White light emission in Tm/Er/Yb tri-doped Y2O3 transparent ceramic

Tm³⁺/Er³⁺/Yb³⁺ triply doped Y₂O₃ transparent ceramics were fabricated by solid state reaction and characterized from the point of view of white light upconversion luminescence. All the samples exhibited high transparency not only in near-infrared band but also in visible region. Strong red (Er³⁺: ⁴F_9/2 → ⁴I_15/2), green (Er³⁺: ²H_11/2, ⁴S_3/2 → ⁴I_15/2) and blue (Tm³⁺: ¹G₄ → ³H₆) upconversion emissions have been observed under 980 nm excitation at room temperature. By varying the concentration of Er³⁺ ion, various colors of upconversion luminescence (pure blue, bluish green, pure green and yellowish green), including white light with CIE-X = 0.295 and CIE-Y = 0.312, can be easily achieved.     

Polarized spectral analysis of Er ions in Er:LiGd(MoO4)2 crystal

The Er³⁺:LiGd(MoO₄)₂ crystal with Ø21 × 33 mm³ was grown by the Czochralski technique, and the absorption spectra, the fluorescence spectra and the fluorescence decay curves were measured at room temperature. Some spectroscopic parameters, such as the parameters of oscillator strengths, the spontaneous transition probabilities, the fluorescence branching ratios, the radiative lifetimes and the emission cross-sections were estimated based on Judd-Ofelt theory and Füchtbauer-Ladenburg method. The infrared emission at 1450-1650 nm, due to ⁴I_13/2 → ⁴I_15/2 transition and the visible emission at 520-569 nm corresponding to ²H_11/2,⁴S_3/2 → ⁴I_15/2 transition were observed in Er³⁺:LiGd(MoO₄)₂ crystals under 979 nm excitation at room temperature. The emission cross-sections are 4.37 × 10⁻²⁰ cm² at 553 nm and 0.584 × 10⁻²⁰ cm² at 1561 nm for π-polarization, and the following measured lifetimes are 4.57 ms and 10.74 μs. The upconversion emissions were attributed to energy transfer between Er³⁺ ions and the excited state absorption.     

Effect of Yb concentration on the structures and upconversion luminescence properties of Y2O3:Er ultrafine phosphors

Y₂O₃:Er³⁺ ultrafine phosphors with a varying Yb³⁺ ion concentration were prepared by a urea homogeneous precipitation method. The results of XRD show that all the samples are of a pure cubic structure and the average crystallite sizes can be calculated as 45, 34, and 28 nm for Y₂O₃:Er³⁺ ultrafine phosphors with Yb³⁺ ion concentrations of 0, 10%, and 20%, respectively. The lattice constant and cell volume of the ultrafine phosphors decrease with enhancing Yb³⁺ ion concentration. The upconversion luminescence spectra of all the samples were studied under 980 nm laser excitation. The strong green and red upconversion emission were observed, and attributed to the ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺, respectively. The intensity of red emission increases with increasing Yb³⁺ ion concentration. The effect of Yb³⁺ ion concentration on the structures and upconversion luminescence mechanism were discussed.     

Effect of Bi doping on the quenching concentration of H11/2/S3/2 level of Er

Bi³⁺ and Er³⁺ codoped Y₂O₃ was prepared by sol-gel method. The upconversion emission was investigated under 980 nm excitation. For samples without Bi³⁺, the quenching concentration of ²H_11/2/⁴S_3/2 level of Er³⁺ is 3.0 mol%. However, by 1.5 mol% Bi³⁺ doping the quenching concentration increases to 5.0 mol%; meanwhile, the green emission is enhanced 1.9 times. The results indicate that both the quenching concentration and the emission intensity of ²H_11/2/⁴S_3/2 level can be increased by Bi³⁺ doping.     

Enhancement of upconversion luminescence of Y2O3:Er nanocrystals by codoping Li-Zn

The upconversion (UC) luminescence in sol-gel synthesized Li⁺, Zn²⁺, or Li⁺-Zn²⁺ codoped Y₂O₃:Er³⁺ nanocrystals were investigated under the excitation of a 970 nm diode laser. Compared to undoped Y₂O₃:Er³⁺ samples, proper doping of Li⁺-Zn²⁺ leads to an drastic increase of the UC luminescence centered at 560 nm by a factor of 28. The UC luminescence enhancement is a result of the increased lifetime of the intermediate state ⁴I_11/2 (Er). The intensity ratio of the green over red emissions (green/red) is also affected by the codoping of Zn²⁺, Li⁺ and Li⁺-Zn²⁺ ions. Our results demonstrated that the Li⁺-Zn²⁺ codoping in Y₂O₃:Er³⁺ phosphors produced remarkable enhancement of the UC luminescence and green/red ratio, making this nanocrystal a promising candidate for photonic and biological applications.     

