Spectral analysis of Pr-, Sm- and Dy-doped transparent GeO2-BaO-TiO2 glass ceramics

In this paper, we present the photoluminescence properties of Pr³⁺-, Sm³⁺- and Dy³⁺-doped germanate glasses and glass ceramics. From the X-ray diffraction measurement, the host glass structure was determined. These glasses have shown strong absorption bands in the near-infrared (NIR) region. Compared to Pr³⁺-, Sm³⁺- and Dy³⁺-doped glasses, their respective glass ceramics have shown stronger emissions due to the Ba₂TiGe₂O₈ crystalline phase. For Pr³⁺-doped glass and glass ceramic, emission bands centered at 530 nm (³P₀→³H₅), 614 nm (³P₀→³H₆), 647 nm (³P₀→³F₂) and 686 nm (³P₀→³F₃) have been observed with 485 nm (³H₄→³P₀) excitation wavelength. Of them, 647 nm (³P₀→³F₂) has shown bright red emission. Emission bands of ⁴G_5/2→⁶H_5/2 (565 nm), ⁴G_5/2→⁶H_7/2 (602 nm) and ⁴G_5/2→⁶H_9/2 (648 nm) for the Sm³⁺:glass and glass ceramic, with excitation at ⁶H_5/2→⁴F_7/2 (405 nm) have been recorded. Of them, ⁴G_5/2→⁶H_7/2 (602 nm) has shown a bright orange emission. With regard to the Dy³⁺:glass and glass ceramic, a bright fluorescent yellow emission at 577 nm (⁴F_9/2→⁶H_13/2) has been observed, apart from ⁴F_9/2→⁶H_11/2 (667 nm) emission transition with an excitation at 454 nm (⁶H_15/2→⁴I_15/2) wavelength. The stimulated emission cross-sections of all the emission bands of Pr³⁺, Sm³⁺ and Dy³⁺:glasses and glass ceramics have been computed based on their measured full-width at half-maxima (FWHM, Δλ) and lifetimes (τ_m).     

Synthesis and photoluminescence properties of Sm-doped CaWO4 nanoparticles

The Sm³⁺-doped CaWO₄ nanoparticles were synthesized by hydrothermal method. The room temperature photoluminescence (PL) spectra of Sm³⁺-doped CaWO₄ nanoparticles doped with different Sm³⁺ concentrations under 405 nm excitation have been investigated. The PL spectra showed four strong emission peaks at 460, 571, 609, and 653 nm. The first emission peak at 460 nm could be due to a structural defect of the lattice, an oxygen-deficient WO₃ complex. The other three emissions at 571, 609, and 653 nm were due to the f-f forbidden transitions of the 4f electrons of Sm³⁺, corresponding to ⁴G_5/2→⁶H_5/2 (571 nm), ⁶H_7/2 (609 nm), and ⁶H_9/2 (653 nm), respectively. In addition, the optimum Sm³⁺ concentration in CaWO₄ nanoparticles for optical emission was determined to be 1.0%. The Sm³⁺⁴G_5/2→⁶H_7/2 (609 nm) emission intensity of Sm³⁺-doped CaWO₄ nanoparticles significantly increased with the increase of Sm³⁺ concentration, and showed a maximum when Sm³⁺ doping content was 1.0%. If Sm³⁺ concentration continued to increase, namely more than 1.0%, the Sm³⁺⁴G_5/2→⁶H_7/2 emission intensity would decrease. The present materials might be a promising phosphor for white-light LED applications.     

Thermal loading induced near-infrared broadband upconversion emission of Sm-doped β-NaYbF4 nano-phosphors

A non-closed hydrothermal synthetic processing is improved to synthesize Sm³⁺ doped β-NaYbF₄ nano-phosphors at 98 °C without any high-temperature and high-pressure treatments as a final step. Novel green, red, and near-infrared broadband (799-873 nm) upconversion emissions of Sm³⁺-doped β-NaYbF₄ nano-phosphors under 980 nm excitation are observed. These UC emissions can be assigned to the Sm³⁺ transitions of ⁴G_J, ⁴F_3/2 and ⁶F_11/2→⁶H_J. The half-width of 873 nm emission band is broadened nearly two-fold through the annealing treatment for nano-phosphors. The upconversion process in Yb³⁺-Sm³⁺ system is discussed based on energy transfer mechanisms.     

