Use of LiF flux in the preparation of Ca3Sc2Si3O12:Ce3+ phosphor by sol-combustion method

LiF flux was added when prepare Ca₃Sc₂Si₃O₁₂:Ce³⁺ phosphors with sol-combustion method using urea as a fuel and chelating agent. Investigation of phase, morphology and photoluminescence of the phosphors reveals that this kind of method can decrease the phase-forming temperature by 400–500 °C and the phosphors show more uniform morphology and more excellent photoluminescence properties compared to conventional solid-state method. As one of the most important parameters for phosphors used in white light emitting diodes, the thermal quenching properties of the prepared samples are compared and discussed. The fabrication of single-color light emitting diodes show the Ca₃Sc₂Si₃O₁₂:Ce³⁺ phosphor prepared by sol-combustion method with LiF flux can be considered as a more promising high efficiency candidate used for white light emitting diodes than the phosphor made by solid-state method.     

Synthesis of Ca3Sc2Si3O12:Ce3+ phosphor by hydrothermal Si alkoxide gelation

Single-phase Ca₃Sc₂Si₃O₁₂:Ce³⁺ green emission phosphor was synthesized by the hydrothermal silicon alkoxide gelation method. Such specimens demonstrated higher emission intensity than the Ca₃Sc₂Si₃O₁₂:Ce³⁺ samples that are prepared by conventional solid-state reaction method. It was also demonstrated that annealing in the presence of graphite as an oxygen scavenger significantly improves the fluorescence properties of this material.     

Long wavelength Ce emission in Y6Si3O9N4 phosphors for white-emitting diodes

Y₆Si₃O₉N₄:Ce³⁺ phosphor was prepared by a solid-state reaction in reductive atmosphere. X-ray powder diffraction (XRD) analysis confirmed the formation of Y₆Si₃O₉N₄:Ce³⁺. Scanning electron microscopy (SEM) observation indicated that the microstructure of the phosphor consisted of irregular fine grains with an average size of about 5 μm. Photoluminescence (PL) measurements showed that the phosphor can be efficiently excited by near ultraviolet (UV) or blue light excitation, and exhibited bright green emission peaked at about 525 nm. Compared with Ce³⁺-doped Y₄Si₂O₇N₂ phosphors, Ce³⁺-doped Y₆Si₃O₉N₄ phosphors showed longer wavelengths of both excitation and emission. The Y₆Si₃O₉N₄:Ce³⁺ is a potential green-emitting phosphor for white LEDs.     

Luminescence characterization of (Ca1−xSrx)(S1−ySey):Eu,M (M = Sc and Y) for high color rendering white LED

The highly efficient red phosphors (Ca_1−xSr_x)(S_1−ySe_y):Eu²⁺,M³⁺ (M = Sc and Y) were prepared, starting from CaCO₃, SrCO₃, Eu₂O₃, Sc₂O₃, Y₂O₃, S, and SeO₂ with a flux, by a conventional solid-state reaction. The optimized red phosphors converted 11.8% (Sc³⁺) and 11.7% (Y³⁺) of the absorbed blue light into luminescence. These quantum values are much higher than Q = 3.0% of CaS:Eu²⁺. For the fabrication of light-emitting diodes (LEDs), the prepared phosphors were coated with MgO from non-aqueous solution to overcome their weakness against moisture. White LEDs were fabricated by pasting the prepared red phosphors and the yellow YAG:Ce³⁺ phosphor on an InGaN blue chip (λ_ems = 446.5 nm). The incorporation of the red phosphor to the YAG:Ce³⁺ phosphor resulted in an improved color rendering index (Ra) from 70 to 80.     

Synthesis,crystal structure and luminescence in Ca<Subscript>3</Subscript>Al<Subscript>2</Subscript>O<Subscript>6</Subscript>

Bluish green emitting phosphor, Ca₃Al₂O₆:Ce³⁺, is prepared by low-temperature combustion method. X-ray diffraction, photoluminescence, scanning electron microscopy techniques are used to characterize the synthesized phosphor. The most efficient bluish green (483 nm) emission is observed under the excitation by near UV light. The emission characteristics are credited to 5d → 4f type transitions in Ce³⁺. The luminescence properties of Eu²⁺ are predicted for the first time from those of Ce³⁺. Also, photoluminescence of Eu³⁺ is studied in the same host. The emission spectrum of Ca₃Al₂O₆:Eu³⁺ shows the peak at 592 (orange) and 614 nm (red) wavelengths. Ca₃Al₂O₆:Ce³⁺phosphor can be a potential blue phosphor for field emission display, solid-state lighting and LED.     