Ultraviolet and violet upconversion luminescence in Ho-doped Y2O3 ceramic induced by 532-nm CW laser

Ultraviolet and violet upconversion luminescence spectra of holmium-doped Y₂O₃ were produced under the excitation of a compact continues-wave 532 nm solid-state laser. Emissions around 306, 362, 412, 390 and 428 nm can be assigned to the transitions of ³D₃ → ⁵I_J (J = 8, 7, 6), ⁵G₄ → ⁵I₈ and ⁵G₅ → ⁵I₈, respectively. Power dependence and upconversion dynamics analysis demonstrated that both the energy transfer upconversion (ETU) and the excited state absorption (ESA) processes were involved in the population of ³D₃ state via the coupled intermediate states ⁵S₂/⁵F₄. Fluorescence spectra in the visible and infrared ranges showed that ⁵G₄ and ⁵G₅ states were populated by the ESA process from ⁵I₆ and ⁵I₇ states, respectively, while the ⁵I₆ and ⁵I₇ states were radiatively populated from the excited ⁵S₂/⁵F₄ states. Upconversion mechanisms have been evaluated based on a rate equation model.     

Structure and upconversion luminescence properties of BaYF5:Yb, Er nanoparticles prepared by different methods

BaYF₅:Yb³⁺, Er³⁺ (BYF) upconversion (UC) luminescence nanoparticles have been prepared using co-precipitation and hydrothermal techniques, respectively. Two different fluoride sources were used to synthesize BYF by the hydrothermal method, and the sizes of the as-prepared spherical particles were about 30 nm (NH₄BF₄ as a fluoride source) and 100 nm (NH₄HF₂ as a fluoride source), respectively. While the nanoparticles prepared by the co-precipitation method are irregular, many clusters and agglomerates can be seen. The UC fluorescence has been realized in all the as-prepared BYF samples upon 980 nm excitation. It is found that their luminescence spectra depend strongly upon the preparation method. Factors affecting the upconversion fluorescent intensity have been also studied. The UC emission transitions for ⁴F_9/2-⁴I_15/2 (red), ²H_11/2-⁴I_15/2 (green) and ⁴S_3/2-⁴I_15/2 (green) in the Yb³⁺/Er³⁺ codoped BYF nanoparticles depending on pumping power have also been discussed.     

Preparation and luminescent characteristics of Sr3RE2(BO3)4:Dy (RE = Y, La, Gd) phosphors for white LED

Dysprosium-activated Sr₃RE₂(BO₃)₄ (RE = Y, La, Gd) phosphors were synthesized by a high temperature solid-state reaction method. The phase uniformity of the phosphors was characterized by X-ray powder diffraction (XRD) and the luminescence characteristics were investigated. The excitation spectra at 575 nm emission show strong spectral bands in the region of 300-500 nm. The emission spectra of the phosphors with 365 nm excitation show three bands centered at 484 nm, 575 nm and 680 nm, which originate from the transitions of ⁴F_9/2 → ⁶H_15/2, ⁴F_9/2 → ⁶H_13/2 and ⁴F_9/2 → ⁶H_11/2 of Dy³⁺, respectively. The effect of Dy³⁺ concentration on the emission intensity of the phosphors was investigated. The fluorescence decay curves for ⁴F_9/2 → ⁶H_13/2 excited at 365 nm and monitored at λ_em of 575 nm were measured. The decay times decreased slowly with increasing Dy³⁺ doping concentration due to a trap capturing to resonance fluorescence transfer of the activated ions and due to the exchange interactions between activated ion pairs. In order to determine the type of interaction between activated ions, the concentration dependence curves (lg(I/x) versus lg x) of Sr₃RE₂(BO₃)₄:Dy³⁺ (RE = Y, La, Gd) were plotted. The concentration quenching mechanism of the ⁴F_9/2 → ⁶H_13/2 (575 nm) transition of Dy³⁺ is the d-d interaction. All results indicate these phosphors are promising white-color luminescent materials.     

