Enhanced luminescence and white light emission from Eu3+‐co‐doped K3Ca2(SO4)3Cl:Dy3+ phosphor with near visible ultraviolet excitation for white LEDs

The luminescent properties of europium (Eu)‐ and dysprosium (Dy)‐co‐doped K₃Ca₂(SO₄)₃Cl halosulfate phosphors were analyzed. This paper reports the photoluminescence (PL) properties of K₃Ca₂(SO₄)₃Cl microphosphor doped with Eu and Dy and synthesized using a cost‐effective wet chemical method. The phosphors were characterized by X‐ray diffraction and scanning electron microscopy. The CIE coordinates were calculated to display the color of the phosphor. PL emission of the prepared samples show peaks at 484 nm (blue), 575 nm (yellow), 594 nm (orange) and 617 nm (red). The emission color of the Eu,Dy‐co‐doped K₃Ca₂(SO₄)₃Cl halophosphor depends on the doping concentration and excitation wavelength. The addition of Eu in K₃Ca₂(SO₄)₃Cl:Dy greatly enhances the intensity of the blue and yellow peaks, which corresponds to the ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transitions of Dy³⁺ ions (under 351 nm excitation). The Eu³⁺/Dy³⁺ co‐doping also produces white light emission for 1 mol% of Eu³⁺, 1 mol% of Dy³⁺ in the K₃Ca₂(SO₄)₃Cl lattice under 396 nm excitation, for which the calculated chromaticity coordinates are (0.35, 0.31). Thus, K₃Ca₂(SO₄)₃Cl co‐doped with Eu/Dy is a suitable candidate for NUV based white light‐emitting phosphors technology. Copyright © 2014 John Wiley & Sons, Ltd.     

A new Pr3+‐activated molybdate‐based phosphor for application to white LEDs with blue excitation

The novel red‐emitting phosphors K_xSr_1?2xMoO₄:Pr³⁺_x (0.00 ≤ x ≤ 0.04) were prepared by solid‐state reaction. The crystallization and particle sizes of samples were investigated by powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). TEM images were in good agreement with the theoretical calculation data from the XRD patterns. Photoluminescence analysis indicated that there were three excitation peaks under 430–500 nm, and all samples showed the intensely red emission at 648 nm corresponding to the ³P₀ → ³F₂ transition of Pr³⁺. The concentrations of doping ions, temperature and polyethylene glycol in the phosphor system can significantly influence the intensity of the red emission. The photoluminescence spectral intensity reached its maximum at x = 0.02. The results showed that the investigated phosphor is a potential red phosphor for white light‐emitting diodes. Copyright © 2010 John Wiley & Sons, Ltd.     

Eu3+‐activated Y2MoO6: a narrow band red‐emitting phosphor with strong near‐UV absorption

Near‐UV excited narrow line red‐emitting phosphors, Eu³⁺‐activated Y₂MoO₆ systems, were synthesized using a simple molten salt reaction. The structure and photoluminescence characteristics were investigated using X‐ray powder diffraction, UV–Vis absorption and fluorescent spectrophotometry. The excitation spectra show strong broad‐band absorptions in the near‐UV to blue light regions which match the radiation of near‐UV light‐emitting diode chips well. Under excitation of either near‐UV or blue light, intense red emission with a main peak of 611 nm is observed, ascribed to the ⁵D₀–⁷F₂ transition of Eu³⁺ ions; the optimal doping concentration is 20 mol%. The chromaticity coordinates (x = 0.65, y = 0.34) of the as‐obtained phosphor are very close to the National Television Standard Committee standard values (x = 0.67, y = 0.33). All these characteristics suggest that this material is a promising red‐emitting phosphor candidate for white‐LEDs based on near‐UV LED chips. Copyright © 2012 John Wiley & Sons, Ltd.     

