Spectroscopy and energy level location of the trivalent lanthanides in LiYP4O12

The excitation and emission properties of the lanthanides Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Tb³⁺, Er³⁺, Tm³⁺, and Yb³⁺ in LiYP₄O₁₂ were studied by vacuum ultra-violet spectroscopy at 10 K. It provides information on the energies of 4f-5d excitation and emission bands. In the case of Er³⁺ spin forbidden emission was observed. Charge transfer excitation bands were identified for Eu³⁺, Sm³⁺, Tm³⁺, and Yb³⁺, and in the case of Yb³⁺ charge transfer luminescence is observed. All data appear to be consistent with each other and have been used to construct a level scheme showing the location of the energy levels of all trivalent and divalent lanthanides in LiYP₄O₁₂.     

Cooperative energy transfer and frequency upconversion in Yb3+-Tb 3+ and Nd 3+-Yb 3+-Tb 3+ codoped GdAl3(BO3)4 phosphors

Polycrystalline GdAl₃(BO₃)₄ phosphors codoped with Yb³⁺/Tb³⁺ and/or Nd³⁺/Yb³⁺/Tb³⁺ have been synthesized by combustion method. Upon excitation with a 980 nm laser diode, an intense green upconversion luminescence has been observed in GdAl₃(BO₃)₄:Yb,Tb phosphor. The quadratic dependence of the luminescence on the pump-laser power indicating a cooperative energy transfer process. Meanwhile, it is noticed that upon excitation with 808 nm laser diode, intense luminescence has clearly been detected in GdAl₃(BO₃)₄:Nd,Yb,Tb phosphor. The luminescence intensity exhibits also a quadratic dependence on incident pump-laser power. However, no green-emission has been observed in GdAl₃(BO₃)₄ phosphors codoped with Yb³⁺/Tb³⁺ or Nd³⁺/Tb³⁺ respectively upon excited at 808 nm laser diode. A proposed upconversion mechanism involving energy transfer from Nd³⁺ to Yb³⁺, and then a cooperative energy transfer process from two excited Yb³⁺ to Tb³⁺ has been presented.     

磷酸盐玻璃中Yb3+和Nd3+之间的声子参助能量转移

本文中报道了磷酸盐玻璃中Nd³⁺,Yb³⁺的时间分辨谱和激发能量的转移。通过实验确定了在不同温度下的转移速率。证实了Nd³⁺→Yb³⁺的能量转移机构为从⁴F_3/2(Nd³⁺)到²F_5/2(Yb³⁺)并同时产生单声子发射的过程;而从Yb³⁺到Nd³⁺关键词：     

A global design of high power Nd-Yb co-doped fiber lasers

A global optimization method - niche hybrid genetic algorithm (NHGA) based on fitness sharing and elite replacement is applied to optimize Nd³⁺-Yb³⁺ co-doped fiber lasers (NYDFLs) for obtaining maximum signal output power. With a objective function and different pumping powers, five critical parameters (the fiber length, L; the proportion of pump power for pumping Nd³⁺, η; Nd³⁺ and Yb³⁺ concentrations, N_Nd and N_Yb and output mirror reflectivity, R_out) of the given NYDFLs are optimized by solving the rate and power propagation equations. Results show that dividing equally the input pump power among 808 nm (Nd³⁺) and 940 nm (Yb³⁺) is not an optimal choice and the pump power of Nd³⁺ ions should be kept around 10-13.78% of the total pump power. Three optimal schemes are obtained by NHGA and the highest slope efficiency of the laser is able to reach 80.1%.     

