Enhancement of Er I13/2 population in Y2O3 by energy transfer to Ce

We report measurements of the energy transfer between Er³⁺ and Ce³⁺ in Y₂O₃. The transition between the Er^{3+ 4}I_11/2 and ⁴I_13/2 excited states can be stimulated by energy transfer to Ce³⁺, augmenting the population in the ⁴I_13/2 state at the expense of that in the ⁴I_11/2 state. Experiments were performed on Y₂O₃ planar waveguides doped with 0.2 at.% erbium and 0–0.42 at.% cerium by ion implantation. From measurements of Er³⁺ decay rates as a function of cerium concentration we derive an energy transfer rate constant of 1.3×10⁻¹⁸ cm³/s. The efficiency of the energy transfer amounts to 0.47 at 0.42 at.% cerium. The energy transfer rate constant measured in Y₂O₃ is two times smaller for Er³⁺→Ce³⁺ than that for Er³⁺→Eu³⁺ in the same material.     

Infrared absorption and Zeeman effect in Nd doped YVO4

Low temperature infrared transmission studies of Nd³⁺ doped YVO₄ were performed, under a magnetic field B c, in the 1800–8000 cm⁻¹ range of the ⁴I_9/2→⁴I_11/2, ⁴I_13/2, and ⁴I_15/2 Nd³⁺ crystal-field transitions. Good agreement is obtained between the experimental and calculated g-factors. Frequencies of the satellites in the ⁴I_9/2→⁴F_3/2 transitions of the Nd³⁺ isolated ion confirm the presence of ferromagnetic interactions between pairs of coupled Nd³⁺ ions that lift the Kramers doublet degeneracies of their ground state and excited multiplets.     

Optical properties of rare earth ion (Nd, Er and Tb)-doped alumina films prepared by the sol–gel method

Rare earth ion (Nd³⁺, Er³⁺ and Tb³⁺)-doped alumina films were prepared by the sol–gel method using aqueous alumina sol. The effects of dopant concentration and treatment temperature on the optical properties, absorption and emission were examined for the doped films. Alumina films prepared by this method gave a high dopant concentration (0–15 mol% per alumina). Significant concentration quenching did not occur in this concentration range. The emissions from ⁵D₃ and ⁵D₄ of Tb³⁺-doped film reflected sensitively a matrix environment around Tb³⁺ ions. Er³⁺- and Nd³⁺-doped alumina films resonantly excited by cw Ti–sapphire laser (800 nm) showed upconversion emission at room temperature. The former gave 548 nm (⁴S_3/2→⁴I_15/2) and 640 nm (⁴F_9/2→⁴I_11/2) signals, and the latter 640 nm (⁴G_7/2→⁴I_11/2), which were dependent on alumina.     

Effect of radiation trapping on the emission properties of Er: I13/2 → I15/2 transition in oxide glasses

The effect of radiation trapping on the emission properties of Er³⁺-doped tellurite and phosphate glasses has been investigated as the function of sample thickness and doping concentration. It was found that radiation trapping exists generally in two glass matrices, even at low doping concentration (0.1 mol% Er₂O₃). The larger effect of radiation trapping in tellurite glasses compared with phosphate glasses is due to its larger emission cross-section at 1.5 μm band and the spectral overlap between the emission and absorption spectra of Er³⁺: ⁴I_13/2 ↔ ⁴I_15/2transition. Due to radiation trapping, the measured lifetime of the Er³⁺: ⁴I_13/2 level in tellurite glasses increases by about 11–37% with increasing the sample thickness at the different erbium doping concentration, while 6–17% for phosphate glasses. And the full-width at half maximum of fluorescence (FWHM) of Er³⁺: ⁴I_13/2 → ⁴I_15/2 transition in tellurite glasses increased by about 15–64% with increasing the sample thickness, while 11–55% for phosphate glasses. It caused a high overestimation on the figure of merits (FOM) for amplifier bandwidth (σ_e × FWHM).     

