Upconversion luminescence in Tm3+/Yb3+co-doped lead tungstate tellurite glasses

This work reports the upconversion luminescence properties of Tm³⁺/Yb³⁺ ions in lead tungstate tellurite (LTT) glasses. Judd–Oflet intensity parameters have been obtained from the absorption band intensities of Tm³⁺ singly-doped and Tm³⁺/Yb³⁺ co-doped LTT glasses. The spontaneous emission probabilities, radiative lifetimes and branching ratios for ¹G₄ and ³H₄ emission levels of Tm³⁺ have been determined. Upconversion luminescence has been observed by exciting the samples at 980 nm (Yb³⁺:²F_7/2→²F_5/2) at room temperature. Four upconversion emission bands corresponding to the ¹G₄→³H₆ (477 nm), ¹G₄→³F₄ (651 nm), ¹G₄→³H₅ (702 nm) and ³H₄→³H₆ (810 nm) transitions have been identified. The relative variation in the intensities of upconversion bands, the different channels responsible for upconversion spectra and the effect of Yb³⁺ ions concentration on the upconversion luminescence of Tm³⁺ ions have also been discussed.     

Infrared-to-visible up-conversion luminescence and energy transfer of RE3+/Yb3+(RE = Ho,Tm) co-doped SrIn2O4

Near-infrared excited up-conversion phosphors of RE³⁺/Yb³⁺(RE = Ho, Tm) co-doped SrIn₂O₄ were synthesized by a solid-state reaction method. X-ray diffraction analysis revealed the phase composition of those samples, and the up-conversion spectroscopic properties were studied in terms of up-conversion emission spectra. Under 980 nm near-infrared laser excitation, strong green emission with the peak at 546 nm was observed in SrIn₂O₄: Ho³⁺/Yb³⁺, which can be assigned to the characteristic ⁵S₂(⁵F₄) → ⁵I₈ transition of Ho³⁺. Furthermore, SrIn₂O₄: Tm³⁺/Yb³⁺ showed bright blue emission with the peak at 486 nm, which is associated with the ¹G₄ → ³H₆ transition of Tm³⁺. The UC power studies indicated that the luminescence of SrIn₂O₄: Ho³⁺/Yb³⁺ and SrIn₂O₄: Tm³⁺/Yb³⁺ are attributed to two-photon and three-photon process, respectively. The possible UC luminescence mechanism and energy transfer in SrIn₂O₄: RE³⁺/Yb³⁺ were discussed.     

Infrared broadband emission of bismuth–thulium co-doped lanthanum–aluminum–silica glasses

The Bi–Tm co-doped SiO₂–Al₂O₃–La₂O₃ (SAL) glasses, which exhibited a broadband near-infrared (NIR) emission was investigated by the optical absorption and photoluminescence spectra. The super broadband near-infrared emission from 1000 to 2100 nm, which covered the whole O, E, S, C and L bands, was observed in the Bi–Tm co-doped samples, as a result of the overlap of the Bi-related emission band (centered at 1270 nm) and the emission from Tm^{3+ 3}H₄→³F₄ transition (1440 nm) as well as Tm^{3+ 3}F₄→³H₆ transition (1800 nm). Relative luminescence intensity at 1270, 1440 and 1800 nm wavelength varied depending on the mixing ratio of Bi and Tm and the full-width at half-maximum (FWHM) extending from 1000 to 1600 nm could be 400 nm. These results indicated that Bi–Tm co-doped SiO₂–Al₂O₃–La₂O₃ glasses could provide potential applications in tunable lasers as well as the broadband optical amplifiers in WDM system.     