Enhancement of photoluminescence properties of green to yellow emitting Y3Al5O12: Ce phosphor by AlN addition for white LED applications

AlN-substituted in Y₃Al₅O₁₂: Ce³⁺ phosphor was synthesized to improve the phosphor efficiency of phosphor-converted white light emitting diodes. The photoluminescence properties of AlN-substitued for Al₂O₃ in Y₃Al₅O₁₂: Ce³⁺ phosphor showed excellent green to yellow emission intensity under 460 nm. The highest emission intensity was observed at an AlN concentration of 0.3 mol and a Ce³⁺ concentration in the optimized flux of 0.20 mol. The green to yellow emitting AlN-substituted in Y₃Al₅O₁₂: Ce³⁺ phosphor can be applied to white LEDs.     

Luminescence properties and preparation of Lu<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> powder doped with Ce and Pr ions

Lu₃Al₅O₁₂:Ce³⁺ phosphor powder, which exhibits green emission band, was synthesized by the high-temperature solid-state reaction method with a flux BaF₂. X-ray diffraction (XRD), photoluminescence (PL) spectra, and fluorescent lifetime spectra were used to characterize the structure and luminescent properties of the sample. The XRD patterns indicated that when prepared at 1550 °C for 3 h with 4 wt% flux, Lu₃Al₅O₁₂:Ce³⁺ phosphors powder is the garnet cubic crystal system structure. Photoluminescence (PL) spectra showed that the Lu₃Al₅O₁₂:Ce³⁺ phosphor powder can be effectively excited by near ultraviolet and blue light, emitting broad band peaking at 505 nm, which is attributed to ²F_5/2?→?²D_5/2 transition. The self-concentration quenching mechanism of Ce³⁺ is the dipole–dipole interaction. Small amount of Pr³⁺ increased red light emission at 610 nm. Photoluminescence (PL) spectra and fluorescent lifetime spectra indicated that there was an efficient energy transfer process between Ce³⁺ and Pr³⁺.     

Enhancement of blue-green photoluminescence in B2O3 fritted ZrO2:Ce3+ phosphor

Blue-green emission of ZrO₂:Ce³⁺ phosphor, prepared by solid-state reaction, is demonstrated. The phosphor presents a strong and broad photoluminescence band centered at 496 nm with excitation at 291 nm. The optimized Ce content is 2.5 mol% for the strongest emission of ZrO₂:Ce³⁺ phosphors prepared without B₂O₃. The PL intensity is enhanced by at least 3 dB by adding 5.0 mol% B₂O₃ within the ZrO₂:Ce³⁺ containing 5.0 mol% Ce during synthesis. Increase of the B₂O₃ flux effectively induces the Ce ions to substitute the Zr ions in ZrO₂ lattice and causes the ZrO₂ lattice distortion. The formation of Ce_0.75Zr_0.25O₂ compound within the ZrO₂:Ce³⁺ occurred when the Ce content is greater than or equal to 2.5 mol% for the phosphors prepared without B₂O₃ and leads to a degradation of the phosphor PL intensity due to the host effect. The addition of B₂O₃ during the preparation of phosphors containing Ce ions lower than or equal to 5.0 mol% essentially restrains the Ce_0.75Zr_0.25O₂ formation and then enhances the blue-green PL.     