Evaluation of the capabilities of several ions to sensitize Nd in the laser material LNA (La0.9Nd0.1MgAl11O19)

In the hexaaluminate laser material La_0.9Nd_0.1MgAl₁₁O₁₉ also known as LMA:Nd the Nd³⁺ fluorescence can be enhanced by codoping the matrix with rare-earth (REⁿ⁺) or transition metal (TM^m+) ions. A large number of potential donor ions D (D = Mn²⁺, Dy³⁺, Tb³⁺, Eu²⁺, Eu³⁺ and Ti³⁺) are studied in the hexaaluminate host. The D→Nd³⁺ energy transfer, t he, luminescent efficiency as well as the back-transfer strongly depend on the overlap of the D emission and Nd³⁺ absorption, the concentration of the two ions and their localization in the crystal host. In this paper the optical properties — absorption and emission — of the D and Nd³⁺ ions as well as the D→Nd³⁺ interactions are considered using a Forster-Dexter's approach, to compare the capabilities of the different donors in the Nd³⁺-doped hexaaluminate host. The C_DNd and R₀ parameters are estimated in each case, and the results discussed in terms of the localization of the donor ions, their absorption and emission as well as their lifetime properties.     

Two- and three-photon upconversion of LaOBr:Er

In this work, the LaOBr:Er³⁺ (0.1%) powders were prepared by solid state reaction. The structural properties of LaOBr:Er³⁺ were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and Raman spectroscopy. The results show that LaOBr:Er³⁺ has low phonon energy, which indicate that LaOBr:Er³⁺ may have high luminescent efficiency. Under excitation into ⁴I_11/2 level of Er³⁺ ions by 980 nm laser, the two- and three-photon upconverted luminescence of LaOBr:Er³⁺ were recorded. The most intense emissions were come from the ²H_11/2, ⁴S_3/2 → ⁴I_15/2 transitions. The upconversion mechanisms were studied in detail through laser power dependence, and results show that excited state absorption is responsible for the upconversion. The upconversion properties indicate that LaOBr:Er³⁺ may be used in upconversion phosphors.     

Spectroscopy of Er and Er–Yb-doped phosphate glasses

Optical absorption and emission properties of Er and Er–Yb-doped phosphate glasses are investigated both at low and room temperature in the near infrared spectral region between 800 and 2000 nm, and the results are thoroughly discussed in connection with the expected transitions originating from the crystal-field split ⁴I_15/2 and ⁴I_13/2 levels of the Er³⁺ ion. Accurate measurements of the ⁴I_13/2 fluorescence lifetimes and the determination of the stimulated emission cross section for the Er transition at 1.5 μm are also reported. Excited state absorption (ESA) from the metastable ⁴I_13/2 level towards the higher energy levels is measured in the 450–1200 nm spectral region. The ESA absorption peaks are in good agreement with the positions of the higher states of the 4f¹¹ Er³⁺ manifold.     

Synthesis and the luminescent properties of europium-activated Ca2SnO4 phosphors

The synthesis and photoluminescent (PL) properties of calcium stannate crystals doped with europium grown by mechanically activated in a high energy vibro-mill have been investigated. The characteristics of Ca₂SnO₄:Eu³⁺ phosphors were found to depend on the amounts of europium ions. The XRD profiles revealed that the system, (Ca_1−xEu_x)₂SnO₄, could form stable solid solutions in the composition range of x = 0–7% after being calcined at 1200 °C. The calcined powders emit bright red luminescence centered at 618 nm due to ⁵D₀ → ⁷F₂ electric dipole transition. Both XRD data and the emission ratio of (⁵D₀ → ⁷F₂)/(⁵D₀ → ⁷F₁) reveal that the site symmetry of Eu³⁺ ions decreases with increasing doping concentration. The maximum PL intensity has been obtained for 7 mol% concentration of Eu³⁺ in Ca₂SnO₄.     

Spectroscopic evaluation of CaYA1O4 doped with trivalent Er, Tm, Yb and Ho for eyesafe laser applications

Spectroscopic properties of relevance for laser applications have been studied for rare earths in CaYA1O₄. Fitting of a theoretical model to observed energy levels yields crystal field parameters and unobserved levels. Structural disorder leads to broad linewidths,but cross sections are larger than in many common hosts. Tm-Tm cross relaxation rates are comparable to those in Tm: YAG, and Yb-Er transfer rates are comparable to those in Yb, Er:phosphate glass. Room temperature Yb-Er upconversion is stronger than in YAG, but modeling shows that neither unconversion nor population of Er⁴I_13/2 is very efficient upon pumping Yb. The host's yellow color intensifies upon annealing in air, a potential problem for visible laser operation. Tm or Ho 2 μm laser operation, or Er 1.5 μ operation upon direct excitation of Er⁴I_13/2, are more promising.     