Optical properties of lithium magnesium borate glasses doped with Dy and Sm ions

Several studies showed the interesting properties of trivalent lanthanide ions when doped in various types of glasses. Optical and physical properties of lithium magnesium borate glasses doped with Dy³⁺ then with Sm³⁺ ions were determined by measuring their absorption and luminescence spectra in the visible region. The absorption spectra of Dy³⁺ showed eight absorption bands with hypersensitive transition at 1265 nm (⁶H_15/2→⁶F_11/2-⁶H_9/2) and three PL emission bands at 588 nm (⁴F_9/2→⁶H_15/2), 660 nm (⁴F_9/2→⁶H_13/2) and 775 nm (⁴F_9/2→⁶H_11/2). Regarding the Sm3⁺, nine absorption bands were observed with hypersensitive transition at 1237 nm (⁶H_5/2–⁶F_7/2); the PL spectrum showed four prominent peaks at ⁴G_5/2→⁶H_5/2 (yellow color), ⁴G_5/2→⁶H_7/2 (bright orange color), ⁴G_5/2→⁶H_9/2 (orange reddish color) and ⁴G_5/2→⁶H_11/2 (red color), respectively. Finally, a series of physical parameters such as the oscillator strengths, refractive index, ions concentration, Polaron radius and other parameters were calculated for each dopant.     

Sol-gel synthesis, structural and optical properties of rare earth ions (Sm or Dy) activated Ca3Ga2Si3O12 powder phosphors

Structural, morphological and optical properties of rare earth ions (RE³⁺=Sm³⁺ or Dy³⁺) activated Ca₃Ga₂Si₃O₁₂ (CaGaSi) phosphors synthesized by the sol-gel method are reported. XRD results confirmed the cubic phase structure of RE³⁺:CaGaSi phosphors. From the SEM images of RE³⁺:CaGaSi phosphors, it is observed that the particles are agglomerated. Photoluminescence spectra of Sm³⁺:CaGaSi phosphors have shown bright orange red emission at 598 nm (⁴G_5/2→⁶H_7/2) with an excitation wavelength of λ_exci=401 nm. In the case of Dy³⁺:CaGaSi phosphors bright yellow emission has been observed at 574 nm (⁴F_9/2→ ⁶H_13/2) with λ_exci=451 nm. From the PL spectral results, the rare earth ion concentration of CaGaSi phosphors is optimized.     

Comparison study of the luminescent properties of the white-light long afterglow phosphors: CaxMgSi2O5+x:Dy(x=1, 2, 3)

A series of Dy³⁺-doped calcium magnesium silicate phosphors: CaMgSi₂O₆:Dy³⁺, Ca₂MgSi₂O₇:Dy³⁺, and Ca₃MgSi₂O₈:Dy³⁺ with white long-lasting afterglow were prepared and investigated. The characteristic intra-configurational 4f emissions of Dy³⁺ were observed in the emission spectra as well as the afterglow spectra under ultraviolet excitation. The combination of the 480 nm blue emission corresponding to the ⁴F_9/2→⁶H_15/2 transition and the 575 nm yellow emission corresponding to the ⁴F_9/2→⁶H_13/2 transition yielded white-light emission. The white-coloured afterglow emission can last more than 1 h for most of the samples under study. The concentration dependence of the ratio of the yellow emission intensity with blue emission intensity was also examined and found to be varied for the different hosts. The thermoluminescence spectra above room temperature are employed for the discussion of the origin of the traps and the mechanism of the persistent luminescence.     

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.     

Photoluminescence characterization of Ce and Dy doped Li2CaGeO4 phosphors

Ce³⁺ and Dy³⁺ activated Li₂CaGeO₄ phosphors were prepared by a solid-state reaction method, and characterized by XRD (X-ray diffraction) and photoluminescence techniques. The characteristic emission bands of Dy³⁺ due to ⁴F_9/2→⁶H_15/2 (blue) and ⁴F_9/2→⁶H_13/2 (yellow) transitions were detected in the emission spectra of Li₂CaGeO₄:Dy³⁺. Ce³⁺ broad band emission was observed in Li₂CaGeO₄:Ce³⁺ phosphors at 372 and 400 nm due to 5d→4f transition when excited at 353 nm. Co-doping of Ce³⁺ enhanced the luminescence of Dy³⁺ significantly and concentration quenching occurs when Dy³⁺ is beyond 0.04 mol%. White-light with different hues can be realized by tuning Dy³⁺ concentration in the phosphors.     