Sr2ZnWO6:Eu3+,Bi3+,Li+: a potential white‐emitting phosphor for near‐ultraviolet white light‐emitting diodes

A series of Sr₂ZnWO₆ phosphors co‐doped with Eu³⁺, Bi³⁺ and Li⁺ were prepared using the Pechini method. The samples were tested using X‐ray diffraction and luminescence spectroscopy. The results show that the samples can be effectively excited by near‐ultraviolet (UV) and UV light. The introduction of Bi³⁺ and Li⁺ significantly enhances the fluorescence emission of Sr₂ZnWO₆:Eu³⁺ and changes the light emitted by the phosphors from bluish‐green to white. When excited at 371 nm, Sr_2–x–zZn_1–yWO₆:xEu³⁺,yBi³⁺,zLi⁺ (x = 0.05, y = 0.05, z = 0.05, 0.1 and 0.15) samples emit high‐performance white light. Intense red–orange emission is also observed when excited by UV light. The obtained phosphor is a potential white‐emitting phosphor that could meet the needs of excitation sources with near‐UV chips. In addition, this phosphor might have promising application as a red–orange emitting phosphor for white light‐emitting diodes based on UV light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Phosphors Ba2LaTaO6:Mn4+ and its alkali metal charge compensation for plant growth illumination

A series of Mn⁴⁺-doped and Mn⁴⁺,K⁺-co-doped Ba₂LaTaO₆ (BLT) double-perovskite phosphors was synthesized using a high-temperature solid-state reaction. The phase purity and luminescence properties were also studied. The optimum doping concentration of Mn⁴⁺ and K⁺ was obtained by investigating the photoluminescence excitation spectra and photoluminescence emission spectra. The comparison of BLT:Mn⁴⁺ phosphors with and without K⁺ ions shows that the photoluminescence intensity of K⁺-doped phosphors was greatly enhanced. This is because there was a charge difference when Mn⁴⁺ ions were doped with Ta⁵⁺ ions in BLT. Mn⁴⁺–K⁺ ion pairs were formed after doping K⁺ ions, which hinders the nonradiative energy transfer between Mn⁴⁺ ions. Therefore, the luminescence intensity, quantum yield, and thermal stability of phosphors were enhanced. The electroluminescence spectra of BLT:Mn⁴⁺ and BLT:Mn⁴⁺,K⁺ were measured. The spectra showed that the light emitted from the phosphors corresponded well with chlorophyll a and phytochrome P_R. The results show that the BLT:Mn⁴⁺,K⁺ phosphors had good luminescence properties and application prospects and are ideal materials for plant-illuminated red phosphors.     

Optical characterization and the energy level scheme for Ce3+‐doped BaY2Si3O10 blue‐emitting phosphor

A series of Ce³⁺‐activated blue‐emitting phosphors BaY₂Si₃O₁₀ (BYSO) was designed and synthesized by a conventional solid‐state method. Upon ultraviolet light (250–370 nm) excitation, the obtained phosphors showed an intense blue emission band centered at 400–427 nm depending on doping concentration, and corresponding to the 5d→4f transition of Ce³⁺. The effects of doping concentration on crystal structure, emitting color, photoluminescence and photoluminescence excitation spectra, as well as the concentration quenching mechanism were studied in detail. The optimal doping concentration of Ce³⁺ in this phosphor was demonstrated to be about 0.75% and the concentration quenching mechanism can be ascribed to electric dipole–dipole interactions with a critical distance of ~38 Å. These fine luminescence properties indicate that BYSO:Ce³⁺ may be a potential blue phosphor for full‐color ultra‐violet (UV) white light emitting diodes (WLEDs).     

Photoluminescence in K3Ca2(SO4)3Cl‐doped Eu3+ phosphor

In this article we report Eu³⁺ luminescence in novel K₃Ca₂(SO₄)₃Cl phosphors prepared by wet chemical methods. The Eu³⁺ emission was observed at 594 nm and 615 nm, keeping the excitation wavelength constant at 396 nm nearer to light‐emitting diode excitation, Furthermore, phosphors were characterized by X‐ray diffraction for the confirmation of crystallinity. The variation of the photoluminescence intensity with impurity concentration has also been discussed. Thus, prominent emission in the red region makes prepared phosphors more applicable for white light‐emitting diodes. Copyright © 2013 John Wiley & Sons, Ltd.     

