Fluorescence improvement of Ba1.3Ca0.7SiO4:Eu,Mn phosphors via Dy addition and their color-tunable properties

A series of novel single-phase white phosphors Ba_1.3Ca_0.69−x−ySiO₄:0.01Eu²⁺,xMn²⁺, yDy³⁺ were synthesized by the solid-state method. The excitation spectra of these phosphors exhibit a broad band in the range of 260–410 nm, which can meet the application requirements for near-UV LED chips (excited at 350–410 nm). The emission spectra consist of two broad bands positioned around 455 nm and 596 nm, which are assigned to 5d→4f transition of Eu²⁺, and ⁴T₁→⁶A₁ transition of Mn²⁺, respectively. The luminescence intensity of phosphors enhances obviously by doping Dy³⁺ ions, and the intensity of two bands reaches an optimum when Dy³⁺ amounts to 2 mol%. In addition, thermoluminescence investigation of phosphor was conducted, getting two shallow trap defects with activation energy of 0.43 eV and 0.45 eV, which demonstrates the energy transfer mechanism of Dy–Eu through the process of hole and electron traps. By precisely tuning the Mn²⁺ content, an optimized white light with color rendering index (CRI) of R_a=84.3%, correlated color temperature (CCT) of T_c=8416 K and CIE chromaticity coordinates of (0.2941, 0.2937) is generated. The phosphor could be a potential white phosphors for near-UV light emitting diodes.     

Preparation of Ca4Mg5(PO4)6:Eu,Mn phosphor and its photoluminescence properties

Eu²⁺ and Mn²⁺ singly doped and Eu²⁺/Mn²⁺-codoped Ca₄Mg₅(PO₄)₆ phosphors were synthesized via combustion synthesis. Mn²⁺-singly doped Ca₄Mg₅(PO₄)₆ phosphor exhibits a single red emission in the wavelength range of 500–700 nm due to the ⁴T₁(⁴G)→⁶A₁(⁶S) transition of Mn²⁺. Eu²⁺/Mn²⁺ co-doped phosphor emits two distinctive luminescence bands: a blue one centered at 442 nm originating from Eu²⁺ and a broad red-emitting one peaked at 609 nm from Mn²⁺. Energy transfers from Eu²⁺ to Mn²⁺ were discovered by directly observing significant overlap of the excitation spectrum of Mn²⁺ and the emission spectrum of Eu²⁺ as well as the systematic relative decline and growth of emission bands of Eu²⁺ and Mn²⁺, respectively. Based on the principle of energy transfer, the relative intensities of blue and red emission could be tuned by adjusting the contents of Eu²⁺ and Mn²⁺.     

The doping concentration dependent tunable yellow luminescence of Sr5(PO4)2(SiO4):Eu

Color tunable yellow-emitting phosphors of Sr_5−5xEu_5x(PO₄)₂SiO₄ (x = 0.05-0.15) were prepared by conventional solid-state reaction method. The X-ray powder diffraction patterns, the photoluminescence excitation and emission spectra were measured. The main excitation bands of the phosphors locate at a broad band extending from 300 to 500 nm, which can match the emission of ultraviolet- and blue-emitting diode chips. The tunable luminescence color was realized by the changing Eu²⁺ doping in Sr₅(PO₄)₂SiO₄. The structure and luminescence properties were investigated. Sr_5−5x(PO₄)₂SiO₄:Eu_5x displays two typical luminescence centers, which originate from two different Sr²⁺ (Eu²⁺) sites in the host. The site-occupation, the luminescence intensity and energy transfer between the Eu²⁺ ions occupying two different crystallographic Sr²⁺ sites were discussed on the base of the luminescence spectra and crystal structure. This is helpful to improve this phosphor for a potential application as a white light emitting diode phosphor.     