Preparation and luminescence properties of Y<Subscript>3−y</Subscript>Al<Subscript>5−x</Subscript>Ga<Subscript>x</Subscript>O<Subscript>12</Subscript>:Ce<Superscript>3+</Superscript><Subscript>y</Subscript> phosphors

Y_3?yAl_5?xGa_xO₁₂:Ce³⁺_y phosphors were prepared by high temperature solid state reaction method. The crystal structures, the influence of Ga³⁺ concentration on the photoluminescence (PL), cathodoluminescence, thermal stability and morphology of the phosphors were studied in detail. The results indicated that diffraction angle of the samples decreased gradually with the increase of Ga³⁺ ions content in XRD pattern. The emission peak of the spectra show a progressive blue-shift, the intensity increased first and then decreased and the optimal Ga³⁺ concentration in Y_2.94Al_5?xGa_xO₁₂:Ce³⁺_0.06 phosphors is x?=?0.75. The critical concentration of Ce³⁺ in YAGG:Ce³⁺ phosphors is affected with the ratio of Ga³⁺ to Al³⁺ and the Y_2.9Al_4.25Ga_0.75O₁₂:Ce³⁺_0.1 phosphor showed the best performance on PL. However, the optimum concentration of Y_3?yAl_5?xGa_xO₁₂:Ce³⁺_y phosphors is x?=?1.5 and y?=?0.04 when they were excited by cathode ray.     

Structural and luminescence study of Ce3+ and Tb3+ doped Ca3Sc2Si3O12 garnets obtained by freeze-drying synthesis method

Ca₃Sc₂Si₃O₁₂ garnets doped with Ce³⁺ and Tb³⁺ ions were synthesized by a freeze-drying precursor method. The structural characterization was performed by X-ray diffraction (XRD) and Raman spectroscopy. Scanning Electron Microscopy (SEM) images of the calcined material were studied. High temperature treatments and doping with RE³⁺ ions resulted in a reduction of the secondary phases (Sc₂O₃) and an increase of the mean size of the nanocrystals, from 75 to 149 nm. These effects were confirmed by means of Raman spectra. Moreover, luminescence features of Ce³⁺ and Tb³⁺ doped samples indicated that these ions are effectively incorporated into the crystalline phase. In addition, the energy transfer processes between Ce³⁺ and Tb³⁺ ions in codoped garnets have been studied.     

Luminescence properties and energy transfer investigations of Ce3+/Tb3+ co-doped BaY2Si3O10 phosphor

A novel phosphor BaY₂Si₃O₁₀ (BYSO): Ce³⁺, Tb³⁺ was synthesized by the conventional solid-state reaction, which displays tunable color emission from blue to blue-green under ultraviolet excitation by adjusting the radio of Ce³⁺ and Tb³⁺ appropriately. Photoluminescence characteristics were carefully investigated. We demonstrate the existence of efficient energy transfer from Ce³⁺ to Tb³⁺ in BaY₂Si₃O₁₀: Ce³⁺, Tb³⁺ phosphor. The energy transfer Ce³⁺ → Tb³⁺ was proved to be governed by dipole–quadrupole interaction.     

A yellow-emitting Ca3Si2O7: Eu phosphor for white LEDs

A series of yellow-emitting phosphors based on a silicate host matrix, Ca_3 − xSi₂O₇: xEu²⁺, was prepared by solid-state reaction method. The structure and photoluminescent properties of the phosphors were investigated. The XRD results show that the Eu²⁺ substitution of Ca²⁺ does not change the structure of Ca₃Si₂O₇ host and there is no impurity phase for x < 0.12. The SEM images display that phosphors aggregate obviously and the shape of the phosphor particle is irregular. The EDX results reveal that the phosphors consist of Ca, Si, O, Eu and the concentration of these elements is close to the stoichiometric composition. The Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be excited at a wavelength of 300-490 nm, which is suitable for the emission band of near ultraviolet or blue light-emitting-diode (LED) chips. The phosphors exhibit a broad emission region from 520 to 650 nm and the emission peak centered at 568 nm. In addition, the shape and the position of the emission peak are not influenced by the Eu²⁺ concentration and excitation wavelength. The phosphor for x = 0.045 has the strongest excitation and emission intensity, and the Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be used as candidates for the white LEDs.     