Photoluminescence properties of LiBaPO4:M3+ phosphor for near‐UV light‐emitting diode (M = Eu and Dy)

A novel phosphor LiBaPO₄ doped with rare earths Eu and Dy prepared by high temperature solid‐state reaction method is reported. The phosphors were characterized by X‐ray powder diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL). The emission and excitation spectra of these materials were measured at room temperature with a spectrofluorophotometer. The excitation spectra of LiBaPO₄:Eu³⁺ phosphor can be efficiently excited by 394 nm, which is matched well with the emission wavelength of near‐UV light‐emitting diode (LED) chip. PL properties of Eu³⁺‐doped LiBaPO₄ exhibited the characteristic red emission coming from ⁵D₀ → ⁷ F₁ (593 nm) and ⁵D₀ → ⁷ F₂ (617 nm) electronic transitions with color co‐ordinations of (0.680, 0.315). The results demonstrated that LiBaPO₄:Eu³⁺ is a potential red‐emitting phosphor for near‐UV LEDs. Emission spectra of LiBaPO₄:Dy³⁺ phosphors showed efficient blue (481 nm) and yellow (574 nm) bands, which originated from ⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2 transitions of the Dy³⁺ ion, respectively. The 574 nm line is more intense than the 481 nm lines, which indicates that the site Dy³⁺ is located with low symmetry. This article summarizes fundamentals and possible applications of optically useful inorganic phosphates with visible photoluminescence of Eu³⁺ and Dy³⁺ ions. Copyright © 2015 John Wiley & Sons, Ltd.     

Tunable white light emission from single‐phased Li2SrSiO4:Dy3+ phosphors by co‐doping with Eu3+

A series of single‐phase full‐color emitting Li₂Sr_1−x−ySiO₄:xDy³⁺,yEu³⁺ phosphors were synthesized by solid‐state reaction and characterized by X‐ray diffraction and photoluminescence analyses. The samples showed emission peaks at 488 nm (blue), 572 nm (yellow), 592 nm (orange) and 617 nm (red) under 393 nm excitation. The photoluminescence excitation spectra, comprising the Eu–O charge transfer band and 4f–4f transition bands of Dy³⁺ and Eu³⁺, range from 200 to 500 nm. The Commission Internationale de I'Eclairage chromaticity coordinates for Li₂Sr_0.98−xSiO₄:0.02Dy³⁺,xEu³⁺ phosphors were simulated. By manipulating Eu³⁺ and Dy³⁺ concentrations, the color points of Li₂Sr_1−x−ySiO₄:xDy³⁺,yEu³⁺ were tuned from the greenish‐white region to white light and eventually to reddish‐white region, demonstrating that a tunable white light can be obtained by Li₂Sr_1−x−ySiO₄:xDy³⁺,yEu³⁺ phosphors. Li₂Sr_0.98−xSiO₄:0.02Dy³⁺, xEu³⁺ can serve as a white‐light‐emitting phosphor for phosphor‐converted light‐emitting diode. Copyright © 2014 John Wiley & Sons, Ltd.     

Zn‐doped CaTiO3:Eu3+ red phosphors for enhanced photoluminescence in white LEDs by solid‐state reaction

Zn‐doped CaTiO₃:Eu³⁺ red phosphors for enhanced photoluminescence in white light‐emitting diodes (LEDs) were synthesized by a solid‐state method. The structure and morphology of the obtained phosphor samples were observed by X‐ray diffraction (XRD) and scanning electron microscopy (SEM), and the impact of Ca, Zn and Eu content on their photoluminescence properties was studied. The results indicated that Zn not only participates in the formation of defects in suitable lattice matrices but also has a role in flux in the transformation from ZnO to Zn₂TiO₄, which is beneficial for the enhancement of photoluminescence properties. Photoluminescence test data showed that the Zn‐doped phosphor is excited efficiently by near‐ultraviolet (NUV) light at wavelengths around 398 nm and emits an intense red light with a broad peak around 616 nm corresponding to the ⁵D₀→⁷F₂ transition of Eu³⁺. The intensity of this phosphor emission is three times stronger than that without Zn‐doping. Furthermore, this phosphor has very good thermal stability, high color purity and a low sintered temperature, all of which suggest its potential as a promising red phosphor for white LEDs. Copyright © 2015 John Wiley & Sons, Ltd.     