Photoluminescence properties of Eu-activated BaCa2Al8O15 nanophosphors

A new blue-emitting nanophosphor of Eu²⁺-activated BaCa₂Al₈O₁₅ was synthesized by the Pechini method. The phosphors were investigated by X-ray powder diffraction (XRD) measurement and confirmed to be a pure crystalline phase of BaCa₂Al₈O₁₅. The photoluminescence excitation and emission spectra, the luminescence decay and the color coordinates were taken to investigate the luminescence characteristics. The dependence of luminescence intensities BaCa₂Al₈O₁₅:Eu²⁺ on the doping concentrations was investigated. This nanophosphor can be efficiently excited by UV light and presents bright blue luminescence. Under the same conditions, the light yield of BaCa₂Al₈O₁₅:Eu²⁺ is about 1.2 times higher than that of blue-emitting phosphor BaMgAl₁₀O₁₇:Eu²⁺. Eu²⁺-activated BaCa₂Al₈O₁₅ nanophosphor exhibits the long-lasting phosphorescence, which was analyzed by measuring the afterglow decay curves. The co-doped Eu³⁺ ions and some defects were suggested to be the possible trap-centers.     

Luminescent properties of a novel afterglow phosphor Sr3Al2O5Cl2:Eu,Ce

A series of Eu²⁺ and Ce³⁺ doped/co-doped Sr₃Al₂O₅Cl₂ afterglow phosphors that presented various bright colors were successfully synthesized via high temperature solid state reaction. The structure and luminescence properties of the obtained samples were characterized by X-ray powder diffraction (XRD), photoluminescence (PL) spectra and decay curves as well as the thermoluminescence (TL) glow curves. The XRD results showed that all the phase could be indexed to the orthorhombic structure with the space group P2₁2₁2₁. After being exposed to a 254 nm or 365 nm mercury lamp, blue/yellow-orange afterglow emissions with broad bands peaking around 620 nm/435 nm, which were ascribed to the characteristic 4f⁶5d–4f⁷/5d¹–4f¹ transitions of Eu²⁺/Ce³⁺, could be observed in phosphors of Sr₃Al₂O₅Cl₂:Eu²⁺/Sr₃Al₂O₅Cl₂:Ce³⁺, respectively. Because of the overlap spectral range between the Sr₃Al₂O₅Cl₂:Eu²⁺ and Sr₃Al₂O₅Cl₂:Ce³⁺ phosphors, the energy transfer (ET) from Ce³⁺ to Eu²⁺ occurred. The related ET process was discussed in detail. Moreover, the incorporation of Ce³⁺ could significantly prolong the afterglow duration of Sr₃Al₂O₅Cl₂:Eu²⁺ phosphor, which was due to the increase of trap concentration. Consequently, 6 h of the afterglow duration could be observed in Sr₃Al₂O₅Cl₂:1.0%Eu²⁺, 0.5%Ce³⁺ sample, exhibiting much longer than that of Sr₃Al₂O₅Cl₂: 1.0%Eu²⁺ (3 h). From the afterglow decay curves and the fitting results, the optimal concentration of Ce³⁺ for the enhanced afterglow property was experimentally determined to be 0.5%.     

Luminescent properties of Sr2B2O5: Tm,Na blue phosphor

A novel blue phosphor, Sr₂B₂O₅: Tm³⁺, Na⁺ for white light-emitting diodes (W-LEDs) was prepared by solid-state synthesis and its structure and luminescence properties were investigated. This phosphor can be effectively excited within the broad near ultraviolet (NUV) wavelength region, from 340 nm to 370 nm, and exhibits a satisfactory blue performance. The emission peaks are observed at 457 nm (blue) and 475 nm (blue), due to the respective transitions of ¹D₂→³F₄ and ¹G₄→H₆. Seven mole percent of doping concentration of Tm³⁺ was shown to be optimal. Concentration quenching occurs when Tm³⁺ concentration is beyond 7 mol%, its mechanism being explained by dipole–dipole interaction of Tm³⁺ and being confirmed by decay property measurements. We have made a deep analysis on the effect of charge compensation reagent on luminescence intensity. Good blue emissions with the CIE chromaticity coordinates (0.173, 0.165) could be achieved. Our results suggest that the Sr₂B₂O₅: Tm³⁺, Na⁺ phosphor is a potential blue-emitting material.     

