The blue-light emission enhancement mechanism of Eu in Eu, Dy: SiO2 matrix

A Eu, Dy co-doped SiO₂ matrix xerogel with blue emission was prepared by the sol–gel method. Strong blue emission located between 425 nm and 525 nm with a peak at 486 nm is observed under UV laser excitation at room temperature, which is related to a 4f → 5d energy transition of Eu²⁺. Such techniques as FT-IR and TGA–DSC were used to measure the microstructure of the luminescent materials. The influence of Dy³⁺ ions on the luminescent property of Eu²⁺ was investigated. The emission intensity of Eu, Dy-codoped samples is stronger than that of Eu doped samples. The emission enhancement mechanism relating to Eu²⁺ is attributed to an energy transfer involving Dy³⁺ → Eu²⁺. Using energy transition theory, we speculate that the mechanism may be one of the resonance transfers via multi-polar interactions, and present a possible energy transfer model. The Eu²⁺ blue emission intensity reaches the maximum when the Dy³⁺ concentration is 0.1 mol%. When the concentration of Dy³⁺ is 0.3 mol%, a fluorescence quenching appears which might be related to the overlap part of Eu²⁺ excitation and emission levels, and also suggests the existence of Eu²⁺ → Eu²⁺ energy transfer.     

White light generation in Al2O3:Ce:Tb:Mn films deposited by ultrasonic spray pyrolysis

Aluminium oxide (Al₂O₃) films doped with CeCl₃, TbCl₃ and MnCl₂ were deposited at 300 °C with the ultrasonic spray pyrolysis technique. The films were analysed using the X-ray diffraction technique and they exhibited a very broad band without any indication of crystallinity, typical of amorphous materials. Sensitization of Tb³⁺ and Mn²⁺ ions by Ce³⁺ ions gives rise to blue, green and red simultaneous emission when the film activated by such ions is excited with UV radiation. The overall efficiency of such energy transfer results to be about 85% upon excitation at 312 nm. Energy transfer from Ce³⁺ to Tb³⁺ ions through an electric dipole-quadrupole interaction mechanism appears to be more probable than the electric dipole-dipole one. A strong white light emission for the Al₂O₃:Ce³⁺(1.3 at.%):Tb³⁺(0.2 at.%):Mn²⁺(0.3 at.%) film under UV excitation is observed. The high efficiency of energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions, resulting in cold white light emission (x = 0.30 and y = 0.32 chromaticity coordinates) makes the Ce³⁺, Tb³⁺ and Mn²⁺ triply doped Al₂O₃ film an interesting material for the design of efficient UV pumped phosphors for white light generation.     

Luminescent properties of Ca2BO3Cl:Eu yellow-emitting phosphor for white light-emitting diodes

The Ca₂BO₃Cl:Eu²⁺ phosphor was synthesized by the general high temperature solid-state reaction and an efficient yellow emission under near-ultraviolet and blue excitation was observed. The emission spectrum shows a single intense broad emission band centered at 573 nm, which corresponds to the allowed f-d transition of Eu²⁺. The excitation spectrum is very broad extending from 350 to 500 nm, which is coupled well with the emission of UV LED (350-410 nm) and blue LED (450-470 nm). The measured emission of In-GaN-based Ca₂BO₃Cl:Eu²⁺ LED shows white light to the naked eye with a chromatic coordinate of (0.33, 0.36). The Ca₂BO₃Cl:Eu²⁺ is a very appropriate yellow-emitting phosphor for white LEDs.     

Synthesis and luminescent properties of SrAl2O4:Eu green-emitting phosphor for white LEDs

SrAl₂O₄:Eu²⁺ phosphor was prepared by a solid-state reaction in CO-reductive atmosphere. X-ray powder diffraction (XRD) analysis confirmed the formation of SrAl₂O₄:Eu²⁺. Field-emission scanning electron-microscopy (FE-SEM) observation indicated that the microstructure of the phosphor consisted of irregular fine grains with an average size of about 7–8 μm. Photoluminescence measurements showed that the phosphor can be efficiently excited by UV–visible light from 350 to 430 nm, and exhibited bright green emission peaked at about 516 nm. Bright green LEDs were fabricated by incorporating the phosphor with an InGaN-based UV chip. All the characteristics indicated that SrAl₂O₄:Eu²⁺ is a good candidate phosphor applied in white LEDs.     

