.结合吸收谱、荧光谱和由Judd-Ofelt理论计算的光谱参数，详细分析了Tm³⁺:NaY(WO₄)₂晶体中上转换能量传递机理和离子浓度对上转换发射的影响.讨论了四种影响上转换发光效率的离子间相互作用机理：³H₅+¹G₄→³H₆+¹D₂，³H₅+³H₅→³H₆+³F₃，¹G₄+³H₆→³F₄+³F₃，¹G₄+³H₆→³F₃+³F₄，并根据Miyakawa-Dexter理论定量计算了各过程的发生概率.论证了交叉弛豫和共协上转换等浓度猝灭效应是影响Tm³⁺离子蓝色上转换荧光发射效率的主要因素. 关键词： 3+离子')" href="#">Tm³⁺离子 4)₂晶体')" href="#">NaY(WO₄)₂晶体 上转换 浓度猝灭     

Nonlinear refractive properties of Yb3+-doped KY(WO4)2 and YVO4 laser crystals

The nonlinear refractive indices of Yb³⁺: KY(WO₄)₂ and Yb³⁺:YVO₄ laser crystals are characterized using a Z-scan technique at a wavelength of 1.08 μm for different polarizations. The results reveal that the nonlinear refractive index of Yb³⁺:YVO₄ is superior to that of Yb³⁺:KY(WO₄)₂ and is found to be 1.9×10^-15 cm²/W and 1.5×10^-15 cm²/W for E⊥c and E∥c polarizations, respectively. PACS 42.65.Hw; 42.55.Rz; 42.65.Re; 42.70.Hj     

Er3+，Tm3+共掺的NaY(WO4)2晶体的光谱分析和上转换发光

在室温下，测量了Er:Tm:NaY(WO₄)₂晶体的吸收光谱、激发光谱、发射光谱以及上转换发光，并运用J-O理论对测量的结果进行了计算，得出了Er:Tm:NaY(WO₄)₂晶体的强度参数.报道了Tm，Er离子间特殊的能量传递和相关上转换，解释了离子间的能级跃迁过程.同时，对于Er增强Tm离子近红外发光的特性也作了充分研究. 关键词： 4)₂晶体')" href="#">Er:Tm:NaY(WO₄)₂晶体 吸收光谱 发射光谱 激发光谱 上转换     

Preparation and photoluminescent properties of doped nanoparticles of ZnS by solid-state reaction

Nanometer-sized Eu³⁺-doped ZnS and Mn²⁺-doped ZnS particles were prepared by solid-state method at low temperature. The structures and properties of those materials were characterized by X-ray diffraction (XRD) and photoluminescent spectroscopy techniques. The XRD patterns reveal that the doped ZnS nanoparticles belong to zinc-blende structure. The concentration of doping ions has little effect on the sizes of the doped ZnS nanoparticles, which mainly depends on the temperature of preparation. The emission peaks from the ⁵D₀→⁷F_J (J=1, 2, and 4) electronic energy transitions of Eu³⁺ were observed in the emission spectra of the ZnS:Eu³⁺ nanoparticles. The intensity ratio of the two peaks from the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions indicates that more Eu³⁺ ions occupy the sites with no inversion symmetry. For the ZnS:Mn²⁺ nanoparticles, an orange emission from the ⁴T₁→⁶A₁ transition of Mn²⁺ is present, indicating that the doping ions occupy the positions of the ZnS lattices. Meanwhile, UV-induced luminescence enhancement was observed for the ZnS:Mn²⁺ nanoparticles, the possible reason of which is discussed primarily.     

Probing of inversion symmetry site in Eu-doped GdPO4 by luminescence study: Concentration and annealing effect

Eu³⁺-doped gadolinium orthophosphate (GdPO₄) (Eu³⁺ at%=0, 2, 5, 7, 10, 15, 20 and 30) nanoparticles have been prepared by ethylene glycol route and subsequently heated at 500 and 900 °C. The crystallite size increases with increasing heat-treatment temperature. Luminescence study shows that magnetic dipole transition (⁵D₀→⁷F₁) is prominent over the electric dipole transition (⁵D₀→⁷F₂), which has been attributed to occupancy of inversion symmetry site by more Eu³⁺ ions in Eu³⁺-doped GdPO₄. The luminescence intensity is enhanced as heat-treatment temperature increases from 500 to 900 °C due to the improved crystallinity. Optimum luminescence is observed for 5–7 at% Eu³⁺ in GdPO₄ nanoparticles. Above this concentration, luminescence intensity decreases due to concentration quenching effect. This is supported by lifetime study.     

Enhancement of upconversion luminescence in Tm/Er/Yb-codoped glass ceramic containing LiYF4 nanocrystals

A transparent Er³⁺–Tm³⁺–Yb³⁺ tri-doped oxyfluoride glass ceramics containing LiYF₄ nanocrystals were prepared. Under 980 nm laser diode (LD) pumping, intensive red, green and blue upconversion (UC) was obtained. The blue, green, and red UC radiations correspond to the transitions ¹G₄→³H₆ of Tm³⁺, ²H_11/2/⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2 of Er³⁺ ions, respectively. This is similar to that in Tm³⁺–Yb³⁺ and/or Er³⁺–Yb³⁺ co-doped glass ceramics. However, the blue UC radiations of the Er³⁺–Yb³⁺ co-doped glass ceramics is two-photon process due to cooperative energy transfer. The UC mechanisms were proposed based on spectral, kinetic, and pump power dependence analyses.     

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.     

Spectroscopic properties of Yb ions in La2(WO4)3 crystal

Yb³⁺-doped La₂(WO₄)₃ single crystals were grown by the Czochralski technique. Absorption and fluorescence spectra of the crystal were recorded at the room temperature. The stimulated emission cross-sections of Yb³⁺ ions were calculated using the reciprocity method and Fuchtbauer-Ladenburg formula, respectively. The fluorescence decay curves of ²F_5/2 manifold of Yb³⁺ ions were recorded at room temperature for both crystal and powder samples. The effect of radiation trapping on the spectroscopic properties is discussed. Comparison with other Yb³⁺-doped laser crystals is made. The results show that Yb³⁺:La₂(WO₄)₃ crystal is a promising laser material.     

Structure dependence of near-infrared stimulated blue emission in polycrystalline Ln2(WO4)3 (Ln=Gd and Lu) doped with Tm and Yb

Tm- and Yb-doped gadolinium tungstate, (Gd_xTm_yYb_1−x−y)₂(WO₄)₃ (x=0.7-0.9; y=0.001-0.01), have been prepared by the polymerized complex method to achieve a homogeneous dispersion of dopants and to stabilize the host structure. Decomposition (900 °C 5 h) of the precursors with x=0.8-0.9 yielded a pure monoclinic phase, while that of x=0.7 resulted in formation of an orthorhombic impurity. The monoclinic phase exhibits bright up-converted blue emission due to the ¹G₄→³H₆ transition of Tm³⁺ (472 nm) upon excitation into the Yb³⁺:²F_7/2→²F_5/2 absorption band as a result of energy transfer from Yb to Tm. The orthorhombic impurity acts as a strong quencher of emission, and the quenching mechanism has been discussed on the basis of structural and spectroscopic properties of orthorhombic Lu₂(WO₄)₃:Tm,Yb prepared by the same method.