Microwave‐assisted sintering synthesis of greenish‐yellow emitting Sr2SiO4:Eu2+ phosphors

Europium ion (Eu²⁺) doped Sr₂SiO₄ phosphors with greenish‐yellow emission were synthesized using microwave‐assisted sintering. The phase structure and photoluminescence (PL) properties of the obtained phosphor samples were investigated. The PL excitation spectra of the Sr₂SiO₄:Eu²⁺ phosphors exhibited a broad band in the range of 260 nm to 485 nm with a maximum at 361 nm attributed to the 5f‐4d allowed transition of the Eu²⁺ ions. Under an excitation at 361 nm, the Sr₂SiO₄:Eu²⁺ phosphor exhibited a greenish‐yellow emission peak at 541 nm with an International‐Commission‐on‐Illumination (CIE) chromaticity of (0.3064, 0.4772). The results suggest that the microwave‐assisted sintering method is promising for the synthesis of phosphors owing to the decreased sintering time without the use of additional reductive agents.     

A novel red‐emitting phosphor,KAl1‐xPO4Cl:Eux3+ (0.1 ≤ x ≤ 1.0)

A series of phosphors KAl_1‐xPO₄Cl:Eu_x³⁺ (0.1 ≤ x ≤ 1.0) was synthesized using a facile combustion method using urea as a fuel and their structural, morphological and photoluminescence properties were investigated. It was found that the particle size was in the range of 1–2 µm with an irregular shape. The f–f transitions of Eu³⁺ in the host lattice were assigned and discussed. The excitation and emission spectra indicated that this phosphor can be efficiently excited by ultraviolet (395 nm), and exhibit reddish orange emission corresponding to the ⁵D₀→⁷F_J (J = 0, 1, 2) transitions of Eu³⁺. The impact of the Eu³⁺ concentration on the relative emission intensity was investigated, and the best doping concentration is 0.5. The present study suggests that the KAl_0.5PO₄Cl: Eu_0.5³⁺ phosphor is a strong candidate as a red component for phosphor‐ converted white light‐emitting diodes (LEDs). Copyright © 2015 John Wiley & Sons, Ltd.     

Photoluminescence,cathodoluminescence and thermal stability of Sm3+‐activated Sr3La(VO4)3 red‐emitting phosphors

A series of Sm³⁺‐activated Sr₃La(VO₄)₃ phosphors were synthesized by a facile sol‐gel method. X‐ray diffraction patterns and photoluminescence (PL)/cathodoluminescence (CL) spectra as well as PL decay curves were employed to characterize the obtained samples. Upon 402 nm light excitation, the characteristic emissions of Sm³⁺ ions corresponding to ⁴G_5/2→⁶H_J transitions were observed in all the as‐prepared products. The PL emission intensity was increased with increase in Sm³⁺ ion concentration, while concentration quenching occurred when the doping concentration was over 4 mol%. The non‐radiative energy transfer mechanism for concentration quenching of Sm³⁺ ions was dominated by dipole–dipole interaction and the critical distance was around 21.59 Å. Furthermore, temperature‐dependent PL emission spectra revealed that the obtained phosphors possessed good thermal stability with an activation energy of 0.19 eV. In addition, the CL spectra of the samples were almost the same as the PL spectra, and the CL emission intensity showed a tendency to increase with increase in accelerating voltage and filament current. These results suggest that the Sm³⁺‐activated Sr₃La(VO₄)₃ phosphors with good color coordinates, high color purity and superior thermal stability may be a potential candidate for applications in white light‐emitting diodes and field‐emission displays as red‐emitting phosphors.     