Optical properties of highly Er-doped sodium-aluminium-phosphate glasses for broadband 1.5 μm emission

Erbium-doped Na₃Al₂P₃O₁₂ (NAP) glasses with compositions 92NAP-(8−x)Al₂O₃-(x)Er₂O₃ (where x = 2-8) were prepared and characterized for absorption, visible and NIR emission and decay time properties. Judd-Ofelt analysis has been carried out to predict radiative properties of luminescent levels of Er³⁺ ions. Comparatively larger photoluminescence lifetimes (7.86 ms) and larger quantum efficiencies (74%) for the laser transition, ⁴I_13/2 → ⁴I_15/2 (at 1.54 μm) are observed. The moisture insensitivity, large Er³⁺ ion doping capability and relatively high-gain and broad emission at 1.5 μm are the most notable features of these glasses to realize efficient short-length optical amplifiers.     

Blue and green emissions with high color purity from nanocrystalline Ca2Gd8Si6O26:Ln (Ln = Tm or Er) phosphors

Blue and green light emissive nanocrystalline Ca₂Gd₈Si₆O₂₆ (CGS):Tm³⁺ and CGS:Er³⁺ phosphors with high color purity were prepared by solvothermal reaction method. The structural and morphological properties of these phosphors were evaluated by the powder X-ray diffraction (XRD) and scanning electron microscopy, respectively. From the XRD results, Tm³⁺:CGS and Er³⁺:CGS phosphors had the characteristic peaks of oxyapatite in the hexagonal lattice structure. The visible luminescence properties of phosphors were obtained by ultraviolet (UV) or near-UV light and low voltage electron beam (0.5-5 kV) excitation. The photoluminescence and cathodoluminescence properties were investigated by changing the variation of Tm³⁺ or Er³⁺ concentrations and the acceleration voltage, respectively. The CGS:Tm³⁺ phosphors exhibited the blue emission due to ¹D₂→³F₄ transition, while the CGS:Er³⁺ phosphors showed the green emission due to ⁴S_3/2→⁴I_15/2 transition. The color purity and chromaticity coordinates of the fabricated phosphors are comparable to or better than those of standard phosphors for lighting or imaging devices.     

Spectroscopic investigation of Er-doped (Gd0.7Y0.3)2SiO5 single crystal for potential application in 1.5 μm laser

The Er³⁺:(Gd_0.7Y_0.3)₂SiO₅ (hereafter abbreviated as Er³⁺:G_0.7Y_0.3SO) single crystals were grown by the Czochralski technique. The unpolarized absorption spectrum and photoluminescence (PL) spectra were measured at room temperature. The Judd-Ofelt phenomenological method was used to estimate the intensity parameters, radiative lifetimes and branching ratios of luminescence. The stimulated emission cross-section of the ⁴I_13/2 → ⁴I_15/2 transition of special interest of ∼1.5 μm laser was calculated by the Fuchtbauer-Ladenburg equation, and the relevant gain cross-sections were also estimated for several inverse-population parameters to evaluate a potential laser activity of the Er³⁺:G_0.7Y_0.3SO system. Also, the potential range of the optical pumping was assessed based on the absorption cross-section at room temperature. Finally the excited state dynamics of the Er³⁺:G_0.7Y_0.3SO system was investigated and experimental lifetimes of ⁴I_13/2 and ⁴I_11/2 levels were measured. Taking into account the satisfactory absorption near 971 and 1529 nm, and the high gain cross-section in the range of 1530-1620 nm, the Er³⁺:G_0.7Y_0.3SO crystal can be considered as a promising active material for laser operation near 1.5 μm.     

Preparation and luminescence characterization of new carbonate (Y2(CO3)3·nH2O:Eu) phosphors via the hydrothermal route

A new Eu³⁺-activated Y₂(CO₃)₃·nH₂O phosphor was successfully prepared via the hydrothermal process using urea as a reaction agent. Y₂(CO₃)₃·nH₂O:Eu³⁺ phosphors displayed an intense red emission at 615 nm due to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions under 254 nm excitation. The intensity of this emission was significantly increased with a rise in the hydrothermal temperatures. The study of photoluminescence properties demonstrated that Y³⁺ ions were replaced by Eu³⁺ ions in the host lattice at the 9-coordination sites. With an increase in heating temperatures, the morphology of Y₂(CO₃)₃·nH₂O:Eu³⁺ powders changed from a spherical to a rod-like shape. Calcination at elevated temperatures resulted in thermal decomposition of Y₂(CO₃)₃·nH₂O:Eu³⁺ to form Y₂O₃:Eu³⁺. The formed Y₂O₃:Eu³⁺ powder exhibited a rod-like morphology with an intense red emission.     