Synthesis and near-infrared luminescence properties of LaOCl:Nd3+/Yb3+

Near-infrared emitting phosphors LaOCl:Nd³⁺/Yb³⁺ were prepared by the solid-state method, and their structures and luminescent properties were investigated by using X-ray diffraction and photoluminescence analysis, respectively. The studies shows that tetragonal LaOCl:Nd³⁺/Yb³⁺ can be synthesized by the solid-state reaction at 600 °C for 3 h. Upon 353 nm UV excitation, LaOCl:Nd³⁺/Yb³⁺ sample shows strong near-infrared emission lines in the region of 1060–1150 nm (corresponding to ⁴F_3/2 → ⁴I_J′ transition of Nd³⁺, J′ = 9/2, 11/2, 13/2, 15/2) and 980–1050 nm (corresponding to ²F_5/2 → ²F_7/2 transition of Yb³⁺). The decreasing emission intensity of Nd³⁺ with increasing doping concentration of Yb³⁺ proved the energy transfer in LaOCl:Nd³⁺/Yb³⁺. The possible near-infrared emission and energy transfer mechanism between Nd³⁺ and Yb³⁺, as well as the energy transfer efficiency of LaOCl:Nd³⁺/Yb³⁺ were discussed.     

Pulsed laser deposition of lysozyme: the dependence on shot numbers and the angular distribution

An efficient near-infrared (NIR) quantum cutting (QC) by converting ultraviolet into NIR via cooperative downconversion (DC) for the (Nd³⁺, Yb³⁺) couple in CaWO₄ is studied since efficient two-step energy transfer occurs from the ⁴G_9/2 level of Nd³⁺ to two neighboring Yb³⁺:²F_5/2 level. The authors have analyzed the measured luminescence spectra and decay lifetimes for different Yb³⁺ concentrations and proposed a mechanism to rationalize the DC effect. The maximum quantum efficiency (QE) of Nd³⁺ is up to 164.03 %. Application of the broadband NIR-QC phosphors might enhance the performance of silicon-based solar cells.     

Optical parameters of Nd3＋：Er3＋：yb3＋ co-doped borosilicate glasses and their energy transfers at high temperature

This paper reports that a series of Nd³⁺:Er³⁺:Yb³⁺ co-doped borosilicate glasses have been prepared and their absorption spectra measured. The J--O intensity parameters Ω_k (k=2, 4, 6), spontaneous radiative lifetime τ_rad, spontaneous transition probability A, fluorescence branching ratio β and oscillator strength f_ed of the Nd³⁺ ions at room temperature are calculated based on Judd--Ofelt (J--O) theory. The temperature dependence of the up-conversion photoluminescence characteristics in a Nd³⁺:Er³⁺:Yb³⁺ co-doped sample is studied under a 978 nm semiconductor laser excitation, and the energy transfer mechanisms among Yb³⁺, Er³⁺ and Nd³⁺ ions are analysed. The results show that the J--O intensity parameters Ω₂ increase when the Nd³⁺ concentration of the Nd³⁺:Er³⁺:Yb³⁺ co-doped borosilicate glasses increases. The possibility of spontaneous transition is small and lifetimes are long at levels of ⁴F_5/2 and ⁴F_3/2. The intensity of Nd³⁺ emissions at 595, 691, 753, 813 and 887 nm are markedly enhanced when the sample temperature exceeds 400 K. The reasons being the cooperation of the secondary sensitization from Er³⁺ to Nd³⁺ and the contribution of a multi-phonon.     

Cooperative emission study in ytterbium doped NdVO4

The infrared and visible cooperative emissions of ytterbium ions are studied in Yb-doped NdVO₄ single crystals. The absorption of optical phonons allows the emissions at room temperature when a Nd:YAG laser is used. Low temperature emissions are observed due to the Nd³⁺→Yb³⁺ energy transfer following an argon ion laser excitation of the Nd³⁺ ions. Analysis of the cooperative emission at low doping concentration (1%) indicates that it is generated by distant pair forming Yb³⁺ ions while at high doping concentration (≥ 5%) close ions magnetically coupled and superexchange mechanisms prevail in the emitting process.     