Photoluminescence properties of Sm in LBTAF glasses

Room temperature visible and near infrared optical absorption and emission spectra of Sm³⁺-doped lead borate titanate aluminum fluoride (LBTAF) glasses with molar composition (50−x) PbO−30H₃BO₃−10TiO₂−10AlF₃−xSm₂O₃ (x=0.1, 0.5, 1.0 and 2.0) have been analyzed. Energy parameters for the 4f⁵ electronic configuration of Sm³⁺: LBTAF glasses have been evaluated using free-ion Hamiltonian model. The experimental oscillator strengths of absorption bands have been used to determine the J-O parameters. Fluorescence spectra were recorded by exciting the samples with 402 nm. Using the J-O parameters and luminescence data, the radiative transition probabilities (A_R), branching ratios (β_R) and stimulated emission cross-sections (σ_e) were obtained. The decay curves of ⁴G_5/2→⁶H_7/2 transition exhibit single exponential for lower concentration (0.1 mol%) and non-exponential for higher concentrations. This concentration quenching has been attributed to the energy transfer through cross-relaxation between Sm³⁺ ions. From the values of the radiative parameters, it is concluded that 1.0 mol% Sm³⁺-doped LBTAF glass may be used for laser active medium with emission wavelength at 600 nm.     

Synthesis and photoluminescence properties of Sm-doped LaMgB5O10 and GdMgB5O10

Luminescence and reflection spectra as well as luminescence kinetics of the 1 mol% Sm³⁺-doped crystalline lanthanum magnesium meta borate (LaMgB₅O₁₀) and gadolinium magnesium meta borate (GdMgB₅O₁₀) were analyzed. Materials were synthesized by conventional solid state route and showed bright orange-red emission under UV excitation. Emission spectra contain sharp and well resolved Sm³⁺⁴G_5/2→⁶H_J transitions indicating a strong crystal-field effect. In case of gadolinium compound energy transfer between Gd³⁺ and Sm³⁺ was detected. The luminescent kinetics of the Sm³⁺ in analyzed powders is characterized by single exponential decay and experimental values vary in the range 2.2-2.4 ms.     

Optical properties of Dy ions in sodium gadolinium tungstates crystal

Dy³⁺-doped NaGd(WO₄)₂ crystal with sizes of about Φ20×40 mm² was grown by the Czochralski technique along the (0 0 1) orientation. Polarized absorption spectra, fluorescence spectra, and fluorescence decay curve of Dy³⁺-doped NaGd(WO₄)₂ have been recorded at room temperature. Based on the Judd-Ofelt (J-O) theory, the intensity parameters from the measured line strengths were evaluated. The J-O parameters were used to predict radiative transition probabilities, radiative lifetimes and branching ratios for various excited levels of Dy³⁺-doped NaGd(WO₄)₂ crystal. The luminescent quantum efficiency of the ⁴F_9/2 level was determined to be approximately 63% for this material. The emission cross-section of the ⁴F_9/2→⁶H_13/2 transition was estimated by using the Füchtbauer-Ladengurg method.     

Infrared to visible upconversion fluorescence in Yb,Tm:YAG single crystal

Absorption spectrum from 400 to 2000 nm and upconversion fluorescence spectra under 940 nm pumping of YAG single crystal codoped with 5 at.% Yb³⁺ and 4 at.% Tm³⁺ were studied at room temperature. The blue upconversion emission centered at 483 nm corresponds to the transition ¹G₄ → ³H₆, the emission band around 646 nm corresponds to the transition ¹G₄ → ³F₄ of Tm³⁺. Energy transfer from Yb³⁺ to Tm³⁺ is mainly nonradiative and the transfer efficiency was experimentally assessed. The line strengths, transition probabilities and radiative lifetimes of ¹G₄ level were calculated by using Judd-Ofelt theory. Gain coefficient calculated from spectra shows that the upconversion corresponding with transitions ¹G₄ → ³H₆ in YAG doped with Yb³⁺ and Tm³⁺ is potentially useful for blue light output.     

