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).     

Luminescence properties of red-emitting praseodymium-activated BaTi4O9 phosphor

The photoluminescence and low-voltage cathodoluminescence characteristics of BaTi₄O₉:Pr³⁺ were investigated. The excitation band of intervalence charge transfer (IVCT) of BaTi₄O₉:Pr³⁺ emerged distinctly at 330 nm. The resultant emissions appeared at 606-643 nm corresponding to the ¹D₂→³H₄ transition. In BaTi₄O₉:Pr³⁺, the emission of ³P₀→³H₄ transition at 490 nm was not observed. The results were in a pure red color emission.     

Energy transfer in LaMgB5O10:Pr,Mn under VUV excitation

Luminescent properties of Pr³⁺ or Mn²⁺ singly doped and Pr³⁺, Mn²⁺ co-doped LaMgB₅O₁₀ are investigated by synchrotron radiation VUV light. When LaMgB₅O₁₀:Pr³⁺ is excited at185 nm, the photon cascade emission between 4f levels of Pr³⁺ is observed. In the excitation spectra of LaMgB₅O₁₀:Mn²⁺ monitoring the 615 nm emission of Mn²⁺, several excitation bands in a spectral range from 330 to 580 nm are recorded, among which the most intense band is centered at 412 nm (⁶A_1g→⁴E_g-⁴A_1g). This band has considerable spectra overlap with the 410 nm emission (¹S₀→¹I₆) of Pr³⁺, which is favorable for energy transfer from Pr³⁺ to Mn²⁺. Such energy transfer is observed in the co-doped sample, converting the violet emission (410 nm) of Pr³⁺ into the red emission (615 nm) of Mn²⁺. The concentration dependence of transfer efficiency is also investigated.     

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.     

Potential PDP phosphors with strong absorption around 172 nm: Rare earth doped NaLaP2O7 and NaGdP2O7

NaLaP₂O₇ and NaGdP₂O₇ powder samples are prepared by solid-state reactions at 750 and 600 °C, respectively, and the VUV-excited luminescence properties of Ln³⁺ (Ln=Ce, Pr, Tb, Tm, Eu) in both diphosphates are studied. Ln³⁺ ions in both hosts show analogous luminescence. For Ce³⁺-doped samples, the five Ce³⁺ 5d levels can be clearly identified. As for Pr³⁺ and Tb³⁺-doped samples, strong 4f-5d absorption band around 172 nm is observed, which matches well with Xe-He excimer in plasma display panel (PDP) devices. As a result, Pr³⁺ can be utilized as sensitizer to absorb 172 nm VUV photon and transfer energy to appropriate activators, and Tb³⁺-doped NaREP₂O₇(RE=La, Gd) are potential 172 nm excited green PDP phosphors. For Tm³⁺ and Eu³⁺-doped samples, the Tm³⁺-O²⁻ charge transfer band (CTB) is observed to be at 177 nm, but the CTB of Eu³⁺ is observed at abnormally low energy position, which might originate from multi-position of Eu³⁺ ions. The similarity in luminescence properties of Ln³⁺ in both hosts indicates certain structural resemblance of coordination environment of Ln³⁺ in the two sodium rare earth diphosphates.     

Synthesis and luminescence investigation of RE (Eu, Tb and Ce)-doped lithium silicate (Li2SiO3)

Synthesis and photoluminescence (PL) investigations of lithium metasilicate doped with Eu³⁺, Tb³⁺ and Ce³⁺ were carried out. PL spectra of Eu-doped sample showed peaks corresponding to the ⁵D₀→⁷F_j (j=1, 2, 3 and 4) transitions under ultraviolet excitation. Strong red emission coming from the hypersensitive ⁵D₀→⁷F₂ transition of Eu³⁺ ion suggested the presence of the dopant ion in structurally disordered environment. Tb³⁺-doped silicate sample showed blue-green emission corresponding to the ⁵D₄→⁷F_j (j=6, 5 and 4) transitions. Ce-doped sample under excitation from UV, showed a broad emission band in the region 350-370 nm with shoulders around 410 nm. The fluorescence lifetimes of Eu³⁺ and Tb³⁺ ions were found out to be 790 and 600 μs, respectively. For Ce³⁺, the lifetime was of the order of 45 ns. PL spectra of the europium- and terbium-doped samples were compared with commercial red (Y₂O₃:Eu³⁺) and green (LaPO₄:Tb³⁺) phosphors, respectively. It was found that the emission from the doped silicate sample was 37% of the commercial phosphor in case of the Tb-doped sample and 8% of the commercial phosphor in case of the Eu-doped sample.     