Influence of calcination temperature on luminescent properties of Sr3Al2O6:Eu, Dy phosphors prepared by sol–gel-combustion processing

The detailed preparation process of Eu²⁺ and Dy³⁺ ion co-doped Sr₃Al₂O₆ phosphor powders with red long afterglow by sol–gel-combustion method in the reducing atmosphere is reported. X-ray diffraction, scanning electron microscopy and photoluminescence spectroscopy are used to investigate the effects of synthesis temperature on the crystal characteristics, morphology and luminescent properties of the as-synthesized Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors. The results reveal that Sr₃Al₂O₆ crystallizes completely when the combustion ash is sintered at 1200 °C. The excitation and the emission spectra indicate that the excitation broad-band lies chiefly in visible range and the phosphor powders emit strong light at 618 nm under the excitation of 472 nm. The light intensity and the light-lasting time of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors are increased when increasing the calcination temperatures from 1050 to 1200 °C. The afterglow of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors sintered at 1200 °C lasts for over 600 s when the excited source is cut off. The red emission mechanism is discussed according to the effect of nephelauxetic and crystal field on the 4f⁶5d¹ → 4f⁷ transition of the Eu²⁺ ions.     

Sr3.5Mg0.5Si3O8Cl4: Eu bluish-green-emitting phosphor for NUV-based LED

Sr₄Si₃O₈Cl₄:Eu²⁺ and Sr_3.5Mg_0.5Si₃O₈Cl₄:Eu²⁺ phosphors were prepared by a conventional solid state reaction (SS). Excited by 370 nm near-ultraviolet light, the phosphors show an efficient bluish-green wide-band emission centering at 484 nm, which originates from the 4f5d¹ → 4f⁷ transition of Eu²⁺ ion. The excitation spectra of the phosphors are a broad band extending from 250 nm to 400 nm. Mg²⁺-codoping greatly enhances the bluish-green emission of the phosphors. An LED was fabricated by coating the Sr_3.5Mg_0.5Si₃O₈Cl₄:0.08Eu²⁺ phosphor onto an ~ 370 nm-emitting InGaN chip. The LED exhibits bright bluish-green emission under a forward bias of 20 mA. The results indicate that Sr_3.5Mg_0.5Si₃O₈Cl₄:0.08Eu²⁺ is a candidate as a bluish-green component for fabrication of NUV-based white LEDs.     

Preparation of SrAl2O4: Eu, Dy nanometer phosphors by detonation method

SrAl₂O₄: Eu²⁺, Dy³⁺ nanometer phosphors were synthesized by detonation method. The particle morphology and optical properties of detonation soot that was heated at different temperatures (600–1100 °C) had been studied systematically by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results indicated SrAl₂O₄: Eu²⁺, Dy³⁺ nanometer powders in monoclinic system (a = 8.442, b = 8.822, c = 5.160, β = 93.415) can be synthesized by detonation method, when detonation soot was heated at 600–800 °C. The particle size of SrAl₂O₄: Eu²⁺, Dy³⁺ is 35 ± 15 nm. Compared with the solid-state reaction and sol-gel method, synthesis temperature of the detonation method is lower about 500 and 200 °C respectively. After being excited under UN lights, detonation soot and that heated at 600–1100 °C can emit a green light.     

Effects of Zn doping on the structural and luminescent properties of Sr4Si3O8Cl4:Eu phosphors

Sr₄Si₃O₈Cl₄: Eu²⁺ phosphors were synthesized by the solid-reaction at high temperature. The emission intensity reaches a maximum at 0.08 mol% of Eu²⁺ concentration. The present paper mainly focused on the effects of Zn²⁺ on the crystallization behavior and photoluminescence (PL) properties of Sr₄Si₃O₈Cl₄:0.08Eu²⁺. Results suggested that no new phase is introduced by co-doping with a small amount of Zn²⁺ ions, but when co-doped with excessive amount of Zn²⁺ ions, Sr₂ZnSi₂O₇ appears. We find that the co-doping of a small amount of Zn²⁺ could remarkably improve the PL intensity of Sr₄Si₃O₈Cl₄:0.08Eu²⁺. When x = 0.05, the intensity of Sr₄Si₃O₈Cl₄:0.08Eu²⁺,xZn²⁺ was increased up to 2.3 times that of pure Sr₄Si₃O₈Cl₄:0.08Eu²⁺, which could be attributed to the flux effect of Zn²⁺ ions, and the Zn²⁺ doping reduces the opportunities of the energy transfer between Eu²⁺.     

CaSc2O4:Eu: A tunable full-color emitting phosphor for white light emitting diodes

We report an intense full-color emission originating from ⁵D_0,1,2,3 to ⁷F_0,1,2,3,4 transitions of Eu³⁺ in CaSc₂O₄ upon 395 nm excitation. The emission spectra vary with increasing Eu³⁺ concentration, demonstrating tunable color coordinates from white to red region in the CIE chromaticity diagram. Considering the relaxation from ⁵D_J to ⁵D_J−1 through cross energy transfer, the Eu³⁺ concentration dependent emission spectra are well simulated based on the analysis of steady state rate equations and the measured lifetimes of the ⁵D_J levels. It is suggested that CaSc₂O₄:Eu³⁺ could be a potential single-phased full-color emitting phosphor for near-ultraviolet InGaN chip pumped white light emitting diodes.     

