Mechanism of energy transfer in Sr2CeO4:Eu3+ phosphor

Blue–white phosphor Sr₂CeO₄ belongs to a particular class of optical materials whose luminescence is governed by optical transitions associated with the electron charge transfer. The originality of its crystallographic structure, a chain-like sequence of luminescent centers, permits an effective transfer of the electronic excitation energy from the host to doped centers. Sr₂CeO₄, рure and doped with Eu³⁺-ions of different concentrations, was synthesized by the Pechini citrate-gel method. The luminescence spectra and luminescence decay curves of Sr₂CeO₄ and Sr₂CeO₄:Eu³⁺ at 300 and 80 K were investigated. The performed experiments revealed the Förster nonradiative energy transfer under the energy migration condition from the crystal host to the doped europium ions.     

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.     

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⁺.     

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.     

Luminescence and energy transfer of Mn co-doped SrSi2O2N2:Eu green-emitting phosphors

Eu²⁺ and Mn²⁺ co-doped SrSi₂O₂N₂ green-phosphors, with promising luminescent properties (examined by their powder diffuse reflection, photoluminescence excitation and emission spectra) suitable for UV converted white LEDs, were produced by high temperature solid-state reaction method. The produced materials exhibited intense broad absorption bands at 220–500 nm and a broad emission band centered at ca. 530 nm, attributed to 4f–5d transitions of Eu²⁺. The emission intensity of Eu²⁺ ions was greatly enhanced by introducing Mn²⁺ ions into SrSi₂O₂N₂:Eu²⁺ due to the energy transfer from Mn²⁺ to Eu²⁺. The energy transfer probability from Mn²⁺ to Eu²⁺ depends strongly on the Mn²⁺ concentration, which is maximized at a Mn²⁺ concentration of 3 mol%. It drastically decreases for higher concentrations. The results indicated that SrSi₂O₂N₂:Eu²⁺, Mn²⁺ is a promising green-emitting phosphor for white-light emitting diodes with near-UV LED chips.     

Preparation and characterization of Sr4Al2O7:Eu, Eu phosphors

A new composition of red strontium aluminate phosphor (Sr₄Al₂O₇:Eu³⁺, Eu²⁺) is synthesized using a solid state reaction method in air and in a reducing atmosphere. The investigation of firing temperature indicates that a single phase of Sr₄Al₂O₇ is formed when the firing temperature is higher than 1300 °C and that a Sr₃Al₂O₆ phase is formed as the main peak below 1300 °C. The effects of firing temperature and doping concentration on luminescent properties are investigated. Sr₄Al₂O₇ phosphors exhibit the typical red luminescent properties of Eu³⁺ and Eu²⁺. A comparison photoluminescence study with Sr₃Al₂O₆ phosphor shows that Sr₄Al₂O₇ has higher emission intensity than Sr₃Al₂O₆ as a result of the higher optimum doping concentration of Sr₄Al₂O₇ phosphor.     

Tuning the luminescence color and enhancement of afterglow properties of Sr(4−x−y)CaxBayAl14O25:Eu,Dy phosphor by adjusting the composition

Color point tuning is an important challenge for improving the practical applications of various displays, especially there are very limited white color single hosts that emits in the white spectrum. In this paper, the possibility of color tuning by substituting part of host lattice cation (Sr²⁺ ions) by Ca²⁺ or Ba²⁺ ions in an efficient strontium aluminate phosphor, Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺, is reported and found to be very promising for displays. A detail study by replacing part of Sr²⁺ with Ca²⁺ or Ba²⁺ has been investigated. X-ray diffraction study showed that crystal structure of Sr₄Al₁₄O₂₅ is preserved up to 20 mol of Ca²⁺ ion exchange while it is limited to 10 mol of Ba²⁺ ions exchange. Substantial shift in the emission band and color were observed by substitution of Sr²⁺ by Ca²⁺ or Ba²⁺ ions. A bluish-white emission and afterglow was observed at higher Ca²⁺ ions substitution. Further, partial Ca²⁺ substitutions (up to 0.8 mol) resulted in enhanced afterglow of Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺ phosphor. However, Ba²⁺ substitution decreased the fluorescence as well afterglow of the Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺ phosphor significantly. The enhanced phosphorescence by partial Ca²⁺ substitution is explained on the basis of increased density of shallow traps associated with higher solubility of Dy³⁺ ions in to the host lattice due to equivalent size of Ca²⁺ and Dy³⁺ ions. Thus, Ca²⁺ substitution in the Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺ phosphor is a promising method for tuning the emission color and improving the afterglow intensity of the phosphor.     