Optical properties and energy transfer among Nd in Nd:Ca2Al2SiO7 crystals for diode pumped lasers

The energy levels of neodymium in the Nd³⁺:Ca₂Al₂SiO₇ (CAS) laser material with gehlenite structure are reported. As the Nd³⁺:Ca₂Al₂SiO₇ compound presents a broad absorption around 806 nm, it is a good candidate for diode pumped laser. The ⁴F_3/2→⁴I_9/2 and ⁴F_3/2→⁴I11/2 emission have been recorded and the fluorescence branching ratios calculated from the Judd-Ofelt analysis are 0.41 and 0.47 respectively. The emission cross section at 1.06 μm (⁴F_3/2→⁴I11/2 transition) is 5 × 10^-20 cm². The decay profiles of the Nd³⁺ emission have been analyzed for several Nd³⁺ concentrations using the kinetic microparameters related to the cross relaxation ( and R₀≈6 Å) and the energy migration probabilities ( ). In the Nd:CAS laser material, the optimal concentration corresponding to the maximum of the fluorescence intensity is determined to be around 2.7 × 10²⁰ Nd³⁺ ions cm^-3. The Nd³⁺-Nd³⁺ interactions are not very strong in this material as the optical concentration value is two times higher than in the Nd:YAG laser material.     

Optically active Er–Yb codoped Y2O3 films produced by pulsed laser deposition

Optically active Er³⁺:Yb³⁺ codoped Y₂O₃ films have been produced on c-cut sapphire substrates by pulsed laser deposition from ceramic Er:Yb:Y₂O₃ targets having different rare-earth concentrations. Stoichiometic films with very high rare-earth concentrations (up to 5.5 × 10²¹ at cm^− 3) have been achieved by using a low oxygen pressure (1 Pa) during deposition whereas higher pressures lead to films having excess of oxygen. The crystalline structure of such stoichiometric films was found to worsen the thicker the films are. Their luminescence at 1.53 μm and up-conversion effects have been studied by pumping the Yb³⁺ at 0.974 μm. The highest lifetime value (up to 4.6 ms) is achieved in films having Er concentrations of ≈ 3.5 × 10²⁰ at cm^− 3 and total rare-earth concentration ≈ 1.8 × 10²¹ at cm^− 3. All the stoichiometric films irrespective of their rare-earth concentration or crystalline quality have shown no significant up-conversion.     

Partition, luminescence and energy transfer of Er/Yb ions in oxyfluoride glass ceramic containing CaF2 nano-crystals

A complete spectroscopic investigation of energy transfer processes in oxyfluoride glass ceramics containing CaF₂ nano-crystals doped with various amounts of Er³⁺ and Yb³⁺ was reported. An enhancement of the 1.53 μm emission and infrared to visible up-conversion fluorescence was confirmed experimentally due to efficient non-radiative energy transfer from Yb³⁺ to Er³⁺ ions concentrated in CaF₂ nano-crystals. The efficiency of Yb³⁺ to Er³⁺ energy transfer in excess of 85% was obtained for 0.5 mol% Er³⁺/2.0 mol% Yb³⁺ co-doped glass ceramic. Using rate equation formulism, the coefficient of Yb³⁺ to Er³⁺ energy transfer was determined to be about 3.5 times higher than that of Er³⁺ to Yb³⁺ energy back transfer, which is sufficient to provide high ⁴I_11/2 population of Er³⁺ to improve the fluorescence of the co-doped glass ceramics.     

Optical properties, fluorescence mechanisms and energy transfer in Tm, Ho and Tm -Ho doped near-infrared laser glasses, sensitized by Yb