The effects of substrate temperature on the structure, morphology and photoluminescence properties of pulsed laser deposited SrAl2O4:Eu,Dy thin films

In this study, SrAl₂O₄:Eu²⁺,Dy³⁺ thin film phosphors were deposited on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique. The films were deposited at different substrate temperatures in the range of 40-700 °C. The structure, morphology and topography of the films were determined by using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). Photoluminescence (PL) data was collected in air at room temperature using a 325 nm He-Cd laser as an excitation source. The PL spectra of all the films were characterized by green phosphorescent photoluminescence at ∼530 nm. This emission was attributed to 4f⁶5d¹→4f⁷ transition of Eu²⁺. The highest PL intensity was observed from the films deposited at a substrate temperature of 400 °C. The effects of varying substrate temperature on the PL intensity were discussed.     

Luminescent properties of trivalent praseodymium-doped lanthanum aluminum germanate LaAlGe2O7

The luminescent characteristics of Pr³⁺-activated LaAlGe₂O₇ were investigated. In response to excitement using 448 nm blue light, the emission spectra involved most of the ³P₀→³H_J transitions. The dominant emission came from the ³P₀→³H₄ transition at 487 nm. ¹D₂ fluorescence quenching was observed in highly doped samples and is related to the cross-relaxation processes among neighboring Pr³⁺ ions. In contrast with conventional Pr³⁺-activated phosphors, the extraordinary excitation spectra showed only intense f-f transition of Pr³⁺ ions, while the 4f-5d transition was eliminated. This is ascribed to photoionization. By analyzing absorption and excitation spectra, it is recognized that no efficient energy transfer occurs between Pr³⁺ and the host lattice in LaAlGe₂O₇.     

Spectroscopic investigations of Nd-, Er-, Er/Yb-, and Tm-ions doped SiO2-Al2O3-CaF2-GdF3 glasses

This paper reports on the absorption, visible and near-infrared luminescence properties of Nd³⁺, Er³⁺, Er³⁺/2Yb³⁺, and Tm³⁺ doped oxyfluoride aluminosilicate glasses. From the measured absorption spectra, Judd-Ofelt (J-O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. Decay lifetime curves were measured for the visible emissions of Er³⁺ (558 nm, green), and Tm³⁺ (650 and 795 nm), respectively. The near infrared emission spectrum of Nd³⁺ doped glass has shown full width at half maximum (FWHM) around 45 nm (for the ⁴F_3/2→⁴I_9/2 transition), 45 nm (for the ⁴F_3/2→⁴I_11/2 transition), and 60 nm (for the ⁴F_3/2→⁴I_13/2 transition), respectively, with 800 nm laser diode (LD) excitation. For Er³⁺, and Er³⁺/2Yb³⁺ co-doped glasses, the characteristic near infrared emission bands were spectrally centered at 1532 and 1544 nm, respectively, with 980 nm laser diode excitation, exhibiting full width at half maximum around 50 and 90 nm for the erbium ⁴I_13/2→⁴I_15/2 transition. The measured maximum decay times of ⁴I_13/2→⁴I_15/2 transition (at wavelength 1532 and 1544 nm) are about 5.280 and 5.719 ms for 1Er³⁺ and 1Er³⁺/2Yb³⁺ (mol%) co-doped glasses, respectively. The maximum stimulated emission cross sections for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ and Er³⁺/Yb³⁺ are 10.81×10⁻²¹ and 5.723×10^-21 cm². These glasses with better thermal stability, bright visible emissions and broad near-infrared emissions should have potential applications in broadly tunable laser sources, interesting optical luminescent materials and broadband optical amplification at low-loss telecommunication windows.     

Enhancement of red spectral emission intensity of Y3Al5O12:Ce phosphor via Pr co-doping and Tb substitution for the application to white LEDs

We have enhanced color-rendering property of a blue light emitting diode (LED) pumped white LED with yellow emitting Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce) phosphor using addition of Pr and Tb as a co-activator and host lattice element, respectively. Pr³⁺ addition to YAG:Ce phosphor resulted in sharp emission peak at about 610 nm through ¹D₂→³H₄ transition. And when Tb³⁺ substituted Y³⁺ sites, Ce³⁺ emission band shifted to a longer wavelength due to larger crystal field splitting. Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and (Y_1−xTb_x)₃Al₅O₁₂:Ce³⁺ phosphors were coated on blue LEDs to fabricate white LEDs, respectively, and their color-rendering indices (CRIs, R_a) were measured. As a consequence of the addition of Pr³⁺ or Tb³⁺, CRI of the white LEDs improved to be R_a=83 and 80, respectively. Especially, blue LED pumped (Y_0.2Tb_0.8)₃Al₅O₁₂:Ce³⁺ white LED showed both strong luminescence and high color-rendering property.     