Time Resolved Fluorescence and Energy Transfer Analysis of Nd<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript>–Er<Superscript>3+</Superscript> Triply-Doped Ba–Al-Metaphosphate Glasses for an Eye Safe Emission (1.54 μm)

This paper reports on the preparation and systematic analysis of energy transfer mechanisms in Nd³⁺–Yb³⁺–Er³⁺ co-doped new series of barium-alumino-metaphosphate glasses. The time resolved fluorescence of Nd³⁺ in triply doped Ba–Al-metaphosphate glasses have revealed that, Yb³⁺ ions could function as quite efficient bridge for an energy transfer between Nd³⁺ and Er³⁺ ions. As a result, a fourfold emission enhancement at 1.54 μm of Er³⁺ ions has been achieved through an excitation of ⁴F_5/2 level of Nd³⁺ at 806 nm for the glass having 3 mol% Yb³⁺ with an energy transfer efficiency reaching up to 94%. Decay of donor (Nd³⁺) ion fluorescence has been analyzed based on theoretical models such as direct energy transfer model (Inokuti–Hirayama) and migration assisted energy transfer models (Burshtein’s hopping and Yokota–Tanimoto’s diffusion). The corresponding energy transfer parameters have been evaluated and discussed. Primarily, electrostatic dipole–dipole (s ~ 6) interactions are found to be responsible for the occurrence of energy transfer process in theses glasses.     

Up-conversion luminescence of Er/Yb/Nd-codoped tellurite glasses

Up-conversion luminescence and energy transfer (ET) processes in Nd³⁺-Yb³⁺-Er³⁺ triply doped TeO₂-ZnO-Na₂O glasses have been studied under 800 nm excitation. Intense green up-conversion emissions around 549 nm, which can be attributed to the Er³⁺: ⁴S_3/2→⁴I_15/2 transition, are observed in triply doped samples. In contrast, the green emissions are hardly observed in Er³⁺ singly doped and Er³⁺-Yb³⁺ codoped samples under the same condition. Up-conversion luminescence intensity exhibits dependence of Yb₂O₃-concentration and Nd₂O₃-concentration. Up-conversion mechanism in the triply doped glasses under 800 nm pump is discussed by analyzing the ET among Nd³⁺, Yb³⁺ and Er³⁺. And a possible up-conversion mechanism based on sequential ET from Nd³⁺ to Er³⁺ through Yb³⁺ is proposed for green and red up-conversion emission processes.     

Nd3+ → Yb3+ energy transfer in a codoped metaphosphate glass as a model for Yb3+ laser operation around 980 nm

A complete spectroscopic investigation of a metaphosphate glass with composition Pb(PO₃)₂ doped with various amounts of Nd³⁺ and Yb³⁺ (1 up to 10 at.%) is reported. Efficient Nd³⁺ → Yb³⁺ energy transfers occur both radiatively and non-radiatively, the latter being dominant and partly resonant and partly phonon-assisted by phonons of the order of 950 cm⁻¹, which fits well with the reported Raman spectrum of the material. These transfers mainly concern the ⁴F_3/2 → ⁴I_9/2 emission and the ²F_7/2 → ²F_5/2 absorption transitions of the Nd³⁺ and Yb³⁺ ions around 900 nm, respectively. They are analysed both via spectral and temporal data. The results show that about 5% Nd³⁺ and 5% Yb³⁺ ions have to be incorporated to reach energy transfers exceeding about 65%, which is in agreement with data recently reported in the case of a YAl₃(BO₃)₄ crystal. Simulations based on the obtained data show that laser thresholds of a few tens of mW should be easily attainable by operating the materials in a channel waveguide configuration.     

Synthesis, characterization and upconversion emission properties of the nanocrystals of Yb/Er-codoped YF3-YOF-Y2O3 system

Nanocrystalline Yb³⁺, Er³⁺-codoped fluoride (YF₃), oxyfluoride (YOF), and oxide (Y₂O₃) phosphors have been synthesized by a facile pyrolysis of a yttrium trifluoroacetate precursor. YF₃, YOF and Y₂O₃ nanoparticles were demonstrated to be good host materials for lanthanides. Varied hosts led to different optical properties. Red, green, and blue up-conversion (UC) was observed upon excitation in the NIR spectral range in all synthesized compounds. The UC mechanisms were also analyzed.     