Enhanced red-emitting phosphor Na<Subscript>2</Subscript>Ca<Subscript>3</Subscript>Si<Subscript>2</Subscript>O<Subscript>8</Subscript>:Eu<Superscript>3+</Superscript> by charge compensation

A series of novel red-emitting Na₂Ca_3???x Si₂O₈:xEu³⁺ phosphors were synthesized by solid state reactions. The phosphors can strongly absorb 395 nm light, and show red emission with a good color purity. The excitation and emission spectra properties of Na₂Ca₃Si₂O₈:Eu³⁺ were characterized. Na₂Ca₃Si₂O₈:Eu³⁺ with self-compensated and alkali metal ions charge compensated approaches (2Ca²⁺→Eu³⁺ + M⁺, M?=?Li⁺, Na⁺, K⁺) have investigated, which found that the red emission of luminescent intensity can be greatly enhanced, and shows superior luminescent property to the commercial Y₂0₃S:Eu³⁺. The present work implies that the efficient charge compensated phosphors are promising candidates as red-emitting phosphor for w-LEDs.     

Synthesis,tunable luminescence and thermal stability of Mg<Subscript>2</Subscript>Al<Subscript>4</Subscript>Si<Subscript>5</Subscript>O<Subscript>18</Subscript>:Ce<Superscript>3+</Superscript>/Mn<Superscript>2+</Superscript> phosphors

Ce³⁺/Mn²⁺ singly doped and codoped Mg₂Al₄Si₅O₁₈ phosphors were synthesized by a solid state reaction. The phase, luminescent properties and thermal stability of the synthesized phosphors were investigated. Ce³⁺ and Mn²⁺ singly doped Mg₂Al₄Si₅O₁₈ phosphors show emission bands locating in blue and yellow–red regions, respectively. In Ce³⁺ and Mn²⁺ codoped Mg₂Al₄Si₅O₁₈, tunable luminescence was obtained because of the energy transfer from Ce³⁺ to Mn²⁺. In Mg₂Al₄Si₅O₁₈:Ce³⁺/Mn²⁺ phosphors with a fixed Ce³⁺ concentration, energy transfer efficiency increases with the increasing Mn²⁺ concentration, which is confirmed by the continually decreasing intensity and shortening decay time of Ce³⁺ emission. Moreover, the luminescent properties and thermal stability provide a great significance on the applications in the field of light emitting diodes.     

The development of Ce3+-activated (Gd,Lu)3Al5O12 garnet solid solutions as efficient yellow-emitting phosphors

Abstract

Ce³⁺-activated Gd₃Al₅O₁₂ garnet, effectively stabilized by Lu³⁺ doping, has been developed for new yellow-emitting phosphors. The powder processing of [(Gd_1?xLu_x)_1?yCe_y]₃Al₅O₁₂ solid solutions was achieved through precursor synthesis via carbonate precipitation, followed by annealing. The resultant (Gd,Lu)AG:Ce³⁺ phosphor particles exhibit typical yellow emission at ～570 nm (5d–4f transition of Ce³⁺) upon blue-light excitation at ～457 nm (the ²F_5/2–5d transition of Ce³⁺). The quenching concentration of Ce³⁺ was determined to be ～1.0 at% (y = 0.01) and the quenching mechanism was suggested to be driven by exchange interactions. The best luminescent [(Gd_0.9Lu_0.1)_0.99Ce_0.01]AG phosphor is comparative to the well-known YAG:Ce³⁺ in emission intensity but has a substantially red-shifted emission band that is desired for warm-white lighting. The effects of processing temperature (1000–1500 °C) on the spectroscopic properties of the phosphors, especially those of Lu³⁺/Ce³⁺, were thoroughly investigated and discussed from the centroid position and crystal field splitting of the Ce³⁺ 5d energy levels.     

Study of the effect of Li<Superscript>+</Superscript> concentration on the photoluminescence properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphors

Y₂O₃:Eu³⁺ phosphors were prepared by hydrothermal method. Effect of the doping concentration of Eu³⁺ on the photoluminescence properties of Y₂O₃:Eu³⁺ phosphor was studied in details. It was found that the strongest emission intensity is achieved as atomic ratio of Y³⁺ to Eu³⁺ is 8. As concentration of Eu³⁺ exceeds the critical concentration, the emission intensity decreases dramatically due to the concentration quenching of Eu³⁺. Also, the effect of Li⁺ on the photoluminescence performance of the Y₂O₃:Eu³⁺ phosphor is studied in this work. According to the results, the doping of Li⁺ may greatly improve the PL performance of the Y₂O₃:Eu³⁺ phosphors due to the flux effect and improved crystallinity caused by the doping of Li⁺.     