Vacuum ultraviolet spectroscopic properties of KSrPO4:Tb

KSrPO₄:Tb³⁺ phosphors were prepared by a solid-state method and their photoluminescence properties were investigated under vacuum ultraviolet excitation. In the excitation spectrum monitoring at 544 nm, the band in the region of 120-162 nm can be attributed to be the overlap of host absorption and charge transfer transition of O²⁻ → Tb³⁺, and the band ranging from 162 to 300 nm was assigned to the f-d transition of Tb³⁺. The photoluminescence spectrum shows that the phosphors exhibited a strong green emission around 544 nm corresponding to the ⁵D₄ → ⁷F₅ transition of Tb³⁺ under the excitation of 147 nm. Optimal emission intensity was obtained when x = 7% in KSr_1-xPO₄:xTb³⁺ and the luminescent chromaticity coordinates were calculated to be (x = 0.317, y = 0.522) for KSr_0.93PO₄:7%Tb³⁺.     

Solvothermal synthesis of monodisperse ultrasmall cubic-structure Ba2YbF7 nanocrystals with intense upconversion

A series of monodisperse ultrasmall Ba₂YbF₇ nanocrystals with intense upconversion emission were synthesized via a facile solvothermal method by using oleic acid as capping ligands. X-ray diffraction (XRD) and transmission electron microscopy (TEM) assays revealed that the as-synthesized Ba₂YbF₇ nanocrystals are of cubic structure, rather than the reported tetragonal structure. The cell parameter of the particles is 5.918 Å. The Er³⁺ or Tm³⁺ doped Ba₂YbF₇ nanocrystals with the size of sub-10 nm can give an intense upconversion emission under the 980 nm laser excitation and the upconversion processes were discussed. The Ba₂YbF₇ nanocrystals show a potential application as a bioimaging agent.     

Preparation, structure and photoluminescence of nanoscaled-Nd: Lu3Al5O12

Nd:Lu₃Al₅O₁₂ (Nd:LuAG) nano-crystalline was synthesized by co-precipitation method. Its phase transformation, structure, absorption and photoluminescence properties were studied. The Nd:LuAG polycrystalline phase is formed above 900 °C and its particle sizes are in the range of 18-36 nm. The structure of Nd:LuAG was refined by Rietveld method. The lattice parameters and the distortion of Lu³⁺-O²⁻ polyhedron in Nd:LuAG are larger than that of in pure LuAG. Because the distortion of Lu³⁺-O²⁻ polyhedron is larger than that of Y³⁺-O²⁻ polyhedron in YAG and the distance of Lu³⁺-O²⁻ is smaller than that of Y³⁺-O²⁻ in YAG, Nd³⁺ in LuAG experiences a stronger crystal field effect, which is proved by the crystal field strength and the chemical environment parameter. The absorption spectrum shows that Nd:LuAG has a broad absorption band at 808 nm with FWHM above 6 nm, which is favorable for improving laser efficiency. The fluorescence lifetime from ⁴F_3/2 → ⁴I_11/2 transition is 320 μs and longer than that of Nd:YAG. The longer lifetime is propitious to energy storage. The emission cross section at 1064 nm is 2.89 × 10⁻¹⁹ cm², taking into account the Boltzmann distribution of the excited state. The emission cross section in Nd:LuAG is also larger than that of Nd:YAG, which is useful for laser operation. All results indicate that Nd:LuAG is a promising crystal material to apply in high energy lasers.     

Enhancement of the upconversion luminescence intensity in Er doped BaTiO3 nanocrystals by codoping with Li ions

Infrared-to-visible upconversion luminescence spectra were investigated in Er³⁺ doped and Er³⁺-Li⁺ codoped BaTiO₃ nanocrystals following excitation with 976 nm. By introducing Li⁺ ions, the upconverted emission intensity is found to be greatly enhanced compared to that of the nanocrystals without Li⁺ ions. The enhanced luminescence might be attributed to the oxygen vacancy generated by Li⁺ ion incorporation in the lattices and the distortion of the local asymmetry around Er³⁺. We observe that excitation power dependence and decay time are increased by the incorporation of Li⁺ ions. Li⁺ ions also can reduce the OH groups in specimen, which decrease nonradiative decay from the ⁴S_3/2 to ⁴F_9/2, enhancing the upconversion emission intensities.     

