Fluorescence properties with red-shift of Eu2+ emission in novel phosphor-silicate apatite Sr3LaNa(PO4)2SiO4 phosphors

A series of Eu²⁺-activated novel phosphor-silicate apatite Sr₃LaNa(PO₄)₂SiO₄ phosphors were synthesized by solid-state reaction. The X-ray diffraction (XRD) and Rietveld refinement, diffuse reflectance spectra, luminescent spectra, decay curves and thermal quenching properties were applied to characterize the obtained phosphors. The XRD result revealed that all the samples possessed only a single phase with hexagonal structure and the doping of Eu²⁺ ions were successfully incorporated into the crystal lattice. The reflectance spectra showed an obvious red-shift of the wavelength from 400 to 700 nm with increasing Eu²⁺ ion concentration. The three different crystallographic sites of Eu²⁺ ions had been confirmed by their lifetimes. All the samples exhibited broad absorption bands from 200 to 450 nm, revealing the phosphor-silicate phosphor interesting for application in the near-UV used phosphor-converted LED chips. These results suggested that the Eu²⁺-activated phosphor-silicate Sr₃LaNa(PO₄)₂SiO₄ phosphors have the potential for near-UV pumped white-light-emitting diodes (w-LEDs).     

Sr3GdLi(PO4)3F:Eu2+, Mn2+: A tunable blue-white color emitting phosphor via energy transfer for near-UV white LEDs

A series of Eu²⁺ and Mn²⁺ co-doping Sr₃GdLi(PO₄)₃F phosphors have been synthesized through high temperature solid state reaction. Eu²⁺ single doped Sr₃GdLi(PO₄)₃F phosphors have an efficient excitation in the range of 230–430 nm, which is in good agreement with the commercial near-ultraviolet (n-UV) LED chips, and gives intense blue emission centering at 445 nm. The critical distance of the Eu²⁺ ions in Sr₃GdLi(PO₄)₃F is computed and demonstrated that the concentration quenching mechanism of Eu²⁺ is mostly caused by the dipole-dipole interaction. By co-doping Eu²⁺ and Mn²⁺ ions in the Sr₃GdLi(PO₄)₃F host, the energy transfer from Eu²⁺ to Mn²⁺ that can be discovered. With the increase of Mn²⁺ content, emission color can be adjusted from blue to white under excitation of 380 nm, corresponding to chromatic coordinates change from (0.189, 0.108) to (0.319, 0.277). The energy transfer from Eu²⁺ to Mn²⁺ ions is proven to be a dipole-dipole mechanism on the basis of the experimental results and analysis of photoluminescence spectra and decay curves. This study infers that the obtained Sr₃GdLi(PO₄)₃F:Eu²⁺, Mn²⁺ phosphors may be a potential candidate for n-UV LEDs.     

Synthesis and luminescence enhancement of red-emitting Sr9Y(PO4)7:Eu3+ phosphor through Gd3+ co-doping for white light-emitting diodes

A series of Sr₉Y(PO₄)₇:Eu³⁺ and Sr₉Y(PO₄)₇:Eu³⁺, Gd³⁺ red-emitting phosphors were prepared via a high-temperature solid-state method, Gd³⁺ ion was co-doped in Sr₉Y(PO₄)₇:Eu³⁺ as sensitizer to enhance the luminescence property. The X-ray diffraction results verify that the structure of the as-prepared samples is consistent with the standard Sr₉Y(PO₄)₇ phase. All the Sr₉Y(PO₄)₇:Eu³⁺ samples show both characteristic emission peaks at 594 nm and 614 nm under near-ultraviolet excitation of 394 nm. The co-doping of Gd³⁺ significantly improves the luminescence intensity of the Sr₉Y(PO₄)₇:Eu³⁺ phosphors due to the crystal field environment effect and energy transfer of Gd³⁺→Eu³⁺ caused by the introduction of Gd³⁺, especially Sr₉Y(PO₄)₇:0.11Eu³⁺, 0.05Gd³⁺, which emission intensity is higher than that of Sr₉Y(PO₄)₇:0.11Eu³⁺ by 1.21 times. The color purity and lifetime of Sr₉Y(PO₄)₇:0.11Eu³⁺, 0.05Gd³⁺ phosphor are 88.26% and 3.7615 ms, respectively. A w-LED device was packaged via coating the as-prepared phosphor on n-UV chip of 395 nm with commercial phosphors. These results exhibit that the Sr₉Y(PO₄)₇:Eu³⁺, Gd³⁺ red-emitting phosphor can be used as a red component in the w-LEDs application.     