Zero-thermal-quenching of LiAl5O8: Eu2+, Mn2+ phosphors by energy transfer and defects engineering

The photoluminescence behavior of inorganic phosphors is generally influenced by thermal stability, which determines the luminescence efficiency of the corresponding devices. Here, a series of Eu²⁺, Mn²⁺ co-doped LiAl₅O₈ blue-green-emitting phosphors with thermal robust are successfully fabricated. The concentration-dependent emission spectra and the decay curves of the as-obtained LiAl₅O₈: Eu²⁺, Mn²⁺ samples manifest the occurrence of the energy transfer from Eu²⁺ to Mn²⁺ ions via dipole-dipole interaction, and the corresponding emitted colors are gradually modulated from blue to green under the excitation of 310 nm. Moreover, the zero-thermal-quenching luminescence is observed when the operation temperature is up to 423 K, which is attributed to the energy release from the trapping centers to emitting centers (Eu²⁺ and Mn²⁺) at high temperature. Furthermore, a warm white light-emitting diodes (WLEDs) device with correlated color temperature of 5061 K, a color rendering index of 80.6 and long-term stability is fabricated by combining UV LED chip (λ_ex = 310 nm), as-obtained LiAl₅O₈: Eu²⁺, Mn²⁺ phosphor, commercially available red phosphor and green phosphor. These results prove the potential application of the as-obtained LiAl₅O₈: Eu²⁺, Mn²⁺ phosphor for UV-pumped WLEDs devices.     

Investigation of Eu2+ luminescence in barium tetraphosphate Ba3P4O13 polycrystalline ceramics

In this paper, Ba₃P₄O₁₃:Eu²⁺ phosphor was synthesized by a solid-state reaction. The photoluminescence (PL) emission spectrum and luminescence decay kinetics confirm that the doped Eu²⁺ ions can occupy two different Ba²⁺ sites. The PL excitation spectrum shows a broad band matching well with the emission of near-UV chip. Ba₃P₄O₁₃:Eu²⁺ is a promising phosphor for near-UV chip excited white LEDs. The doped Eu³⁺ ions can also be reduced to Eu²⁺ ions in air atmosphere at high temperature. Charge compensation mechanism is applied to explain this kind of abnormal reduction.     

Photoluminescence properties of NUV light excited Ba(Mg1/3Nb2/3)O3:Eu3+ red phosphor with high color purity

In this work, a new red phosphor with high color purity, Eu³⁺ ions doped Ba(Mg_1/3Nb_2/3)O₃ phosphor has been prepared by wet chemical method. The structure analysis suggests BMN:x%Eu phosphors have a hexagonal phase and Ba²⁺ ions are replaced by Eu³⁺ ions in BMN. Upon excitation of NUV light, the BMN:x%Eu phosphors emit strong red light around 615?nm, derived from the ⁵D₀-⁷F₂ transition of Eu³⁺ ions. The relationship between luminescent properties and structure of BMN:x%Eu was discussed. The Judd-Ofelt intensity parameters (Ω₂, Ω₄) were calculated to analyze the asymmetry of the Eu³⁺ ions site occupancy further, and the quantum efficiency of BMN:3%Eu was found to be 77.26%. In addition, the decay curve indicates the decay time(τ) of BMN:3%Eu is determined to be 1.34?ms and Eu³⁺ ions occupy only one type of site. The CIE chromaticity coordinate (0.656,0.344) of BMN:3%Eu is quite close to the red phosphors standard value (0.670, 0.330), which indicates BMN:x%Eu can be a suitable red phosphor used in NUV-based white LEDs.     

High luminescent brightness and thermal stability of red emitting Li3Ba2Y3(WO4)8:Eu3+ phosphor

A series of Li₃Ba₂Y_3−x(WO₄)₈:xEu³⁺ (x=0.1, 1, 1.5, 2 and 2.8) phosphors were synthesized by a high temperature solid-state reaction method. Under the excitation of near ultraviolet (NUV) light, the as-prepared phosphor exhibits intense red luminescence originating from the characteristic transitions of Eu³⁺ ions, which is 1.8 times as strong as the commercial Y₂O₂S:Eu³⁺ phosphor. The optimal doping concentration of Eu³⁺ ions here is confirmed as x=1.5. The electric dipole-quadrupole (D-Q) interaction is deduced to be responsible for concentration quenching of Eu³⁺ ions in the Li₃Ba₂Y₃(WO₄)₈ phosphor. The analysis of optical transition and Huang-Rhys factor reveals a weak electron-phonon coupling interaction. The temperature-dependent emission spectra also indicate that the as-prepared Li₃Ba₂Y₃(WO₄)₈:Eu³⁺ phosphor has better thermal stability than that of the commercial Y₂O₂S:Eu³⁺ phosphor. Therefore, our results show that the as-prepared Li₃Ba₂Y₃(WO₄)₈:Eu³⁺ phosphor is a promising candidate as red emitting component for white light emitting diodes (LEDs).     