KBaPO4:Ln (Ln=Eu, Tb, Sm) phosphors for UV excitable white light-emitting diodes

This letter reports the novel three emission bands based on phosphate host matrix, KBaPO₄ doped with Eu²⁺, Tb³⁺, and Sm³⁺ for white light-emitting diodes (LEDs). The phosphors were synthesized by solid-state reaction and thermal stability was elucidated by measuring photoluminescence at higher temperatures. Eu²⁺-doped KBaPO₄ phosphor emits blue luminescence with a peak wavelength at 420 nm under maximum near-ultraviolet excitation of 360 nm. Tb³⁺-doped KBaPO₄ phosphor emits green luminescence with a peak wavelength at 540 nm under maximum near-ultraviolet excitation of 370 nm. Sm³⁺-doped KBaPO₄ phosphor emits orange-red luminescence with a peak wavelength at 594 nm under maximum near-ultraviolet excitation of 400 nm. The thermal stabilities of KBaPO₄:Ln (Ln=Eu²⁺, Tb³⁺, Sm³⁺), in comparison to commercially available YAG:Ce³⁺ phosphor were found to be higher in a wide temperature range of 25-300 °C.     

Enhanced luminescence of Ca3B2O6:Dy phosphors by Na-codoping for LED applications

The Ca_2.95−yDy_0.05B₂O₆:yNa⁺ (0≤y≤0.20) phosphors were synthesized at 1100 °C in air by the solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), photoluminescence excitation (PLE), photoluminescence (PL) spectra and thermoluminescence (TL) spectra. The PLE spectra show the excitation peaks from 300 to 400 nm due to the 4f-4f transitions of Dy³⁺. This mercury-free excitation is useful for solid-state lighting and light-emitting diodes (LEDs). The emission of Dy³⁺ ions on 350 nm excitation was observed at 480 nm (blue) due to the ⁴F_9/2→⁶H_15/2 transitions, 575 nm (yellow) due to ⁴F_9/2→⁶H_13/2 transitions and 660 nm (red) due to weak ⁴F_9/2→⁶H_11/2 emissions. The PL results from the investigated Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors show that Dy³⁺ emissions increase with the increase of the Na⁺ codoping ions. The integral intensity of yellow to blue (Y/B) can be tuned by controlling Na⁺ content. By the simulation of white light, the optimal CIE value (0.328, 0.334) can be achieved when the content of Na⁺-codoping ions is y=0.2. The results imply that the Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors could be potentially used as white LEDs.     

Emission analysis of Dy and Pr:Bi2O3-ZnF2-B2O3-Li2O-Na2O glasses

In this paper, we present the spectral results of Dy³⁺ and Pr³⁺ (1.0 mol%) ions doped Bi₂O₃-ZnF₂-B₂O₃-Li₂O-Na₂O glasses. Measurements of X-ray diffraction (XRD), differential scanning calorimetry (DSC) profiles of these rare-earth ions doped glasses have been carried out. From the DSC thermograms, glass transition (T_g), crystallization (T_c) and melting (T_m) temperatures have been evaluated. The direct and indirect optical band gaps have been calculated based on the glasses UV absorption spectra. The emission spectrum of Dy³⁺:glass has shown two emission transitions ⁴F_7/2→⁶H_15/2 (482 nm) and ⁴F_7/2→⁶H_13/2 (576 nm) with an excitation at 390 nm wavelength and Pr³⁺:glass has shown a strong emission transition ¹D₂→³H₄ (610 nm) with an excitation at 445 nm. Upon exposure to UV radiation, Dy³⁺ and Pr³⁺ glasses have shown bright yellow and reddish colors, respectively, from their surfaces.     