Tunable single-phased white-emitting Sr3Y(PO4)3:Dy3+ phosphors for near-ultraviolet white light-emitting diodes

Single-component white-emitting Sr₃Y(PO₄)₃:Dy³⁺ phosphors were synthesized by a high-energy deformation process. X-ray diffraction patterns showed the resulting crystallized phase to be of cubic structure, space group I-43d (no. 220). The broad-band excitation spectra between 250 and 500 nm were observed by monitoring the emission wavelength at 576 nm, which matches well with commercial near-UV or blue LED chips. Under a 352 nm excitation, the emission peaks were observed at 483 nm (blue), 576 nm (yellow), and 666 nm (red), corresponding to the ⁴F_9/2 → ⁶H_15/2, ⁴F_9/2 → ⁶H_13/2, and ⁴F_9/2 → ⁶H_11/2 transitions of Dy³⁺ ions. The optimized doping concentration of Dy³⁺ ion was 8 mol%. By controlling the Dy³⁺ ion concentration, tunable colors from white to yellow were obtained in Sr₃Y(PO₄)₃:Dy³⁺ phosphors. These results reveal that studied materials may be a promising candidate for white LED applications.     

Crystal structure,luminescent properties and white light emitting diode application of Ba3GdNa(PO4)3F:Eu2+ single-phase white light-emitting phosphor

A series of single-phase white-light-emitting phosphors, Eu²⁺-activated Ba₃GdNa(PO₄)₃F phosphors were synthesized by solid-state reactions. The crystal structure of Ba₃GdNa(PO₄)₃F was been identified by Rietveld refinement of X-ray diffraction pattern. The Eu²⁺-activated Ba₃GdNa(PO₄)₃F phosphors exhibit broad excitation spectra from 250 to 420 nm, which matched well with the n-UV LED chips. Under the excitation of 365 nm, the emission spectrum almost covered the entire visible region including two emission bands peaked at 472 nm and 640 nm. Three different Eu²⁺ emission centers in Ba₃GdNa(PO₄)₃F:Eu²⁺ phosphor were confirmed by their fluorescence decay lifetimes. The optimal concentration of Eu²⁺ in Ba₃GdNa(PO₄)₃F:xEu²⁺ was 3 mol% and the corresponding concentration quenching mechanism was verified to be exchange coupling interaction. Furthermore, the white light-emitting diode fabricated with Ba₃GdNa(PO₄)₃F:0.05Eu²⁺ phosphor and a 370 nm UV chip has a CIE of (0.3267, 0.2976) with a color-rendering index of 78.4 at the CCT of 5287 K.     

Gel-combustion assisted synthesis of eulytite-type Sr3Y(PO4)3 as a single host for narrow-band Eu3+ and broad-band Eu2+ emissions

A series of eulytite-type Sr₃Y_1-x(PO₄)₃:xEu³⁺ (x = 0–0.13) and Sr_3-yY(PO₄)₃:yEu²⁺ (y = 0–0.10) phosphors were successfully synthesized via gel-combustion and subsequent calcination in O₂ and Ar/H₂ atmospheres at 1250 °C, respectively. Detailed crystal structure analysis via Rietveld refinement showed that the phosphors were crystallized in the cubic system (space group I-43d, No. 220), in which the Eu³⁺ and Eu²⁺ activators reside at the Y³⁺ and Sr²⁺ sites, respectively. The trivalent Eu³⁺ ions (CN = 6) exhibited typical narrow-band luminescence via intra-4f⁶ transitions, with the red emission at ~ 615 nm being dominant (⁵D₀ → ⁷F₂ transition, FWHM = 15.9 ± 0.2 nm). The divalent Eu²⁺ ions (CN = 6 and 9) showed broad-band luminescence ranging from light-blue to blue via 4f⁶5d¹ → 4f⁷ transitions (FWHM = 115 ± 2 nm). The optimal Eu³⁺ and Eu²⁺ concentrations were determined to be 10 at% (x = 0.10) and 7 at% (y = 0.07), respectively, and the mechanisms of concentration quenching were discussed. The excitation/emission properties, fluorescence decay kinetics, CIE chromaticity, and particularly the rarely addressed thermal stability of the phosphors were investigated in detail.     