Scintillation and anomalous emission in elpasolite Cs2LiLuCl6:Ce

The luminescence and scintillation properties of Cs₂LiLuCl₆:0.5%Ce³⁺ are presented. Special attention is devoted to a 9.4 ns fast emission at 275 nm that can only be excited via the highest cubic field 5d_e state of Ce. Contrary to Cs₃LuCl₆ and Cs₂LiYCl₆, where the same type of fast emission was observed, the emission in Cs₂LiLuCl₆ is still observed at room temperature. Assuming that the 5d_e state is located inside the host conduction band (CB), we propose that the emission originates from a mixed state at or just below the bottom of the CB and ends at the 4f ground state of Ce³⁺. To proof this model we studied the thermal quenching of the anomalous luminescence and performed X-ray photoelectron spectroscopy. A model for a temperature-activated energy transfer from the anomalous state to the lowest 5d_t excited state of Ce³⁺ explains most of the results. Besides the 275 nm emission, the material shows 5d_t-4f Ce³⁺ emission at 370 and 406 nm and 2 ns fast core-valence luminescence when excited with 16-22 eV photons. The scintillation properties of Cs₂LiLuCl₆:Ce are briefly discussed.     

Temperature-dependent photoluminescence spectra of Er-Tm-codoped Al2O3 thin film

Er-Tm-codoped Al₂O₃ thin films with different Tm to Er concentration ratios were synthesized by cosputtering from separated Er, Tm, Si, and Al₂O₃ targets. The temperature dependence of photoluminescence (PL) spectra was studied. A flat and broad emission band was achieved in the 1.4-1.7 μm and the observed 1470, 1533 and 1800 nm emission bands were attributed to the transitions of Tm³⁺: ³H₄ → ³F₄, Er³⁺: ⁴I_13/2 → ⁴I_15/2 and Tm³⁺: ³F₄ → ³H₆, respectively. The temperature dependence is rather complicated. With increasing measuring temperature, the peak intensity related to Er³⁺ ions increases by a factor of five, while the Tm³⁺ PL intensity at 1800 nm decreases by one order of magnitude. This phenomenon is attributed to a complicated energy transfer (ET) processes involving both Er³⁺ and Tm³⁺ and increase of phonon-assisted ET rate with temperature as well. It should be helpful to fully understand ET processes between Er and Tm and achieve flat and broad emission band at different operating temperatures.     

Relocalization of Ce 5d electrons from host conduction band

Single crystal fibers of Ce³⁺ doped SrAl₂O₄ and CaAl₄O₇ were prepared through the laser heated pedestal growth method. Sites dependent Ce³⁺ emissions were found at 385 nm (427 nm) and 420 nm (325 nm) in SrAl₂O₄ and CaAl₄O₇ hosts, respectively. The Ce³⁺ emissions at 385 nm and 420 nm in the two hosts exhibited strong afterglows. They could persist for more than 10 h. The long persistence and sites dependence of Ce³⁺ emissions were originated from charge compensation of doping Ce³⁺ into divalent cation sites. The lifetimes of Ce³⁺ emissions in both hosts were found to depend on the laser excitation wavelengths. With 266 nm laser excitation, Ce³⁺ 5d electrons were delocalized into the host's conduction band, resulting in a prolonged decay time. The 355 nm laser excitation did not delocalize the 5d electrons and hence the measured lifetimes were the intrinsic Ce³⁺ emission lifetimes that were 17 and 35.5 ns in SrAl₂O₄ and CaAl₄O₇ hosts, respectively. The prolonged Ce³⁺ emission lifetime on 266 nm laser excitation was because of the relocalization of the 5d electrons from the host conduction band. The lifetimes of Ce³⁺ 5d electrons within the conduction band were found to be 34 and 44 ns in SrAl₂O₄ and CaAl₄O₇ hosts, respectively.     

Luminescence of La3F3[Si3O9]:Ce

The luminescence properties of Ce³⁺ in La₃F₃[Si₃O₉] are reported. Excitation and emission bands corresponding to 4f¹→5d¹ transitions of Ce³⁺ were identified. The center of gravity of the 5d states lies at remarkable high energy (43.2×10³ cm⁻¹) for Ce³⁺ in a silicate compound. This high value is attributed to the combined oxygen/fluoride coordination of the Ce³⁺ ion. Emission from the lowest 4f5d level to the ²F_5/2 and ²F_7/2 levels was found at 32.4×10³ and 30.4×10³ cm⁻¹. These results are compared with literature data on silicates and fluorides. From the values found for Ce³⁺, predictions are made for the positions of the 4f5d bands of Pr³⁺ and Er³⁺ in La₃F₃[Si₃O₉]. For both ions, it is concluded that in this host lattice emission is expected from high lying 4fⁿ energy levels.     