Crystalline and photoluminescence characteristics of YVO4:Sm thin films grown by pulsed laser deposition under oxygen pressure

YVO₄:Sm³⁺ films were deposited on Al₂O₃ (0 0 0 1) substrates at various oxygen pressures changing from 13.3 to 46.6 Pa by using the pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by means of X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. The XRD pattern confirmed that YVO₄:Sm³⁺ film has zircon structure and the AFM study revealed that the films consist of homogeneous grains ranging from 100 to 400 nm. The room temperature photoluminescence (PL) spectra showed that the emitted radiation was dominated by a reddish-orange emission peak at 602 nm radiating from the transition of (⁴G_5/2→⁶H_7/2). The crystallinity, surface morphology, and photoluminescence spectra of thin-film phosphors were highly dependent on the deposition conditions, in particular, the substrate temperature. The surface roughness and photoluminescence intensity of these films showed similar behavior as a function of oxygen pressure.     

Synthesis and characterization of BaAl2O4:Eu co-doped with different rare earth ions

Combustion method was used in this study to prepare BaAl₂O₄:Eu²⁺ phosphors co-doped with different trivalent rare-earths (Re³⁺=Dy³⁺, Nd³⁺, Gd³⁺, Sm³⁺, Ce³⁺, Er³⁺, Pr³⁺ and Tb³⁺) ions at an initiating temperature of 600 °C. The phosphors were annealed at 1000 °C for 3 h. As confirmed from the X-ray diffraction (XRD) data, both as prepared and post annealed samples crystallized in the well known hexagonal structure of BaAl₂O₄. All samples exhibited bluish-green emission associated with the 4f⁶5d¹→4f⁷ transitions of Eu²⁺ at ∼500 nm. Although the highest intensity was observed from Er³⁺ co-doping, the longest afterglow (due to trapping and detrapping of charge carriers) was observed from Nd³⁺ followed by Dy³⁺ co-doping. The traps responsible for the long afterglow were studied using thermoluminescence (TL) spectroscopy.     

Upconversion luminescence and mechanisms in Yb-sensitized Tm-doped oxyhalide tellurite glasses

Effect of Yb₂O₃ content on upconversion luminescence and mechanisms in Yb³⁺-sensitized Tm³⁺-doped oxyhalide tellurite glasses were investigated under 980 nm excitation. Intense blue and relatively weak red upconversion emission centered at 476 and 649 nm corresponding to the transitions ¹G₄→³H₆ and ¹G₄→³H₄ of Tm³⁺, respectively, are simultaneously observed at room temperature. The results show that upconversion blue and red emission intensities of Tm³⁺ first increase, reach its maximum at Yb₂O₃%=3 mol%, and then decrease with increasing Yb₂O₃ content. The effect of Yb₂O₃ content on upconversion intensity is discussed, and possible effect mechanisms are evaluated. The investigated results were conducing to increase upconversion luminescence efficiency of Tm³⁺.     

Spectral hole burning and fluorescence in femtosecond laser induced Sm-doped glasses

The femtosecond laser was used to irradiate sol-gel derived Sm³⁺-doped Al₂O₃-SiO₂ glasses, in which the Sm³⁺ was reduced into Sm²⁺ ions. The fluorescence line narrowing was applied to investigate the coordination sphere of the Sm²⁺ ion. The spectral hole burning was performed on ⁷F₀→⁵D₀ transition of the Sm²⁺. The depth and width of the burnt holes were ∼27% and ∼4 cm⁻¹ FWHM at 7 K, respectively. Hole spectra were stable up to room temperature. The hole-burning efficiency was superior to that of Sm²⁺ in H₂ treated glasses and comparable to that in X-ray in terms of hole-burning dynamics.     

Y3Al5O12 ceramic absorbers for the suppression of parasitic oscillation in high-power Nd:YAG lasers

The objective of this study was to identify a material suitable to absorb radiation at the wavelength of neodymium-doped Yttrium Aluminum Garnet (Y₃Al₅O₁₂:YAG), 1064 nm. M-(M= Sm³⁺, Co²⁺, Co³⁺, Cr³⁺, and Cr⁴⁺) doped highly transparent YAG ceramics were fabricated, and their absorption spectra were measured. Unlike Co²⁺ and Cr³⁺-doped ceramic samples, Co³⁺ and Cr⁴⁺ and Sm³⁺-doped:YAG ceramics were found to have significant absorption at 1064 nm. However, the Sm³⁺-doped YAG clearly emerged as the best candidate because it is also transparent at 808 nm, the pumping wavelength laser diode (LD), and also at most absorption bands used for flash-lamp pumping.