Effect of BaF2 powder addition on the synthesis of YAG phosphor by mechanical method

Here, we report on the effect of BaF₂ powder addition on the mechanical synthesis of Ce³⁺-doped Y₃Al₅O₁₂ (Y_2.97Al₅O₁₂:Ce_0.03³⁺, YAG:Ce³⁺) phosphors for white light emitting diodes. The YAG phosphors were synthesized by the mechanical method using an attrition-type mill. When BaF₂ was added at 6 wt% to the raw powder materials and milled, the synthesis of YAG:Ce³⁺ was favorably achieved at the vessel temperature of 255 °C, which was about 1200 °C lower than the YAG phosphor synthesis temperature by solid-state reaction. The synthesized YAG:Ce³⁺ phosphor revealed the maximum internal quantum yield of 57%.     

Structural and optical characterization of RE (Eu<Superscript>2+</Superscript>, Ce<Superscript>3+</Superscript>) doped SrMg<Subscript>2</Subscript>Al<Subscript>6</Subscript>Si<Subscript>9</Subscript>O<Subscript>30</Subscript> nanocrystalline phosphor

This article present the reports on optical study of Eu²⁺ and Ce³⁺ doped SrMg₂Al₆Si₉O₃₀ phosphors, which has been synthesized by combustion method at 550 °C. Here SrMg₂Al₆Si₉O₃₀:Eu²⁺ emission band observed at 425 nm by keeping the excitation wavelength constant at 342 nm, whereas SrMg₂Al₆Si₉O₃₀:Ce³⁺ ions shows the broad emission band at 383 nm, under 321 nm excitation wavelength, both the emission bands are assigned due to 5d–4f transition respectively. Further, phase purity, morphology and crystallite size are confirmed by XRD, SEM and TEM analysis. However, the TGA analysis is carried out to know the amount of weight lost during the thermal processing. The CIE coordinates of SrMg₂Al₆Si₉O₃₀:Eu²⁺ phosphor is observed at x?=?0.160, y?=?0.102 respectively, which may be used as a blue component for NUV-WLEDs. The critical distance of energy transfer between Ce³⁺ ions and host lattice is found to be 10.65 Å.     

Photoluminescence properties of green-emitting Eu2+-activated Ba3Si6O12N2 oxynitride phosphor for white LED applications

Eu²⁺-activated Ba₃Si₆O₁₂N₂ green-emitting phosphors were synthesized by a solid-state reaction method. X-ray diffraction patterns showed that the synthesized phosphor sintered at 1200 °C for 12 h was a Ba₃Si₆O₁₂N₂ pure phase. The synthesized phosphors were excited in UV to blue light. The emission spectra showed a broad green emission band when excited with a light at 465 nm. The highest emission intensity was observed at a Eu²⁺ concentration of 0.25 mol and the NH₄Cl concentration of the optimized flux was found to be 9 wt.%. The obtained green-emitting Ba₃Si₆O₁₂N₂:Eu²⁺ phosphors could be applied to white LED applications.     

Co-existence phenomenon of Ce3+/Ce4+ and Tb3+ in Ce/Tb co-doped Zn2(BO3)(OH)0.75F0.25 phosphor: Luminescence and energy transfer

A serials of Zn₂(BO₃)(OH)_0.75F_0.25 (ZBF), Tb³⁺, Ce^3+/4+ single-doped ZBF and Tb³⁺/Ce^3+/4+ co-doped ZBF novel phosphors with belt-like morphology were obtained through hydrothermal reaction without any surfactant. The obtained samples were characterized by XRD, SEM, EDS, TEM, TGA, XPS, DR, PL, and DT. The TGA curve shows that the phosphor is thermal stability. XPS results show that Tb³⁺ is present in the Tb-doped phosphor, and the Ce³⁺/Ce⁴⁺ mixed valence is present in the Ce-doped phosphor. The PL results indicate that ZBF host material and ZBH:Ce^3+/4+ can emit blue light, ZBF:Tb³⁺ can emit green light. Compared with the Tb³⁺ single doped phosphor, the Tb³⁺/Ce^3+/4+ co-doped phosphors shown stronger emission and shorter decay time, which is attributed to the effective energy transfer from the Ce^3+/4+ to Tb³⁺ ions.