Near-infrared broadband luminescence and energy transfer in Bi–Tm–Er co-doped lanthanum aluminosilicate glasses

The Bi–Tm–Er co-doped SiO₂–Al₂O₃–La₂O₃ (SAL) glasses, which exhibited a broadband near-infrared (NIR) emission, were investigated by the optical absorption and photoluminescence spectra. A super broadband NIR emission extending from 0.95 to 1.6 μm with a full-width at half-maximum (FWHM) of 430 nm which covered the whole O, E, S, C and L bands, was observed in Bi–Tm–Er co-doped samples under 808 nm excitation, as a result of the overlap of the Bi-related emission band (centered at 1270 nm) and the emission from Tm^{3+ 3}H₄→³F₄ transition (1450 nm) as well as Er^{3+ 4}I_13/2→⁴I_15/2 transition (1545 nm). In addition, a super broadband emission with amplitude relatively flat from 0.95 to 2.1 μm has been observed. The possible energy transfer between Bi-related centers, Tm³⁺ ions and Er³⁺ ions was proposed.     

Positive influence of Tm3+ on effective Er3+: 3 μm emission in fluoride glass under 980 nm excitation

Er³⁺ and Tm³⁺ singly doped and codoped new fluoride glasses were prepared by traditional melt-quenching method. Efficient 3 μm emission was obtained under 980 nm laser excitation. It is worthy to notice that one of the two ions can be the sensitizer to the other one by depressing the Er³⁺: 1.5 μm emission through the energy transfer process from Er³⁺:⁴I_13/2 level to Tm³⁺:³F₄ level. On the basis of measured absorption spectra, the Judd-Ofelt intensity parameters and radiation emission probability were calculated to evaluate the spectroscopic properties. Additionally, the micro-parameters together with the phonon assistance of Er³⁺:⁴I_13/2 → Tm³⁺:³F₄ and Er³⁺:⁴I_11/2 → Tm³⁺:³H₅ processes were quantitatively analyzed by using Dexter model. The theoretical micro-parameters results meet well with the experiments which indicates that Er³⁺/Tm³⁺ codoped fluoride glass is a potential kind laser glass for 3 μm laser.     

Polarized emission and absorption cross-section calculation in LiNbO3:Tm3+

Absorption and emission cross-sections are essential spectroscopic parameters that determine the performance of rare-earth solid state lasers and amplifiers. A precise characterization of such parameters is of great interest in order to proceed with the necessary optimization stage which will assure the development of photonic devices with high efficiency. In particular, in order to model Tm³⁺ infrared lasers under 800 nm pumping, the absorption and emission cross-sections associated with optical transitions involving the ³H₄ and ³F₄ manifolds are needed. In this work, the classical McCumber theory is applied to evaluate the polarized absorption and emission cross-sections of Tm³⁺ ions in LiNbO₃.     

Increase of the blue upconversion emission in YAG:Tm3+ nanopowders by codoping with Yb3+ ions

The YAG nanopowders were prepared by a co-precipitation method using nitrate and ammonium hydrogen carbonate as raw materials. To obtain homogenous precipitate, reverse-strike (adding salt solutions to the precipitant solution) technique was adopted. Therefore, single (Tm³⁺) and codoped (Tm³⁺–Yb³⁺) YAG nanopowders with a size between 40–90 nm have been obtained.Blue upconversion emission at around 480 nm has been found in YAG: Tm³⁺ nanopowders under excitation to the ³H₄ level of Tm³⁺ at around 800 nm. However, this upconversion emission in nanopowders codoped with Tm³⁺–Yb³⁺ ions is increased by a factor of about 10. The analysis of the temporal evolution of the involved levels and the dependence of the upconversion intensity on the pump power at 800 nm allowed to distinguish the upconversion mechanism. In YAG: Tm³⁺ nanopowders the upconversion mechanism is due to excited state absorption processes. However, in the codoped samples, Yb³⁺ ions acts as the sensitizers; in consequence, the blue upconversion is strongly increased.     

Highly efficient upconversion emission and luminescence switching from Yb3+/Tm3+ co-doped water-free low silica calcium aluminosilicate glass

We present highly efficient 480 and 800 nm upconversion emissions in Tm³⁺/Yb³⁺ co-doped water-free low silica calcium aluminosilicate glass under excitation at 976 nm. As a result of this efficient upconversion process, a luminescent switching with the excitation intensity has been observed. The switching is explained and discussed using rate equations analysis and saturation effects. By means of fitting of the experimental data point, it was possible to obtain the value of the energy transfer parameter related to the transition ²F_5/2, ³H₄→²F_7/2, ¹G₄. The value of this parameter is higher than that of materials like YLF. This switching mechanism could be used in the development of sensors and networks for optical processing and optical communications.     