The optical properties of the rare elements Tm³⁺, Ho³⁺ and Yb³⁺ were systematically investigated in various glasses. The Tm³⁺ doped aluminozircofluoride glass shows higher quantum efficiency, longer lifetime and stronger fluorescence intensity than Tm³⁺ doped YSGG crystal and other Tm³⁺ doped glasses for the ³H₄ → ³H₆ transition. Similar quantum efficiency, longer lifetime and stronger fluorescence intensity were also found in Ho³⁺ doped aluminozircofluoride glass for the ⁵I₇ → ⁵I₈ transition. The higher quantum efficiencies of Tm³⁺ and Ho³⁺ in aluminozircofluoride glass are due to the longer lifetime and the lower phonon energy. The fluorescence mechanisms and energy transfer in the Yb³⁺ -Tm³⁺ system, Yb³⁺ -Ho³⁺ system and Yb³⁺ - Tm³⁺ -Ho³⁺ system were studied. The very strong fluorescence intensities in the Yb³⁺ -Tm³⁺ system for Tm³⁺ and the Yb³⁺ -Tm³⁺ -Ho³⁺ system for Ho³⁺ which are 1.68 times that of Tm³⁺ doped YSGG crystal and 2.25 times that of Tm³⁺---Ho³⁺ codoped YSGG crystal are attributed to the efficient Yb³⁺ → Tm³⁺, Yb³⁺ → Ho³⁺ and Tm³⁺ → Ho³⁺ energy transfer processes. The fluorescence processes are described by cross relaxations of ²F_5/2 → ³H₅ → ³H₄ → ³H₆ → ²F_7/2 and²F_5/2 → ³H₅ (or ²F_5/2 → ⁵I₆ → ³H₅) → ³H₄ → ⁵I₇ → ⁵I₈ → ³H₆ → ²F_7/2.     

Temperature dependent luminescence in (Eu, Dy) doped tellurite glass

This short paper reports both the photoluminescence and the lifetime measurements of a prominent emission transition (⁵D₀→⁷F₂) of Eu³⁺ both in the presence and absence of the codopant rare earth ion (Dy³⁺) in an optical glass of the composition (79−x)TeO₂+6AlF₃+15LiF+xLn₂O₃ as a function of temperature down to 10 K.     

VUV spectroscopy of a new fluoride system NaF–(Er, Y)F3

Emission and excitation spectra as well as luminescence decay kinetics of a new complex fluoride system Na_0.4(Y_1−xEr_x)_0.6F_2.2 (x=0.01, 0.1, 1) have been studied in the vacuum ultraviolet (VUV) spectral range. It has been shown that these crystals have intense VUV luminescence due to the interconfiguration 5d–4f transitions in Er³⁺ ion. The spin-allowed 5d–4f luminescence of Er³⁺ in this system is very weak, i.e., in these crystals there exists an efficient non-radiative relaxation from higher-lying 5d states of Er³⁺ to the lowest 5d level responsible for spin-forbidden luminescence. This makes the studied new fluoride system a promising active medium for the production of VUV solid state laser with optical pumping. Due to rather large bandwidth of Er³⁺ 5d–4f luminescence in this system there is a possibility for the construction of tuneable VUV laser.     

Optical properties and laser performance of neodymium doped fluoroapatites SrxCa5−x(PO4)3F (x = 0, 1, 2, 3, 4, and 5)

Nd doped fluoroapatites Sr_xCa_5−x(PO₄)₃F(S_xC_5−xPF, X = 0, 1, 2, 3, 4, and 5) single crystals have been grown by the Czochralski technique. Their polarized absorption and emission spectra have been recorded at room temperature and used to calculate the absorption and stimulated emission cross sections. Broadening of the absorption and emission bands is observed for Nd³⁺ in the solid solutions SPF-CPF compared to Nd³⁺ in CPF or SPF. 1% Nd:S_xC_5−xPF, X = 0, 2, 3, 4, and 5, laser rods have been tested in a cavity longitudinally pumped by a 1 W AlGaAs laser diode and compared to Nd:YAG and Nd:YVO₄ rods. All fluoroapatites exhibit very good laser performance with low thresholds and high slope efficiencies, higher than in the case of YAG and equal to the YVO₄ samples. The dependance of the laser output power versus the diode temperature has also been measured for all materials. The laser output was found to be as sensitive to the diode temperature fluctuations for fluoroapatites as for YAG.     