Near UV-based LED fabricated with Ba5SiO4(F,Cl)6:Eu as blue- and green-emitting phosphor

A series of halosilicate phosphor, Ba₅SiO₄(F,Cl)₆:Eu²⁺, were synthesized by a solid state reaction. Excited by 370-nm light, Ba₅SiO₄Cl₆:Eu²⁺ exhibits a broad emission band peaking at 440 nm. Partial substitution of Cl⁻ with F⁻ in the host lattice leads to red-shift in the emission band with centering wavelength from 440 nm to 503 nm. The possible mechanism for the luminescence change was discussed based on the XRD patterns. Blue and green LEDs were fabricated by combination of a 370 nm-emitting near UV chip and the optimal Ba₅SiO₄Cl₆:Eu²⁺ and Ba₅SiO₄(F₃Cl₃):Eu²⁺, respectively. This series of phosphors is considered as a promising blue and green component used in fabrication of near UV-based white LEDs.     

Influence of excitation wavelengths on luminescent properties of Sr3Al2O6:Eu, Dy phosphors prepared by sol-gel-combustion processing

Eu²⁺ and Dy³⁺ ion co-doped Sr₃Al₂O₆ red-emitting long afterglow phosphor was synthesized by sol-gel-combustion methods using Sr(NO₃)₂, Al(NO₃)₃·9H₂O, Eu₂O₃, Dy₂O₃, H₃BO₃ and C₆H₈O₇·H₂O as raw materials. The crystalline structure of the phosphors were characterized by X-ray diffraction, luminescent properties of phosphors were analyzed by fluorescence spectrophotometer. The effect of excitation wavelengths on the luminescent properties of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors was discussed. The emission peak of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphor lays at 516 nm under the excitation of 360 nm, and at 612 nm under the excitation of 468 nm. The results reveal that the Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphor will emit a yellow-green light upon UV illumination, and a bright red light upon visible light illumination. The emission mechanism was discussed according to the effect of nephelauxetic and crystal field on the 4f⁶5d¹ → 4f⁷ transition of the Eu²⁺ ions in Sr₃Al₂O₆. The afterglow time of (Sr_0.94Eu_0.03Dy_0.03)₃ Al₂O₆ phosphors lasts for over 600s after the excited source was cut off.     

GeO2 dopant induced enhancement of red emission in CaAl12O19:Mn phosphor

In order to search efficient red-emitting phosphors for white LEDs application, CaAl₁₂O₁₉:Mn⁴⁺ phosphors have been prepared by a combustion method assisted with GeO₂ flux. The influence of GeO₂ concentration and annealing temperature on the structure and luminescence intensity for the phosphors has been investigated. The mechanism for luminescence enhancement has been discussed. At GeO₂ doping concentration of 1.5 mol%, the red emission intensity increases by 81% under 330 nm UVA excitation. More isolated luminescence center Mn⁴⁺ ions rather than pairs of Mn⁴⁺-Mn²⁺ ions are formed in the lattice with the introduction of GeO₂ at high temperature oxidation, leading to the enhancement of the red emission. A feasible new way to enhance the red emission in CaAl₁₂O₁₉:Mn⁴⁺ phosphor is obtained.     

Luminescence properties of Eu-activated Ca12Al10.6Si3.4O32Cl5.4: A promising phosphor for solid state lighting

In this article, we synthesized and characterized a novel bluish green phosphor for white light-emitting diodes, Eu²⁺-activated Ca₁₂Al_10.6Si_3.4O₃₂Cl_5.4. The phosphor shows broad and strong absorption in the region (320-450 nm), which is essential for improving the efficiency and quality of white light-emitting diodes. When excited at 380 nm, the phosphor shows two emission bands at around 425 and 500 nm. The main emission peak of Eu²⁺-activated Ca₁₂Al_10.6Si_3.4O₃₂Cl_5.4 exhibits red shift in comparison with that of Eu²⁺-activated Ca₁₂Al₁₄O₃₃, which is due to the introduction of Si and Cl ions. The results show Ca₁₂Al_10.6Si_3.4O₃₂Cl_5.4 is a promising host candidate for the phosphors.     

Yellow-emitting phosphor of Sr3B2O6:Eu for application to white light-emitting diodes

This work focuses on the development of Eu²⁺-doped strontium (Sr)-borate as a yellow-emitting phosphor and its application to the fabrication of white light-emitting diodes (LEDs). Synthesis of Eu²⁺-doped Sr-borate phosphors was finely tuned for obtaining the efficient yellow luminescence through varying host composition, Eu concentration, and firing temperature. The 1300 °C-fired Eu²⁺-doped Sr₃B₂O₆, which was found to be the most efficient candidate to date, was used for white LED fabrication. Their optical properties were evaluated, resulting in warm white lights with CIE chromaticity coordinates of (0.340–0.372, 0.287–0.314) and color rendering indices of 75–77 under the forward currents of 5–40 mA.     