Molten salt synthesis and luminescence of Dy3+‐doped Y3Al5O12 phosphors

Dy³⁺‐doped Y₃Al₅O₁₂ phosphors were prepared at a relatively low temperature using molten salt synthesis. The phase of the prepared Dy³⁺‐doped Y₃Al₅O₁₂ phosphors was confirmed using X‐ray powder diffraction. Results indicated that Dy³⁺ doping did not change the Y₃Al₅O₁₂ phase. Following excitation at 352 nm, emission spectra of the Dy³⁺‐doped Y₃Al₅O₁₂ phosphors consisted of blue, yellow, and red emission bands. The influence of Dy³⁺ concentration and excitation wavelength on emission was investigated. The ratio of yellow light to blue light varied with change in Dy³⁺ doping concentration, due to changes in the structure around Dy³⁺. Emission intensities also changed when the excitation wavelength was changed. This variation is luminescence generated a system for tunable white light for Dy³⁺‐doped Y₃Al₅O₁₂ phosphors.     

Novel red colour emitting Ca0.995Mg2(SO4)3:0.5Eu2+ phosphor under ultraviolet,blue, and green excitation for plant growth LEDs

In the recent few years, Eu²⁺- and Mn⁴⁺-activated phosphors are widely used as potential colour converters for indoor plant cultivation lighting application due to their marvellous luminescence characteristics as well as low cost. In this investigation, we synthesized novel red colour-emitting Ca_(2−x)Mg₂(SO₄)₃:xmol% Eu²⁺ (x = 0–1.0 mol%) phosphors via a solid-state reaction method in a reducing atmosphere. The photoluminescence (PL) excitation spectra of synthesized phosphors exhibited a broad excitation band with three excitation bands peaking at 349 nm, 494 nm, and 554 nm. Under these excitations, emission spectra exhibited a broad band in the red colour region at ~634 nm. The PL emission intensity was measured for different concentrations of Eu²⁺. The maximum Eu²⁺ doping concentration in the Ca₂Mg₂(SO₄)₃ host was observed for 0.5 mol%. According to Dexter theory, it was determined that dipole–dipole interaction was responsible for the concentration quenching. The luminous red colour emission of the sample was confirmed using Commission international de l'eclairage colour coordinates. The results of PL excitation and emission spectra of the prepared phosphors were well matched with excitation and emission wavelengths of phytochrome P_R. Therefore, from the entire investigation and obtained results it was concluded that the synthesized Ca_0.995Mg₂(SO₄)₃:0.5mol%Eu²⁺ phosphor has huge potential for plant cultivation application.     

Luminescence characterization of KBaPO4:RE (RE = Sm3+,Eu3+,Dy3+) phosphors

KBaPO₄ luminescent powdered phosphors doped with rare earth elements (RE = Sm³⁺,Eu³⁺,Dy³⁺) were successfully synthesized using a wet chemical method to identify the most suitable phosphor for solid‐state lighting based on the measurement of their emission spectra at excitation wavelengths. The X‐ray diffraction pattern of the as‐prepared KBaPO₄ was well matched with its standard JCPDS file no. 330996, indicating the formation of the desired compound. Scanning electron microscopy images revealed irregular morphology, the material crystallized particles aggregated and were non‐uniform with particle sizes ranging from 1 to 100 μm. Photoluminescence excitation and emission spectra clearly indicated that the phosphor containing the Sm³⁺‐activated KBaPO₄ phosphors could be efficiently excited at 403 nm and exhibited an emission mainly including two wavelength peaks at 559 nm and 597 nm. The phosphor containing the Eu³⁺‐activated KBaPO₄ phosphors could be efficiently excited at 396 nm and exhibited a bright red emission mainly including two wavelength peaks at 594 nm and 617 nm. The phosphor containing the Dy³⁺‐activated KBaPO₄ phosphors could be efficiently excited at 349 nm and exhibited wavelength peaks at 474 nm and 570 nm.     