Color tuning in (Ca1−xSrx)8MgLu(PO4)7:Eu2+,Mn2+ phosphor via host composition design and energy transfer

In this work, a series of Eu²⁺-doped (Ca_1−xSr_x)₈MgLu(PO₄)₇ and Eu²⁺/Mn²⁺-codoped Ca_6.5Sr_1.5MgLu(PO₄)₇ phosphors were prepared via the combustion-assisted solid-state reaction process. XRD patterns and Rietveld refinements were used to verify the incorporations of Sr into Ca₈MgLu(PO₄)₇:Eu²⁺. Upon the same excitation wavelength of 380 nm, the emission peaks of Eu²⁺-doped (Ca_1−xSr_x)₈MgLu(PO₄)₇ (0≤x≤1) phosphors red-shifted from 453 to 519 nm with increasing Sr/Ca ratio. The red-shift of the Eu²⁺ emission with increasing Sr/Ca ratio was ascribed to the change of Eu²⁺ emission at different lattice sites. With variation of the Mn²⁺ content, the emission color of Eu²⁺/Mn²⁺ codoped Ca_6.5Sr_1.5MgLu(PO₄)₇ phosphors exhibited the luminescence tunable from greenish blue to white and eventually to red. The energy transfer from Eu²⁺ to Mn²⁺ in Ca_6.5Sr_1.5MgLu(PO₄)₇ host matrix was demonstrated to be of a resonant type via a dipole- dipole mechanism with the critical distance of ∼16.7 Å. By the Sr substitution for Ca and properly tuning by the relative composition change of Eu²⁺/Mn²⁺, chromaticity coordinates of (0.329, 0.326) can be reached at near UV light excitation. The combination of host composition design and energy transfer may provide a novel strategy to obtain white light and tunable luminescence.     

Warm white-light generation in Ca9MgNa(PO4)7:Sr2+, Mn2+, Ln (Ln=Eu2+, Yb3+, Er3+, Ho3+, and Tm3+) under near-ultraviolet and near-infrared excitation

To obtain warm white-light emission, a series of Ca₉MgNa(PO₄)₇:Sr²⁺, Mn²⁺, Ln (Ln=Eu²⁺, Yb³⁺, Er³⁺, Ho³⁺, and Tm³⁺) phosphors were designed and their photoluminescence properties under near-ultraviolet and near-infrared excitation were studied. For near-ultraviolet excitation, blue-white emission is produced initially in the Eu²⁺ single-doped Ca₉MgNa(PO₄)₇, whose excitation band can well match with the near ultraviolet LED chip. By introducing Sr²⁺ ions into Ca₉MgNa(PO₄)₇:Eu²⁺, the Eu²⁺ emission band beyond 500 nm is enhanced obviously. Correspondingly, the emitting light color is tuned to nearly white. To generate warm white light further, Mn²⁺ is doped into the Ca_8.055MgNa(PO₄)₇:0.045Eu²⁺, 0.9Sr²⁺ and the correlated color temperature is decreased largely. For near-infrared excitation, the green, red, and blue emissions have been obtained in the Yb³⁺-Er³⁺, Yb³⁺-Er³⁺, and Yb³⁺-Er³⁺ co-doped Ca₉MgNa(PO₄)₇ phosphors, respectively. And warm white light is also produced in the Ca₉MgNa(PO₄)₇:Yb³⁺, Er³⁺, Ho³⁺, Tm³⁺ under 980 nm excitation.     

Energy transfer and multicolor tunable emission in single-phase Tb3+, Eu3+ co-doped Sr3La(PO4)3 phosphors

A series of green-to-red color-tunable Sr₃La(PO₄)₃:Tb³⁺, Eu³⁺ phosphors were prepared by high temperature solid-state method. The crystal structures, photoluminescence properties, fluorescence lifetimes, and energy transfer of Sr₃La(PO₄)₃:Tb³⁺, Eu³⁺ were systematically investigated in detail. The obtained phosphors show both a green emission from Tb³⁺ and a red emission from Eu³⁺ with considerable intensity under ultraviolet (UV) excitation (~377 nm). The emission colors of the phosphors can be tuned from green (0.304, 0.589) through yellow (0.401, 0.505) and eventually to red (0.557, 0.392) due to efficient Tb³⁺-Eu³⁺ energy transfer (ET). The Tb³⁺→Eu³⁺ energy transfer process was demonstrated to be quadrupole-quadrupole mechanism by Inokuti-Hirayama model, with maximum ET efficiency of 86.3%. The results indicate that the Sr₃La(PO₄)₃:Tb³⁺, Eu³⁺ phosphors might find potential applications in the field of lighting and displays.     