A reddish orange stoichiometric phosphor LiEu(PO3)4 for white light-emitting diodes

Stoichiometric phosphors LiGd_1−xEu_x(PO₃)₄(x=0, 0.2, 0.4, 0.6, 0.8, 1.0) were synthesized via traditional solid state reactions. The X-ray powder diffraction measurements show that all prepared samples are isostructural with LiNd(PO₃)₄. Eu³⁺ doped phosphors can emit intense reddish orange light under the excitation of near ultraviolet light from 370 to 410 nm. The strongest two at 591 and 613 nm can be attributed to the transitions from excited state ⁵D₀ to ground states ⁷F₁ and ⁷F₂, respectively. The typical chromaticity coordinates (x=0.620, y=0.368) of Eu³⁺ doped phosphors are in red area. The recorded absorbance spectra indicate that there is effective absorbance in the near UV region for all Eu³⁺ doped samples. Present research indicates that LiGd_1–xEu_x(PO₃)₄ is a promising phosphor for white light-emitting diodes.     

Garnet-based red emitting phosphors Li6MLa2Nb2O12: Eu (M=Ca,Sr, Ba): Photoluminescence improvement by changing crystal lattice

A series of novel red emitting phosphors Li₆M(La_1−xEu_x)₂Nb₂O₁₂ (M=Ca, Sr, Ba; 0≤x≤0.3) were synthesized by solid state reaction, and their structures and photoluminescence properties were investigated in detail. The excitation spectrum of Li₆M(La_1−xEu_x)₂Nb₂O₁₂ revealed two mainly excitation bands at 393 nm and 464 nm, which match well with the two popular emissions from near-UV and blue LED chips. Upon the 464 nm light excitation, Li₆MLa₂Nb₂O₁₂:Eu³⁺ phosphors exhibit a red emission centered at 608 nm, originated from the ⁵D₀–⁷F₂ transition of Eu³⁺ ions. The Eu³⁺ surrounding crystal lattice environment in the garnet-based host was changed by altering the c sites element with different radii alkaline earth Ba, Sr, and Ca. The evident photoluminescence enhancement was observed in Li₆M(La_1−xEu_x)₂Nb₂O₁₂ phosphors with the decreasing of the c sites ionic radius. The emission intensity of the optimized Li₆Ca(La_0.8Eu_0.2)₂Nb₂O₁₂ (λ_exc=464 nm) phosphor is about two times higher than that of Y₂O₃:Eu³⁺ (λ_exc=467 nm) under blue light excitation. In addition, the quenching mechanism and the relationship between the structure and photoluminescence property were also discussed.     

Luminescence and structure of Eu2+-doped Ba2CaMg2Si6O17

Eu²⁺-activated Ba₂CaMg₂Si₆O₁₇ phosphors were synthesized by conventional solid-state reaction. The phase formation was confirmed by X-ray powder diffraction measurement. The photoluminescence excitation and emission spectra were investigated. The phosphor presents blue-emitting luminescence. The crystallographic sites of Eu²⁺ ions in Ba₂CaMg₂Si₆O₁₇ host were discussed on the base of luminescence properties and the crystal structure. The lightly Eu²⁺-doped sample shows one luminescence center for the Eu²⁺ ions on Ba²⁺ sites, while there are two luminescence centers for the Eu²⁺ ions on both the Ba and Ca sites in heavily Eu²⁺-doped sample. The dependence of luminescence intensity on temperatures and the activation energy (ΔE) for the thermal quenching were reported. The phosphor shows an excellent thermal stability on temperature quenching because of the special layered structure of Ba²⁺ ions in the interlayer between SiO₄ layers.     