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.     

Spectroscopic investigations of OH− influence on near-infrared fluorescence quenching of Yb3+/Tm3+ co-doped sodium-metaphosphate glasses

Energy transfer processes were studied in two sets of Yb³⁺ and Tm³⁺ co-doped sodium-metaphosphate glasses, prepared in air and nitrogen atmospheres. Using Förster, Dexter, and Miyakawa theoretical models, the energy transfer parameters were calculated. The main ion–ion energy transfer processes analyzed were energy migration among Yb³⁺ ions, cross-relaxations between Yb³⁺ and Tm³⁺ ions, and interactions with OH^? radicals. The results indicated that Yb→Tm energy transfer favors 1.8 μm emissions, and there is no evidence of concentration quenching up to 2% Tm₂O₃ doping. As expected, samples prepared in nitrogen atmosphere present higher fluorescence quantum efficiency than those prepared in air, and this feature is specially noted in the near-infrared region, where the interaction with the OH^? radicals is more pronounced.     

Optical temperature sensor through infrared excited blue upconversion emission in Tm3 +/Yb3 + codoped Y2O3

An analysis of the intense blue upconversion emission at 476 and 488 nm in Tm^3 +/Yb^3 + codoped Y₂O₃ under excitation power density of 86.7 W/cm² available from a diode laser emitting at 976 nm, has been undertaken. Fluorescence intensity ratio (FIR) variation of temperature-sensitive blue upconversion emission at 476 and 488 nm in this material was recorded in the temperature range from 303 to 753 K. The maximum sensitivity derived from the FIR technique of the blue upconversion emission is approximately 0.0035 K^? 1. The results imply that Tm^3 +/Yb^3 + codoped Y₂O₃ is a potential candidate for the optical temperature sensor.     

Spectroscopic characterization of Tm3+:TeO2–K2O–Nb2O5 glasses for 2-μm lasing applications

We have performed detailed experiments to investigate the spectroscopic properties of a new type of tellurite based host doped with thulium: Tm₂O₃:(0.70)TeO₂–(0.15)K₂O–(0.15)Nb₂O₅ having Tm₂O₃ concentrations of 0.125, 0.25, 0.5, and 1.0 mol%. By performing a Judd–Ofelt analysis of the absorption bands, we obtained average radiative lifetimes of 2.57±0.20 and 0.35±0.01 ms for the ³H₄ and ³F₄ levels, respectively. Furthermore, we also observed that an increase in the Tm₂O₃ concentration from 0.125 to 1.0 mol% results in a decrease of the measured fluorescence lifetime from 814 to 439 μs and from 258 to 47 μs for the ³H₄ and ³F₄ levels, respectively, due to efficient non-radiative decay. The highest quantum efficiency of 32% was obtained for the sample doped with 0.125 mol% Tm₂O₃ for the ³H₄ level. Results show that cross relaxation becomes important as the ion concentration is increased, leading to the quenching of the 1460-nm band and enhancement of the 1860-nm emission. The highest emission cross section of 6.85×10^?21 cm² measured for the 1860-nm band reveals the potential of this host for the development of 2-μm lasers in bulk glass as well as fiber media.     

Luminescent properties of Eu2+and Dy3+ ions in Ba4Al2O7 phosphor for solid state lighting

In this paper we report the combustion synthesis of rare earth (RE=Eu, Dy) doped Ba₄Al₂O₇ phosphors. Prepared phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), CIE color co-ordinates and their photoluminescence (PL) properties were also investigated. In case of Ba₄Al₂O₇: Eu²⁺, the emission spectra show unique band centered at 495 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺, and PL emission spectra of Dy³⁺ ion under 348 nm excitation give two bands centered at 478 nm (blue) and 575 nm (yellow), which originate from the transitions of ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 of Dy³⁺, respectively. The results indicate that the Eu²⁺ and Dy³⁺ activated Ba₄Al₂O₇ phosphor could find application in solid state lighting.     

