Luminescence study of the 4f5d configuration of Nd in LiYF4, LiLuF4 and BaY2F8 crystals

Ultraviolet fluorescence of Nd³⁺ ions induced by triphotonic excitation process was studied in Nd-doped LiYF₄, LiLuF₄ and BaY₂F₈ crystals using a technique of time-resolved spectroscopy. The observed ultraviolet luminescence was due to transitions between the bottom of 4f²5d configuration and 4f³ states of Nd³⁺ ions. Narrow emission lines superposed to the broadband emissions were observed. A detailed analysis of luminescence spectrum revealed that the narrow emissions are due to parity and spin allowed radiative transitions from the Stark levels of ⁴K_11/2(5d) state created by the electrostatic interaction between the 5d electron and the two electrons of the 4f² configuration. The narrow emissions are related to the high spin state (S=3/2) which gives f-f characteristics to the f-d broadband emissions. The narrow emissions superposed to the wide emission correspond to 18%, 34% and 43% of the integrated broadband emission at 262 nm observed in LiYF₄, LiLuF₄ and BaY₂F₈ crystals, respectively. Although the 5d-4f² interaction is observed to be weaker than 5d-crystal field interaction, it is stronger enough to select only the radiative transitions from 4f²5d configuration to 4f³ states that preserves the total spin S=3/2.     

Tm and Tm-Tb-doped germanate glasses for S-band amplifiers

The mechanism involved in the Tm³⁺(³F₄)→Tb³⁺(⁷F_0,1,2) energy transfer as a function of the Tb concentration was investigated in Tm:Tb-doped germanate (GLKZ) glass. The experimental transfer rate was determined from the best fit of the ³F₄ luminescence decay due to the Tm→Tb energy transfer using the Burshtein model. The result showed that the 1700 nm emission from ³F₄ can be completely quenched by 0.8 mol% of Tb³⁺. As a consequence, the ⁷F₃ state of Tb³⁺ interacts with the ³H₄ upper excited state of Tm³⁺ slighting decreasing its population. The effective amplification coefficient β(cm⁻¹) that depends on the population density difference Δn=n(³H₄)-n(³F₄) involved in the optical transition of Tm³⁺ (S-band) was calculated by solving the rate equations of the system for continuous pumping with laser at 792 nm, using the Runge-Kutta numerical method including terms of fourth order. The population density inversion Δn as a function of Tb³⁺ concentration was calculated by computational simulation for three pumping intensities, 0.2, 2.2 and 4.4 kWcm⁻². These calculations were performed using the experimental Tm→Tb transfer rates and the optical constants of the Tm (0.1 mol%) system. It was demonstrated that 0.2 mol% of Tb³⁺ propitiates best population density inversion of Tm³⁺ maximizing the amplification coefficient of Tm-doped (0.1 mol%) GLKZ glass when operating as laser intensity amplification at 1.47 μm.     

Population inversion between the H4 and the F4 excited states of Tm investigated by means of numerical solutions of the rate equations system in Tm-doped and Tm, Ho-codoped fluoride glasses

Population inversion between the ³H₄ and the ³F₄ excited states of Tm³⁺ ions responsible for the 1.5 μm emission in Tm³⁺ singly doped (0.5%) and Tm³⁺, Ho³⁺-codoped fluoride (ZBLAN) glasses and its dependence on the Ho³⁺ concentration (x=0.2-1%) was investigated by means of numerical solution of the rate equations system for continuous pumping at 797 nm. Mean lifetimes of donor and acceptor states were evaluated by using the integration method applied to the best fitting of fluorescence curves previously reported. Lifetime values were used to obtain the rate constants of all non-radiative energy-transfer processes involved and a complete set of rate equations better describing the observations was given. The rate equations were solved by numerical method and the population inversion between the ³H₄ and the ³F₄ excited states of Tm³⁺ was calculated to examine the beneficial effects on the gain associated with Ho³⁺ codoping. The results have shown that Tm³⁺ population inversion is reached only for high Ho³⁺-codoping (?0.3 mol%). Highest population inversion (∼1.6×10¹⁸ Tm³⁺ ions cm⁻³) was obtained in Tm(0.5%), Ho(1%)-codoped (ZBLAN) pumped by 2.8 kW cm⁻². This population inversion density is ∼6.4 times higher than that one observed in Tm:Tb:GLKZ, Tm:Tb:Ge-Ga-As-S-CsBr and Tm:Ho:Ge-Ga-As-S-CsBr for a similar pumping condition (∼2.5×10¹⁷ cm⁻³). In addition, Tm(0.5%):Ho(1%):ZBLAN presents the highest population inversion that linearly increases with the pumping intensity; this behavior does not show saturation effect at least for the maximum intensity of 12 kW cm⁻² employed. The use of 1 mol% of Ho³⁺-codoping maximizes the potential gain of Tm³⁺-doped (0.5%) ZBLAN to produce stimulated emission near 1.5 μm, making this material suitable for using it as fiber optical amplifier and/or fiber laser operating in 1.4-1.5 μm region of the spectrum.