Arrays of micro-cavities activated with laser ions

We have combined different rare earth ions (Er³⁺, Nd³⁺ and Yb³⁺) in two dimensional ferroelectric patterns to obtain periodical fluorescent arrays. High refractive-index Er³⁺ doped CaTiO₃ nanocrystals have been embedded into Nd³⁺ or Yb³⁺ doped LiNbO₃ substrates pre-patterned with a two dimensional arrays of micro-voids. The process of incorporation and consolidation of the optically active nanoparticles into the alternate domain structures leads to luminescent ring-shaped arrangements with innovative geometries and to a micrometer spatial control of the trivalent rare earth ion emitters. Multicolor emission systems and the possibility of chromatic switching at the micrometer scale among the different compounds forming the two dimensional structure is demonstrated.     

Hydrothermal synthesis and the enhanced blue upconversion luminescence of NaYF4:Nd3+,Tm3+,Yb3+

Nd³⁺, Tm³⁺ and Yb³⁺ co-doped NaYF₄ upconversion (UC) material was synthesized by the hydrothermal method. The structure of the sample was characterized by the X-ray diffraction, and its UC luminescence properties were investigated in detail. Under the 980 nm semiconductor laser excitation, its UC spectra exhibited distinct emission peaks at 451 nm, 475 nm and 646 nm respectively. On the basis of the comparison of UC spectra between NaYF₄:Nd³⁺,Tm³⁺,Yb³⁺ and NaYF₄:Tm³⁺,Yb³⁺, it was indicated that the existence of Nd³⁺ ion enhanced the blue emission intensity. The law of luminescence intensity versus pump power proved that the blue emission at 475 nm, and the red emission at 646 nm were the two-photon processes, while the blue emission at 451 nm was a three-photon process.     

Study on up-conversion emissions of Yb/Tm co-doped GdF3 and NaGdF4

The Yb³⁺/Tm³⁺ co-doped GdF₃ and NaGdF₄ samples were synthesized through a combination method of a co-precipitation and an argon atmosphere annealing procedures. X-ray diffraction analysis indicated that the Yb³⁺/Tm³⁺ co-doped GdF₃ sample crystallized well and was orthorhombic phase, and the Yb³⁺/Tm³⁺ co-doped NaGdF₄ sample was hexagonal phase. With a 980-nm semiconductor continuous wave laser diode as the excitation source, the up-conversion emission spectra of the two samples in the wavelength range of 240-510 nm were recorded. In the up-conversion emissions of the samples, Yb³⁺ transferred energies to Tm³⁺ resulting in their ultraviolet, violet, and blue up-conversion emissions. And, Tm³⁺ simultaneously transferred energies to Gd³⁺, which finally resulted in ultraviolet up-conversion emissions of Gd³⁺. The study on the excitation power dependence of up-conversion fluorescence intensity indicated that there were multi-photon (three-, four-, five-, and six-) processes in the up-conversion emissions of the samples. And the up-conversion emissions of Gd³⁺ and Tm³⁺ in the Yb³⁺/Tm³⁺ co-doped GdF₃ and NaGdF₄ samples were compared studied, too.     

NIR luminescence from Er/Yb, Tm/Yb, Er/Tm and Nd ions-doped zincborotellurite glasses for optical amplification

In this paper, we report the near-infrared luminescence from the Er³⁺/Yb³⁺, Tm³⁺/Yb³⁺, Er³⁺/Tm³⁺ and Nd³⁺ ions-doped TeO₂-ZnO-B₂O₃-Li₂O-Na₂O glasses for optical amplification. The X-ray diffraction (XRD) and differential scanning calorimetry (DSC) profiles of the host glass matrix have been carried out. From the DSC thermogram, glass transition (T_g), crystallization (T_c) and melting (T_m) temperatures have been evaluated. The near-infrared spectra of Er³⁺/Yb³⁺, Tm³⁺/Yb³⁺, Er³⁺/Tm³⁺ and Nd³⁺ ions-doped glasses have shown full-width at half-maxima (FWHM) around 58, 127, 87 and 35 nm, respectively. These glasses with better thermal stability and broad near-infrared emissions should have potential applications in broadly tunable laser sources and broadband optical amplification at low-loss telecommunication windows.     