Spectroscopic analysis and the effects of color centers on the laser performance of Nd: CaZn2Y2Ge3O12

Spectroscopic and EPR investigations of Nd³⁺-doped CaZn₂Y₂Ge₃O₁₂ (CAZGAR) have been performed. The absorption, fluorescence, excitation spectra and fluorescence lifetime have been measured at room temperature. The Judd-Ofelt theory has been applied to the measured optical absorption intensities to predict the radiative decay rates, branching ratios, and peak stimulated emission cross section from the metastable ⁴F_3/2 state to the ⁴I_9/2 manifold. The fluorescence lifetime of the ⁴F_3/2 level of Nd³⁺ at low concentration in this host was measured to be 285 ± 10 μs, which is longer than that for Nd³⁺: YAG. Color centers located at zinc octahedral sites have been produced in these crystals by ultraviolet irradiation and have been detected by EPR techniques. The effects of the color centers on the potential laser characteristics of this materials are discussed.     

Preparation and optical properties of sol–gel derived Er-doped Al2O3–Ta2O5 films

Thin films of the system xAl₂O₃–(100 − x)Ta₂O₅–1Er₂O₃ were prepared by a sol–gel method and a dip-coating technique. The influences of the composition and the crystallization of the films on Er³⁺ optical properties were investigated. Results of X-ray diffraction indicated that the crystallization temperature of Ta₂O₅ increased from 800 to 1000 °C with increased values of x. In crystallized films, the intensities of the visible fluorescence and upconversion fluorescence tend to decrease with an increase in x values, due to the high phonon energy of Al₂O₃; the strongest fluorescence is observed in a crystallized film for x = 4 heat treated at 1000 °C. In amorphous films obtained by heat treatment at relatively low temperatures the Er³⁺ fluorescence could not be observed because strong fluorescence from organic residues remaining in the films thoroughly covered the Er³⁺ fluorescence. On the other hand, the Er³⁺ upconversion fluorescence in the amorphous films was observed to be stronger than that in the crystallized films. The strongest upconversion fluorescence is observed in an amorphous film for x = 75 heat treated at 800 °C.     

Spectra and laser properties of Er, Yb:phosphate glasses

The effects of Al₂O₃, Yb₂O₃, Er₂O₃ and OH on spectral properties of P₂O₅·Na₂O·SrO·Al₂O₃·Yb₂O₃·Er₂O₃ erbium phosphate glass were studied. 5, 8, 13 mol% Al₂O₃, 4, 5, 6, 7 and 8 mol% Yb₂O₃ and 0.05, 0.2, 0.4 mol% Er₂O₃ were used. It was found Al₂O₃ improves fluorescent lifetime of Er³⁺ ions, but the integrated absorption cross-section of Er³⁺ ions decreases with the increase of Al₂O₃ concentration. Evaluating from energy transfer efficiency of Yb³⁺ to Er³⁺ and spectral parameters of Yb³⁺ and Er³⁺, lower Al₂O₃ content, 6 mol% Yb₂O₃ and 0.2–0.4 mol% Er₂O₃ are preferred for LD pumped microchip laser application. OH groups in glass greatly affect fluorescent intensity and lifetime of Er³⁺, Yb³⁺:phosphate glass. The OH absorption coefficient at 3000 cm⁻¹ should be <1 cm⁻¹ for laser applications. Pumped with a 2 W, 974 nm InGaAs laser diode, CW laser centered at 1530 nm with slope efficiency of 10.6% and maximum output of 43 mW was achieved in our 2 mm thick Er³⁺, Yb³⁺:phosphate glass at room temperature.     

In situ co-precipitation synthesis and photoluminescence of YxGd1−xVO4:Tm microcrystalline phosphors by hybrid precursors

Y_xGd_1−xVO₄:Tm³⁺ (5 mol%) phosphors were prepared by in situ co-precipitation technology with the different content ratio of Y/Gd (x = 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, respectively). During the process, rare earth coordination polymers with o-hydroxylbenzoate were used as precursors, composing with polyethylene glycol (PEG) as dispersing media. After heat-treatment of the resulting multicomponent hybrid precursors at 900 °C, the samples were obtained. SEM indicated the particles present good crystalline state, whose crystalline grain sizes were about 0.2–2 μm. Under the excitation of 257 nm, all the materials show the characteristic emission of Tm³⁺ which is the strong blue emission centered at 475 nm originating from ¹G₄ → ³H₆ of Tm³⁺. Besides this, concentration quenching appears in the system of YVO₄:Tm³⁺ and GdVO₄:Tm³⁺. And when x reaches 0.5, the system of Y_xGd_1−xVO₄:Tm³⁺ shows the strongest blue emission.