Photoluminescence investigations of Li2SiO3:Ln (Ln=Er3+, Eu3+, Dy3+, Sm3+) phosphors

In this study, we report a comprehensive structural and photoluminescence (PL) study on lithium metasilicate (Li₂SiO₃) phosphor ceramics doped with four rare earth (RE) ions. X-ray diffraction (XRD) patterns show a dominant phase, characteristic of the orthorhombic structure Li₂SiO₃ compound and the presence of dopants has no effect on the basic crystal structure of the material. The first excited state Er³⁺ luminescence at 1.54 μm arises from a sharp atomic-like radiative transition between the ⁴I_13/2 state and the ⁴I_15/2 state (ground level) under a 532 nm line of an Ar ion laser excitation. Sm doped samples showed Sm³⁺ emission characteristics corresponding to the some ⁴G_5/2→⁶H_j (j=5/2,9/2,11/2) transitions indicating a strong crystal-field effect. PL spectra of Eu doped material exhibited peaks corresponding to the ⁵D₀→⁷F_j (j=0,1,2,3 and 4) transitions under 405 nm excitation. The dominant red color emission at 612 nm from the hypersensitive (⁵D₀→⁷F₂) transition of Eu³⁺ indicates the inversion antisymmetry crystal field around Eu³⁺ ion, which is favorable to improve the red color purity. Dy doped samples showed the Dy³⁺ emission characteristic due to the ⁴F_9/2→⁶H_13/2 transition. Their relative intensity ratios also suggested the presence of a symmetric environment around the metal ion. We suggest that lithium metasilicate has enough potential candidates to be a phosphor material.     

Enhanced Up-Conversion Emission in Al<Superscript>3+</Superscript> Co-Doped ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript>:Yb<Superscript>3+</Superscript>,Tm<Superscript>3+</Superscript> Powder Phosphors

Yb³⁺-Tm³⁺ co-doped up-conversion powder phosphors using Zn(Al_xGa_1-x)₂O₄ (ZAGO) as the host materials were synthesized via solid-state reaction successfully. In addition, the morphology, structural characterization and up-conversion luminescent properties were all investigated by scanning electron microscope (SEM), x-ray diffraction (XRD) and fluorescence spectrophotometer (F-7000), respectively. Under the excitation of a 980 nm laser, all as-prepared powders can carry out blue emission at about 477 nm (corresponding to ¹G₄ → ³H₆ transition of Tm³⁺ ions), and red emission at about 691 nm (attributed to ³F₃ → ³H₆ transition of Tm³⁺ ions). Also, the influence of doping Al³⁺ ions were investigated. In brief, the doping of Al³⁺ ions has no effect on the position of emission peak. Howbeit the up-conversion efficiency and intensity of ZAGO:Yb,Tm phosphors are stronger than ZGO:Yb,Tm and ZAO:Yb,Tm phosphors, while the crystallinity is the opposite. More particularly, all as-prepared powder phosphors emit strong luminescence, which is observable by the naked eye, demonstrating the potential applications in luminous paint, luminescent dye, etc.     

Desvitrification on an oxyfluoride glass doped with Tm3+ and Yb3+ ions under Ar laser irradiation

Desvitrification in a Tm³⁺ and Yb³⁺ codoped oxyfluoride glass has been obtained by exciting with a continuous Argon laser radiation increasing the average laser power from 144 to 2900 mW. Excitation spectra inside a locally damaged zone in a 1 mol% Tm³⁺ and 2.5 mol% Yb³⁺ codoped glass have been measured under excitation in the wavelength range 750–830 nm detecting the ²F_5/2 (Yb³⁺) level. This curve is the result of the contribution of two different kinds of centers, the fluoride nanocrystals and the glassy phase of the glass ceramic sample created due to the irradiation. The weight of the contributions of each of the centers depends on the excitation wavelength, and from the analysis of the decay of the luminescence it can be concluded that approximately 80% of the Tm³⁺ ions are located in the nanocrystals and therefore less than 20% in the glassy phase.     