Energy transfer induced white‐light‐emitting phosphor by co‐doping Ce3+, Tb3+ and Mn2+ into the single Ba9Lu2Si6O24 host

In the Ba₉Lu₂Si₆O₂₄ (BLS) host, Ce³⁺ shows cyan emissions peaking at 490 nm under 400 nm excitations. BLS:Tb³⁺ only can be effectively excited by 254 nm light and gives rise to green emissions at 553 nm. However, both the cyan and green emissions can be obtained in BLS:Ce³⁺,Tb³⁺ under 400 nm excitations due to effective energy transfers from Ce³⁺ to Tb³⁺. BLS:Mn²⁺ shows red emissions peaking at 610 nm under 414 nm excitations. By co‐doping Ce³⁺, Tb³⁺ and Mn²⁺, tunable full‐color emissions were obtained. The BLS:0.3Ce³⁺,0.6Tb³⁺,0.15Mn²⁺ single phosphor exhibits a white light with a high color rendering index of 85 and a correlated color temperature of 5480 K under 400 nm excitation.     

Photoluminescence properties of a new orange–red‐emitting Sm3+–La3SbO7 phosphor

The antimonate compound La₃SbO₇ has high chemical stability, lattice stiffness and thermal stability. Orange–red‐emitting antimonate‐based phosphors La₃SbO₇:xSm³⁺ (x = 0.02, 0.05, 0.08, 0.10, 0.15, 0.20 and 0.25) were synthesized. The phase structure and photoluminescence properties of these phosphors were investigated. The emission spectrum obtained on excitation at 407 nm contained exclusively the characteristic emissions of Sm³⁺ at 568, 608, 654 and 716 nm, which correspond to the transitions from ⁴G_5/2 to ⁶H_5/2, ⁶H_7/2, ⁶H_9/2 and ⁶H_11/2 of Sm³⁺, respectively. The strongest emission was located at 608 nm due to the ⁴G_5/2→⁶H_7/2 transition of Sm³⁺, generating bright orange–red light. The critical quenching concentration of Sm³⁺ in La₃SbO₇:Sm³⁺ phosphor was determined as 10% and the energy transfer between Sm³⁺ was found to be through an exchange interaction. The International Commission on Illumination chromaticity coordinates of the La₃SbO₇:0.10Sm³⁺ phosphors are located in the orange–red region. The La₃SbO₇:Sm³⁺ phosphors may be potentially used as red phosphors for white light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Investigation on luminescence properties of Eu2+‐doped Ba3Al2O5Cl2 phosphor for near‐UV‐excited white LEDs

Ba₃Al₂O₅Cl₂:Eu²⁺ phosphor was prepared by combustion synthesis (CS). The prepared phosphor was excited at 329 nm; the phosphors shows an efficient bluish‐green wide‐band emission centred at 490 nm, which originates from the 4f⁶d¹ → 4f⁷ transition of Eu²⁺ ions. The excitation spectra of the phosphors have a band centred at 329 nm. It was also characterized by XRD, FT–IR for confirmation of phase purity, and FT–IR analysis indicated the vibrations of metal–oxygen (M–O) groups. SEM shows the morphology of the phosphor at the submicron scale. The results indicate that Ba₃Al₂O₅Cl₂:Eu²⁺ phosphor may be applicable for solid‐state lighting purposes. Copyright © 2012 John Wiley & Sons, Ltd.     

Structural and photoluminescence study of Mn2+‐activated CaYAl3O7 blue phosphors

The structural and photoluminescence properties of CaYAl₃O₇ phosphor material doped with varying concentration of Mn²⁺ have been studied. The phosphor material was synthesized by the combustion method at 500 °C and was characterized using X‐ray diffraction, Fourier transform infrared spectroscopy and photoluminescence spectroscopy (PL). X‐ray diffraction showed that the crystallites have average sizes in the range of ~58–70 nm. Corresponding Fourier transform infrared spectroscopy investigations confirm the phase formation and the presence of aluminate group (Al‐O bands) in CaYAl₃O₇:Mn²⁺ phosphor. Under the excitation at 356 nm wavelength, the PL spectra show the occurrence of two emission peaks obtained in the blue region at 389 nm and 412 nm, which is attributed to the 4 T1(G) → 6A1 transition of Mn²⁺ ion. Upon increasing Mn²⁺ concentration, the relative PL intensity shows an initial decrement followed by an increase displaying the effect of concentration quenching. Overall the results suggest the possibility of using this material in white lighting devices and plasma display panels. Copyright © 2013 John Wiley & Sons, Ltd.