Improved luminescence from Y2Sn2O7:Tb nanoparticles co-doped with Sb ions

Very small nanoparticles (size 3-5 nm) of Y₂Sn₂O₇, Y₂Sn₂O₇:Tb³⁺ and Sb³⁺ co-doped Y₂Sn₂O₇:Tb³⁺ were prepared at a relatively low temperature of 700 °C. Y₂Sn₂O₇ host is characterised by an emission around 436 nm, which is arising from the oxygen vacancies present in the lattice. Tb³⁺ emission improves significantly when Sb³⁺ ions are co-doped with Y₂Sn₂O₇:Tb³⁺ nanoparticles. Incorporation of Sb³⁺ ions at the Y³⁺ site of Y₂Sn₂O₇ lattice and associated lattice distortion around Tb³⁺/Y³⁺ ions brought about by the difference in the stable coordination number of Sb³⁺ and Y³⁺ ions are responsible for the improved Tb³⁺ emission from the co-doped samples.     

Novel blue-emitting phosphor NaMg4(PO4)3:Eu, Ce with energy transfer

A blue-emitting phosphor of NaMg₄(PO₄)₃:Eu²⁺, Ce³⁺ was prepared by a combustion-assisted synthesis method. The phase formation was confirmed by X-ray powder diffraction measurement. Photoluminescence excitation spectrum measurements show that the phosphor can be excited by near UV light from 230 to 400 nm and presents a dominant luminescence band centered at 424 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions at room temperature. Effective energy transfer occurs in Ce³⁺/Eu²⁺ co-doped NaMg₄(PO₄)₃ due to large spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺, and Ce³⁺ plays a role as a sensitizer. Ce³⁺-Eu²⁺ co-doped NaMg₄(PO₄)₃ powders can possibly be applied as blue phosphors in the fields of lighting and display.     

Efficient Bi → Nd energy transfer in Gd2O3:Bi,Nd

Bi³⁺,Nd³⁺ co-doped Gd₂O₃ were prepared by solid state reaction and the optical properties were investigated. The results show that the near-infrared emission of Nd³⁺ ions is significantly enhanced by the introducing of Bi³⁺ in co-doped samples. An efficient energy transfer from Bi³⁺ to Nd³⁺ corresponds to the near-infrared emission enhancement. The energy transfer efficiency reaches 64.1% for the sample with the strongest near-infrared emission, which has the optimized doping concentrations of 0.5% for Bi³⁺ and 2% for Nd³⁺. The interesting optical properties make Bi³⁺,Nd³⁺ co-doped Gd₂O₃ promising as the luminescent down-conversion layers in front of c-Si solar cells to enhance the performance of the solar cells.     

Synthesis and characterization of nanocrystalline manganese pyrophosphate Mn2P2O7

Mn₂P₂O₇ polyhedral particles were synthesized by simple and cost-effective method using manganese nitrate hydrate and phosphoric acid in the presence of nitric acid with further calcinations at the temperature of 800 °C. The crystallite size obtained from X-ray line broadening is 31 ± 13 nm for the Mn₂P₂O₇. The X-ray diffraction and SEM results indicated that the synthesized nanoparticles have only the structure without the presence of any other phase impurities. The FT-IR and FT-Raman spectra show characteristic bands of the P₂O₇⁴⁻ anion. The UV–Vis–NIR spectrum confirms the octahedral coordination of Mn²⁺ ion.     

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.     

Luminescence properties of Eu ions doped in Y2−xGdxO3 thin films grown by pulsed laser deposition method

Luminescence properties of Y_2−xGd_xO₃:Eu³⁺ (x = 0 to 2.0) thin films are investigated by site-selective laser excitation spectroscopy. The films were grown by pulsed laser deposition method on SiO₂ (100) substrates. Cubic phase Y₂O₃ and Gd₂O₃ and monoclinic phase Gd₂O₃ are identified in the excitation spectrum of the ⁷F₀ → ⁵D₀ transition of Eu³⁺. The emission spectra of the ⁵D₀ → ⁷F_J (J = 1 and 2) transition from individual Eu³⁺ centers were obtained by tuning the laser to resonance with each excitation line. The excitation line at around 580.60 nm corresponds to the line from Eu³⁺ with C₂ site symmetry of cubic phase. New lines at 578.65 and 582.02 nm for the C_S sites of Gd₂O₃ with monoclinic phase are observed by the incorporation of Gd in Y₂O₃ lattice. Energy transfer occurs between Eu³⁺ ions at the C_S sites and from Eu³⁺ ions at the C_S sites to those at the C₂ site in Y_2−xGd_xO₃.