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.     

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.     

Photoluminescence mechanisms of color-tunable Sr2CeO4: Eu3+, Dy3+ phosphors based on experimental and first-principles investigation

We report single-phased color-tunable phosphors (Sr₂CeO₄: Eu³⁺, Dy³⁺) synthesized by a polymer-network gel method for UV–LED. The photoluminescence properties and possible energy transfer mechanisms of Eu³⁺ and Dy³⁺ in Sr₂CeO₄ were investigated by experiments and first principles calculations. The results show that the ⁵D₀ → ⁷F₂ emission of Eu³⁺ is enhanced by the increase in the amount of Eu³⁺ ions and Eu³⁺ substitution makes more stable defect than Dy³⁺ substitution does. The photoluminescence mechanism of Sr_1.994−xEu_xDy_0.006CeO₄ can be explained by the energy transfer model with the consideration of the defect conditions in the crystals.     

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.     

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.     

Dynamical processes of energy transfer in red emitting phosphor CaMoO4:Sm, Eu

Upon ⁴K_11/2 excitation of Sm³⁺ at 405 nm, the performance of energy transfer from Sm³⁺ to Eu³⁺ in the red emitting phosphor CaMoO₄:Eu³⁺, Sm³⁺ significantly extends its excitation region for better matching the near-UV LED. Photoluminescence spectra indicate that the energy transfer pathway concerns the relaxation from ⁴K_11/2 to ⁴G_5/2 of Sm³⁺ and subsequent transfer to ⁵D₀ of Eu³⁺ rather than ⁵D₁ of Eu³⁺. The fluorescent decay pattern of Sm³⁺⁴G_5/2 level in CaMoO₄:0.5% Sm³⁺, 2% Eu³⁺ is studied at 77 K based on the Inokuti-Hirayama formula, revealing an electronic dipole-dipole interaction between Sm³⁺ and Eu³⁺. The coefficient for the energy transfer is obtained to be 8.5 × 10⁻⁴⁰ s⁻¹ cm⁶. The fluorescence rise and decay pattern of Eu³⁺⁵D₀ level as Sm³⁺ is only excited at 77 K is well described by the dynamical processes of the energy transfer.     

Bright white upconversion luminescence from Er-Tm-Yb doped CaSnO3 powders

Bright white upconversion luminescence from Er³⁺-Tm³⁺-Yb³⁺ doped CaSnO₃ powders is obtained under the diode laser excitation of 980 nm. It is composed of three primary colors of red, green and blue emissions, which originate from the transitions of ⁴F_9/2 → ⁴I_15/2, (²H_11/2, ⁴S_3/2) → ⁴I_15/2 of Er³⁺ ions and ¹G₄ → ³H₆ of Tm³⁺ ions, respectively. The efficient upconversion emission is attributed to the energy transfer between Yb³⁺ and Er³⁺ or Tm³⁺ions. Moreover, it is observed that Tm³⁺ acts as the quenching center for the green upconversion luminescence from Er³⁺ ions, and the sensitizer for the red and blue luminescence when the Tm³⁺ doping content is less than 0.3 mol%. This is interpreted in terms of the efficient energy transfer between Tm³⁺ and Er³⁺ ions. The calculated color coordinates fall within the white region in the standard 1931 CIE chromaticity diagram, indicating the potential applications of Er³⁺-Tm³⁺-Yb³⁺ doped CaSnO₃ in the field of displaying and lasers, etc.     