Luminescence from the Pr 4f5d and S0 states in LiLaP4O12

The photoluminescence and excitation spectra of Pr³⁺ activated LiLaP₄O₁₂ has been investigated in the 10-300 K temperature region. At all temperatures, the luminescence consists of optical transitions emanating from both the Pr³⁺ 4f¹5d¹ and the ¹S₀ states. However, at low temperatures the emission spectrum is dominated by the intraconfiguration emission transitions emanating from the Pr³⁺¹S₀ state. With increasing temperature, there is an exchange of intensity between the two emitting states; emission transitions from the ¹S₀ state exhibit strong intensity quenching while the 4f¹5d¹→4f² emission transitions reveal intensity gain. These results are explained on the basis of thermal population of the 4f¹5d¹ state by the ¹S₀ state. The energy barrier of 0.05 eV (403 cm⁻¹) for the nonradiative process is determined from the temperature dependence of the ¹S₀ lifetime.     

Luminescence and energy transfer processes in Lu2SiO5:Ce scintillator

The energy transfer processes in Lu₂SiO₅:Ce³⁺ luminescence was investigated through the temperature dependent luminescence under excitation with VUV-UV. Ce1 center emission peaking at 393 and 422 nm and Ce2 center emission peaking at 462 nm were observed. Ce2 center emission is enhanced with the temperature, which can be explained by the rate of energy transfer from Ce1 center increases when the temperature rises. The Ce1 emission shows the thermal quenching effect under the direct excitation of Ce³⁺ at 262 nm. However, under the interband excitation of 183 nm, the Ce1 center emission exhibits undulating temperature dependence. This is because the emission is governed by thermal quenching and possible thermal enhancement of the transport of free carriers with the rising temperature.     

Luminescent characteristics of CaTiO3:Pr thin films prepared by pulsed laser deposition method with various substrates

CaTiO₃:Pr³⁺ films were deposited on different substrates such as Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica using pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by XRD and SEM measurements. The films grown on the different substrates have different crystallinity and morphology. The FWHM of (2 0 0) peak are 0.18, 0.25, 0.28, and 0.30 for Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica, respectively. The grain sizes of phosphors grown on different substrates were estimated by using Scherrer's formula and the maximum crystallite size observed for the thin film grown on Al₂O₃ (0 0 0 1). The room temperature PL spectra exhibit only the red emission peak at 613 nm radiated from the transition of (¹D₂ → ³H₄) and the maximum PL intensity for the films grown on the Al₂O₃ (0 0 0 1) is 1.1, 1.4, and 3.7 times higher than that of the CaTiO₃:Pr³⁺ films grown on MgO (1 0 0), Si (1 0 0), and fused Sillica substrates, respectively. The crystallinity, surface morphology and luminescence spectra of thin-film phosphors were highly dependent on substrates.     

Luminescence in LaBaB9O16 prepared by combustion synthesis

LaBaB₉O₁₆ phosphors activated by various ions belonging to ns², 3dⁿ and 4fⁿ configurations were prepared by combustion synthesis. Phosphors’ synthesis and luminescence spectra are reported. Most of the activators displayed intense characteristic emission. Pr³⁺→Gd³⁺, Ce³⁺→Tb³⁺, Ce³⁺→Dy³⁺, Ce³⁺→Mn²⁺ and Bi³⁺→Mn²⁺ energy transfers were also observed. In particular, Ce³⁺→Tb³⁺ energy transfer leads to an efficient green emitting phosphor.     

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.     

Luminescence properties of LiPrxCe1−xP4O12

LiPr_1−xCe_xP₄O₁₂ (x=0, 0.002, 0.02; 0.1) powder samples were prepared using the melt solution technique. Luminescent parameters of LiPr_1−xCe_xP₄O₁₂ phosphors have been investigated under ultraviolet-vacuum ultraviolet (3-12 eV) synchrotron radiation and X-rays excitation at room and near liquid He temperatures. Excitation luminescence spectra of Ce³⁺ emission, luminescent spectra and decay curves from the lower excited state levels of the 4f¹5d¹ and 5d¹ electronic configuration of the Pr³⁺ and Ce³⁺, respectively, clearly indicate energy transfer from Pr³⁺ to Ce³⁺. Energy migration proceeds via the Pr-sublattice followed by nonradiation transfer from Pr³⁺ to Ce³⁺ ions.