Noninvasive Temperature Measurement in Dental Materials Using Nd3+, Yb3+ Doped Nanoparticles Emitting in the Near Infrared Region

In this work, the application of near infrared (NIR)-emitting NaYbF₄:1%Tm³⁺@NaLuF₄:30%Nd³⁺ core–shell nanoparticles is reported for noninvasive probing and monitoring the temperature during photopolymerization of dental materials. When excited at 808 nm, the synthesized nanoparticles emit NIR photoluminescence (PL) with two distinctive peaks at 865 and 980 nm which correspond to radiative transitions from the doped Nd³⁺ and Yb³⁺ ions, respectively. Luminescence intensity ratio between these two bands is found to vary with temperature due to temperature-dependent electronic excitation energy transfer between Nd³⁺ and Yb³⁺ ions at the core/shell interface. This finding allows luminescence ratiometric evaluation of the in situ temperature during photopolymerization of resin cement (doped with nanoparticles) in a veneer placement procedure. In addition, the NIR emission also enables PL imaging of the distribution of the adhesive under the veneer. The results highlight that rare-earth ions–doped nanoparticles with both excitation and emission in the NIR spectral range are advantageous for both PL-based nanothermometry and imaging due to the reduced attenuation of NIR light by dental ceramics.     

Temporal dynamics of upconversion luminescence in Er3+, Yb3+ co-doped crystalline KY(WO4)2 thin films

Crystalline Er³⁺ and Yb³⁺ singly and doubly doped KY(WO₄)₂ thin films were grown by low-temperature liquid-phase epitaxy. Absorption, luminescence, excitation and temporal evolution measurements were carried out for both Er³⁺ and Yb³⁺ transitions from 10 K to room temperature. Green Er³⁺ upconversion luminescence was observed after Yb³⁺ and Er³⁺ excitation. The mechanisms responsible for the upconversion phenomena detected in each case were identified.     

Cooperative down-conversion of UV light in disordered scheelitelike Yb-doped NaGd(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> and NaLa(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals

Concentration series of disordered scheelitelike Yb:NaGd(MoO₄)₂ and Yb:NaLa(MoO₄)₂ single crystals are grown by the Czochralski method. The actual concentrations of Yb³⁺ ions in the crystals are determined by optical-absorption spectroscopy. The luminescence of Yb³⁺ ions in these crystals in the region of 1 μm is studied under UV and IR excitation. In the case of UV excitation, this luminescence appears as a result of nonradiative excited state energy transfer from donor centers of unknown nature to ytterbium. The character of the concentration dependence of Yb³⁺ luminescence indicates that the energy transfer at high Yb concentrations occurs with active participation of a cooperative mechanism, according to which the excitation energy of one donor center is transferred simultaneously to two Yb³⁺ ions. In other words, the quantum yield of this transfer exceeds unity, which can be used to increase the efficiency of crystalline silicon (c-Si) solar cells.     

Photothermally Induced Bistability of Emission of Yb-doped Ca4NdO(BO3)3 Single Crystals

We report on studies of changes in the emission spectra (excited at 808 nm) of the Yb-doped Ca₄NdO(BO₃)₃ single crystals due to the photothermal effects caused by the pulsed Nd:YAG laser. Increase of the sample's surface temperature after laser treatment leads to significant enhancement of the 1040 to 1060 nm emission (ascribed to the Nd^{3+ 4}F_3/2 → ⁴I_9/2, ⁴I_11/2 transitions) and simultaneous decrease of the 975 to 1050 nm emission (corresponding to the Yb^{3+ 2}F_5/2 → ²F_7/2 transition). We explain such an increase of the Nd³⁺ luminescence by thermally activated Yb³⁺ → Nd³⁺ energy transfer.