Sensitized high-order ultraviolet upconversion emissions of Gd by Er in NaYF4 microcrystals

High-order ultraviolet (UV) upconversion (UC) emissions of Gd³⁺ and Er³⁺ ions were observed in NaYF₄:Yb³⁺/Gd³⁺/Er³⁺ microcrystals under 980 nm excitation. These UC emissions came from six- and five-photon UC processes at low pump power range, which were confirmed by the pumping power dependences of UC fluorescence intensities. In these high-order UC processes, energy transfer (ET) processes of Er³⁺ → Gd³⁺ played crucial roles in populating the excited states of Gd³⁺ ions. Experiments on concentration variation and dynamic analysis revealed the ET processes between Er³⁺ and Gd³⁺ in detail. Some of possible population routes for populating excited Gd³⁺ ions were proposed based on spectral and dynamic analysis.     

Spectroscopy features of Pr and Er ions in Li2O-ZrO2-SiO2 glass matrices mixed with some sesquioxides

The glasses of the composition Li₂O-ZrO₂-SiO₂: Pr₂O₃/Er₂O₃ mixed with three interesting sesquioxides (viz., Al₂O₃, Sc₂O₃, Y₂O₃) were synthesized. Optical absorption and fluorescence spectra (in the spectral range 350-2100 nm were studied at ambient temperature. The Judd-Ofelt theory was applied to characterize the absorption and luminescence spectra of Pr³⁺ and Er³⁺ ions in these glasses. Following the luminescence spectra, various radiative properties like transition probability A, branching ratio β and the radiative life time τ for different emission levels of two rare earth ions have been evaluated. The radiative life times for the upper levels ³P₀ (Pr³⁺) and ⁴S_3/2 (Er³⁺) have also been measured and quantum efficiencies were estimated. The variations observed in these parameters were discussed in the light of changing environment of rare earth ions due to mixing of different sesquioxides in the glass network.     

Eu/Sm ions co-doped white light luminescence SrSiO3 glass-ceramics phosphor for White LED

Eu²⁺/Sm³⁺ co-doped silicate glass was prepared by high temperature melting under reducing atmosphere and the Eu²⁺/Sm³⁺ co-doped SrSiO₃ transparent glass-ceramics were obtained after heat-treatment. X-ray diffraction (XRD) and Raman spectra confirmed the formation of SrSiO₃ nano-crystals in the glass matrix. The photoluminescence excitation (PLE) spectra and photoluminescence (PL) spectra of the samples were measured. A broad emission band from 400 nm to 550 nm due to the 4f⁶5d¹ → 4f⁷ transitions of Eu²⁺ was observed, as well as several sharp emission peaks at 563 nm, 600 nm, 646 nm and 713 nm ascribed to the 4f → 4f transitions of Sm³⁺. The luminescence properties of the glass ceramics with different molar ratio of Eu²⁺/Sm³⁺ were studied and the corresponding chromaticity coordinates were calculated. The ultraviolet light-emitting diode (UV-LED) excitable glass-ceramics emitting white light were obtained by tuning the relative emission intensity of Eu²⁺ and Sm³⁺. The results indicate that the Eu²⁺/Sm³⁺ co-doped SrSiO₃ transparent glass-ceramics can be used as a potential matrix material for White LED under UV-LED excitation.     

Morphology and phase evolvement of Yb/Er co-doped NaYF4 microtubes prepared with YF3 submicrospindles as precursor

Hexagonal phase NaYF₄ microtubes co-doped with Yb³⁺ and Er³⁺ were synthesized through a hydrothermal process with YF₃ submicrospindles as precursor. The X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) were utilized to characterize the structure and morphology of the as-prepared products. XRD results show that pure cubic NaYF₄ crystals can be obtained when reaction time is 2 h. While the product is mixture of cubic and hexagonal phase NaYF₄ when reaction time is from 7 to 20 h. Continuing to increase the reaction time to 24 h, the pure hexagonal NaYF₄ crystals were formed. The FE-SEM and TEM results show that the morphology of pure cubic NaYF₄ is spherical clusters composed of spherical nanoparticles with average diameter of about 100 nm and the pure hexagonal NaYF₄ crystals have tubular structure with out diameter of about 0.3-0.5 μm, inner diameter of about 0.5-1 μm and length ranging from 3 to 12 μm. The luminescence properties of Yb³⁺/Er³⁺ co-doped cubic and hexagonal phase NaYF₄ microcrystals were also studied. Under 980-nm excitation, the upconversion luminescence (UCL) intensity of hexagonal phase NaYF₄ microtubes is much stronger than that of cubic phase clusters. Moreover, both red and green upconversion are ascribed to the two-photon process. Therefore, hexagonal phase NaYF₄ microtubes with high UCL efficiency may have a potential application in photonic device.