Substitution site and photoluminescence spectra of Eu-substituted SrTiO3 prepared by Pechini method

Eu³⁺-substituted SrTiO₃ (Sr_1 − xEu_xTiO₃) without second phase has been successfully prepared by Pechini method. X-ray diffraction patterns have suggested that solid-solubility limit would be 1-2 mol% due to large ionic radius difference between Eu³⁺ and Sr²⁺. Photoluminescence spectra of Sr_1 − xEu_xTiO₃ have shown the intense ⁵D₀-⁷F₁ transition higher than ⁵D₀-⁷F₂ transition, which indicates that Eu³⁺ was substituted for Sr²⁺ site.     

Radioluminescence of SrAl2O4:Ln (Ln = Eu, Sm, Dy) phosphor ceramic

Phosphors for radiation detection require efficient energy transfer from the ionization track to the luminescent centers. In this work, the radioluminescence (RL) spectra of SrAl₂O₄ phosphor ceramics doped with individual trivalent rare earth element (REE) ions (Sm, Eu and Dy) are reported at the room temperature. Although there is some intrinsic UV/blue emission from the host lattice, the dominant signals are from the rare-earth sites, with signals characteristic of the REE²⁺ and REE³⁺ states. The shapes of the emission bands are different for each dopant. The sharp emission properties show that the SrAl₂O₄ is a suitable host for rare-earth ion doped phosphor material.     

Photoluminescence properties of RE-activated Na3GdP2O8 (RE = Tb, Dy, Eu, Sm) under VUV excitation

RE³⁺-activated monoclinic Na₃GdP₂O₈ (RE³⁺ = Tb³⁺, Dy³⁺, Eu³⁺, Sm³⁺) phosphors have been synthesized by a solid-state reaction method. Their photoluminescence properties in the vacuum ultraviolet (VUV) region were investigated. By analyzing their excitation spectra, the host-related absorption band was determined to be around 166 nm. The f-d transition bands and the charge transfer bands for Na₃GdP₂O₈:RE³⁺ (RE³⁺ = Tb³⁺, Dy³⁺, Eu³⁺, Sm³⁺) were assigned and corroborated. For the sample Na₃GdP₂O₈:5%Tb³⁺, the strong bands at around 202 and 221 nm are assigned to the 4f-5d spin-allowed transitions and the weak band at 266 nm is related to the spin-forbidden transition of Tb³⁺. For Na₃GdP₂O₈:5%Dy³⁺, the broad band at 176 nm could be related to the f-d transitions of Dy³⁺ and the O²⁻ → Dy³⁺ charge transfer band (CTB) besides the host-related absorption. In the excitation spectrum of Eu³⁺ doped sample, the O²⁻ → Eu³⁺ CTB is observed to be at 245 nm. For the Sm³⁺ doped sample, the O²⁻ → Sm³⁺ CTB is not distinguished obviously and is overlapped with the host-related absorption band.     

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.     

Influence of Ce on the luminescence properties of Er/Yb:YVO4 crystals

YVO₄ single crystals doped with Ce³⁺, Er³⁺ and Yb³⁺ ions were grown by the Czochralsski technology. The luminescence properties of Er³⁺/Yb³⁺:YVO₄ single crystals with different concentration of Ce³⁺ were studied, and the energy transfer mechanism between Er³⁺, Yb³⁺ and Ce³⁺ was discussed based on their energy level properties. The branching ratios of the ⁴I_11/2 → ⁴I_13/2 transition in different samples were calculated. The results indicate that codopants of Ce³⁺ greatly enhance the population rate of the ⁴I_13/2 level due to the fast resonant energy transfer between Er³⁺ and Ce³⁺, i.e., ⁴I_11/2(Er³⁺) + ²F_7/2(Ce³⁺) → ⁴I_13/2(Er³⁺) + ²F_5/2(Ce³⁺).