Optical characteristics of Tb-doped InBO3 nanocrystals

InBO₃ nanocrystals doped with Tb³⁺ ions are prepared via the sol–gel method. The structure, morphology, and optical properties of the nanocrystals are characterized by X-ray diffraction, high-resolution transmission electron microscopy, field-emission scanning electron microscopy, and photoluminescence analysis. The results show that a hexagonal InBO₃ phase forms at above 650 °C. A second phase of In₂O₃ begins to appear with Tb doping of over 3 mol%. The ⁵D₄→⁷F₅ (553 nm) transitions of Tb³⁺ ions in the InBO₃ host are observed at 2 mol%. The decay time of Tb-doped InBO₃ nanocrystals is about 2.1 ms. For Tb-doped InBO₃ nanocrystals excited at 237 nm and 553 nm wavelengths, the 2 mol% doping level yields the highest saturation of green emission. The emission shifts from green to yellow when the doping concentration is increased from 1 to6 mol%, due to the ⁵D₄→⁷F₅ transition.     

Spectroscopic properties of Tm3+/Ho3+ co-doped NaLa(WO4)2 single crystal

Tm³⁺/Ho³⁺ co-doped NaLa(WO₄)₂ single crystal was successfully grown by the Czochralski method. The crystal was characterized by room temperature absorption spectra, fluorescence spectra around 2 μm, up-conversion fluorescence and luminescence decay measurements. Spectroscopic properties related to the laser operation around 2 μm of Ho³⁺ ions have been evaluated. The energy level scheme and energy transfer processes of Tm³⁺ and Ho³⁺ were analyzed. The obtained spectroscopic results show the crystal is a potentially host for Ho³⁺ 2 μm infrared laser.     

Blue upconversion luminescence in 12 CaO·7 Al2O3:Tm3 +/Yb3 + polycrystals

The effect of Yb^3 + concentration on the fluorescence of 12 CaO·7 Al₂O₃:Tm^3 +/Yb^3 + polycrystals is investigated. Under the excitation of 980 nm laser, the strong blue (477 nm) emission band is observed and attributed to ¹G₄ → ³H₆ of Tm^3 +. The ratio of blue to red emission increases with the increasing of Yb^3 + and remains constant at 10 mol% Yb^3 +. The pump dependence and upconversion mechanisms show that the two-photon cooperative upconversion process is responsible for the enhancement of the blue upconversion emission. The Commission Internationale de l'eclairage chromaticity coordinates (x, y) illustrate that the 12 CaO·7 Al₂O₃:1 mol% Tm^3 +/10 mol% Yb^3 + can emit high-purity blue light.     

Synthesis,photoluminescence and thermoluminescence properties of LiNa3P2O7:Tb3+ green emitting phosphor

The alkaline phosphate based LiNa₃P₂O₇:Tb³⁺ phosphors are prepared by solid state reaction method. X-ray diffraction (XRD) analysis shows that all the powders possess orthorhombic structure. Fourier transform infrared (FTIR) spectroscopy studies suggest that the phosphor belong to the diphosphate family. The morphology of the phosphors is identified by scanning electron microscopy (SEM). Upon 378 nm excitation, the LiNa₃P₂O₇:Tb³⁺ phosphors shown emission bands at 482, 545, 588 and 620 nm corresponding to the transitions ⁵D₄→⁷F₆, ⁵D₄→⁷F₅, ⁵D₄→⁷F₄ and ⁵D₄→⁷F₃, respectively. The optimized concentration of Tb³⁺ in LiNa₃P₂O₇ phosphor is found to be 9 mol%. The concentration quenching mechanism was proved to be the exchange interaction between two nearest Tb³⁺ ions with the critical distance (R_c) of 1.18 nm. The Commission International de l'Eclairage (CIE) coordinates evidence that the phosphors emit in the green light region. Thermoluminescence properties of the prepared phosphors are studied by pre-irradiating the powders with different doses of UV irradiation. The kinetic parameters of TL glow curves are calculated using Chen's peak shape method.