Structure,magnetic and electrical transport properties of the perovskites Sm1−xCaxFe1−xMnxO3

The structure of series Sm_1−xCa_xFe_1−xMn_xO₃ (0.0 ≤ x ≤ 1.0) compounds was investigated. The lattice parameters increase with coupled substitution Sm³⁺ by Ca²⁺ and Mn⁴⁺ for Fe³⁺. The variation of parameter, c, is larger than that of a and b, respectivly. The detailed analysis of magnetic properties of series Sm_1−xCa_xFe_1−xMn_xO₃ (0.1 ≤ x ≤ 0.9) shows that local magnetic interaction between Fe³⁺ and Fe³⁺ and Mn⁴⁺ and Mn⁴⁺ at below magnetic transition temperature is antiferromagnetic. Above magnetic transition temperature the presence of large magnetic cluster is proposed and the sizes of magnetic clusters decrease with Mn⁴⁺. The electrical transport behaviors related with small polaron hopping and variable range hopping models.     

Structural and luminescence properties of RE (RE = Eu, Tb):(MgCa)2Bi4Ti5O20 ceramics

Rare-earth ions (Eu³⁺, Tb³⁺) activated magnesium calcium bismuth titanate [(MgCa)₂Bi₄Ti₅O₂₀] ceramics were prepared by conventional solid state reaction method for their structural and luminescence properties. By using XRD patterns, the structural properties of ceramic powders have been analyzed. Emission spectrum of Eu³⁺:(MgCa)₂Bi₄Ti₅O₂₀ ceramic powder has shown strong red emission at 615 nm (⁵D₀ → ⁷F₂) with an excitation wavelength λ_exci = 393 nm and Tb³⁺:(MgCa)₂Bi₄Ti₅O₂₀ ceramic powder has shown green emission at 542 nm (⁵D₄ → ⁷F₅) with an excitation wavelength λ_exci = 376 nm. In addition, from the measurements of scanning electron microscopy (SEM), Fourier transform-infrared (FTIR) and energy dispersive X-ray analysis (EDAX) results the morphology, structure and elemental analysis of these powder ceramics have been studied.     

Enhanced luminescence of novel Ca3B2O6:Dy phosphors by Li-codoping for LED applications

The Ca_3−xB₂O₆:xDy³⁺ (0.0 ≤ x ≤ 0.105) and Ca_2.95−yDy_0.05B₂O₆:yLi⁺ (0 ≤ y ≤ 0.34) phosphors were synthesized at 1100 °C in air by solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), photoluminescence excitation (PLE) and photoluminescence (PL) spectra. The PLE spectra show the excitation peaks from 300 to 400 nm is due to the 4f-4f transitions of Dy³⁺. This mercury-free excitation is useful for solid state lighting and light-emitting diodes (LEDs). The emission of Dy³⁺ ions upon 350 nm excitation is observed at 480 nm (blue) due to the ⁴F_9/2 → ⁶H_15/2 transitions, 575 nm (yellow) due to ⁴F_9/2 → ⁶H_13/2 transitions and a weak 660 nm (red) due to ⁴F_9/2 → ⁶H_11/2 emissions, respectively. The optimal PL intensity of the Ca_3−xB₂O₆:xDy³⁺ phosphors is found to be x = 0.05. Moreover, the PL results from Ca_2.95−yDy_0.05B₂O₆:yLi⁺ phosphors show that Dy³⁺ emissions can be enhanced with the increasing codopant Li⁺ content till y = 0.22. By simulation of white light, the CIE of the investigated phosphors can be tuned by varying the content of Li⁺ ions, and the optimal CIE value (0.300, 0.298) is realized when the content of Li⁺ ions is y = 0.22. All the results imply that the Ca_2.95−yDy_0.05B₂O₆:yLi⁺ phosphors could be potentially used as white LEDs.     

Enhanced photoluminescence property of Dy co-doped BaAl2O4:Eu green phosphors

Eu²⁺-doped BaAl₂O₄ green phosphors were prepared by a conventional solid-state reaction and the effects of Dy³⁺ co-doping on the photoluminescence property were investigated. The phosphors were characterized by X-ray powder diffraction (XRD), fluorescence spectroscopy, field-emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS). XRD showed that all prepared samples exhibited a hexagonal BaAl₂O₄ phase. Fluorescence spectroscopy showed that the photoluminescence efficiency increased with increasing Eu²⁺ concentration until 3 mol% then decreased at higher concentrations due to concentration quenching effect. Moreover, Dy³⁺ co-doping increased the photoluminescence efficiency of the Eu²⁺-doped BaAl₂O₄ phosphor.     

Synthesis,structure and luminescence properties of a novel red fluorescent material Ba2MgB2O6:Eu3+

The crystal structure of Ba_2-xMgB₂O₆:xEu³⁺ phosphors, synthesized using a solid-state reaction, have been confirmed by X-ray diffraction analysis. This study focuses on the site occupancy preference of Eu³⁺ ions within the matrix, which was determined using bond energy theory, fluorescent spectra, and a consideration of energy transport and decay curves. The impact of Eu³⁺ ion concentration on luminescence has been assessed, and an optimal concentration (x = 0.22) identified. The critical distance, R_c was 9.6 Å, with a calculated θ value of 19.67, indicating that quadrupole-quadrupole interaction plays a critical role in the quenching Ba_2-xMgB₂O₆:xEu³⁺ phosphors. The Ba_2-xMgB₂O₆:xEu³⁺ phosphors exhibited a color purity of 99.26%, and a quantum efficiency of 49.68%. The activation energy Ea was determined to equal 0.2987 eV. The results have established Ba_1.78MgB₂O₆:0.22Eu³⁺ as a red fluorescent powder with high quantum efficiency and a millisecond fluorescence lifetime.     

Solvothermal synthesis of red and green emitting Ca1.65Sr0.35SiO4:Eu and Ca1.65Sr0.35SiO4:Eu phosphors for solid-state lighting applications

A novel and facile synthetic approach has been trialed, and attempted with success in the preparation of two phosphors namely, a red emitting CaSrSiO₄:Eu³⁺ and a green emitting CaSrSiO₄:Eu²⁺. These phosphors were successfully synthesized using a simple co-precipitating solvo-thermal strategy wherein tetraethyl orthosilicate (TEOS) as silica source and the acetate precursors of strontium (Sr²⁺), calcium (Ca²⁺) and europium (Eu³⁺) are utilized. The material so obtained is subjected to an extensive photoluminescence behavior study. The concentration of the dopant (Eu³⁺and Eu²⁺) plays a significant role in the determination of photoluminescence behavior and hence a systematic and in-depth experimental studies were done and the results are synchronized. On interpretation of the output, it came to light that an intense emission signals sparked in the red region (590 and 615 nm) in the case of phosphor doped with Eu³⁺, which is excited under near ultra violet (395 nm) and blue (466 nm) region. In case of the CaSrSiO₄ sample doped with Eu²⁺_, an intense broad green signal (~510 nm) is obtained under the excitation range of 350–430 nm. The results obtained are quite encouraging and made a strong confirmation as, the solvo-thermally synthesized CaSrSiO₄, which is activated by the dopants namely Eu³⁺ and Eu²⁺ possesses an immense potential and it is exactly tapped by the adopted methodology. Despite its strong impact, it will also assure a strong revolution in the fabrication and thus the commercialization of white LEDs as both the red and green emitting phosphor.     

The luminescence and structural characteristics of Eu-doped NaBaPO4 phosphor

Eu³⁺-doped NaBaPO₄ was prepared by a high-temperature solid-state reaction. The phase formation was confirmed by X-ray powder diffraction measurements. The laser site-selective excitation and emission spectra have been investigated in the ⁵D₀ → ⁷F₀ region by using a pulsed, tunable and narrowband dye laser. The excitation spectra corresponding to the ⁷F₀ → ⁵D₀ transition consist of two transitions at 579.6 nm Eu(I) and 578.9 nm Eu(II), indicating the Eu³⁺ ions occupy two crystallographic sites of Ba²⁺ ions. The decay lifetimes of the two Eu³⁺ sites were measured. Two crystallographic sites for Eu³⁺ ions doped in NaBaPO₄ lattice were assigned from the luminescence characteristic and structure features. Meanwhile, the charge compensation mechanism of Eu³⁺ doping in NaBaPO₄ was discussed.