Near-UV light excited Eu3+, Tb3+, Bi3+ co-doped LaPO4 phosphors: Synthesis and enhancement of red emission for WLEDs

A series of single-phase Eu³⁺, Tb³⁺, Bi³⁺ co-doped LaPO₄ phosphors were synthesized by solid-state reaction at 800 °C. Crystal structures of the phosphors were investigated by X-ray diffraction (XRD). A monoclinic phase was confirmed. The excitation (PLE) and emission (PL) spectra showed that the phosphors could emit red light centered at 591 nm under the 392 nm excitation, which is in good agreement with the emission wavelength from near-ultraviolet (n-UV) LED chip (370–410 nm). The results of PLE and PL indicated that the co-doped Tb³⁺ and Bi³⁺could enhance emission of Eu³⁺ and the fluorescent intensities of the phosphors excited at 392 nm could reach to a maximum value when the doping molar concentration of Tb³⁺ and Bi³⁺ is about 2.0% and 2.0%, respectively. The co-doping Tb³⁺ and Bi³⁺ ions can strengthen the absorption of near UV region. They can also be efficient to sensitize the emission of Eu³⁺, indicating that the energy transfer occurs from Tb³⁺ and Bi³⁺ to Eu³⁺ ions. From further investigation it can be found that co-doping Tb³⁺ and Bi³⁺ ions can also induce excitation energy reassignment between ⁵D₀–⁷F₁ and ⁵D₀–⁷F₂ in these phosphors, and result in more energy assignment to ⁵D₀–⁷F₂ emission in LaPO₄:Eu³⁺, Tb³⁺, Bi³⁺. Our research results displayed that La_0.94PO₄:Eu³⁺_0.02, Tb³⁺_0.02, Bi³⁺_0.02 could be a new one and could provide a potential red-emitting phosphor for UV-based white LED.     

Synthesis and photoluminescence enhancement of Ca3Sr3(VO4)4:Eu3+ red phosphors by co-doping with La3+

In this study, a series of red-emitting Ca₃Sr₃(VO₄)₄:Eu³⁺ phosphors co-doped with La³⁺ was prepared using the combustion method. The microstructures, morphologies, and photoluminescence properties of the phosphors were investigated. All Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ samples synthesized at temperatures greater than 700 ℃ exhibited the same standard rhombohedral structure of Ca₃Sr₃(VO₄)₄. Furthermore, the Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ phosphor was effectively excited by near-ultraviolet light of 393 nm and blue light of 464 nm. The strong excitation peak at 464 nm corresponded to the ⁷F₀→⁵D₂ electron transition of Eu³⁺. The strong emission peak observed at 619 nm corresponded to the ⁵D₀→⁷F₂ electron transition of Eu³⁺. Co-doping with La³⁺ significantly improved the emission intensity of Ca₃Sr₃(VO₄)₄:Eu³⁺ red phosphors. The optimum luminescence of the phosphor was observed at Eu³⁺ and La³⁺ concentrations of 5% and 6%, respectively. Moreover, co-doping with La³⁺ also improved the fluorescence lifetime and thermal stability of the Ca₃Sr₃(VO₄)₄:Eu³⁺ phosphor. The CIE chromaticity coordinate of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺, 0.06La³⁺ was closer to the NTSC standard for red phosphors than those of other commercial phosphors; moreover, it had greater color purity than that of all the samples tested. The red emission intensity of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺, 0.06La³⁺ at 619 nm was ~1.53 times that of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺ and 2.63 times that of SrS:Eu²⁺. The introduction of charge compensators could further increase the emission intensity of Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ red phosphors. The phosphors synthesized herein are promising red-emitting phosphors for applications in white light-emitting diodes under irradiation by blue chips.     

Synthesis and photoluminescence properties of Sr3(PO4)2:Re3+, Li+ (Re = Eu,Sm) red phosphors for white light-emitting diodes

Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) red phosphors were prepared via a high temperature solid state reaction, and their structure and luminescence properties were investigated. X-ray diffraction patterns indicate that the phase of as-prepared samples is in good agreement with standard Sr₃(PO₄)₂ structure. Under 395 nm excitation, the emission of Sr₃(PO₄)₂:Eu³⁺ consists of a strong peak centered at 622 nm and two weak peaks centered at 598 nm and 660 nm, which correspond to ⁵D₀→⁷F₂, ⁵D₀→⁷F₁ and ⁵D₀→⁷F₃ transitions, respectively. Also, the emission spectrum of Sr₃(PO₄)₂:Sm³⁺ shows three main peaks at 568 nm, 603 nm and 651 nm, which are attributed to ⁴G_5/2→⁶H_I/2 (I = 5, 7, 9) transitions of Sm³⁺. Furthermore, luminescence properties of Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) samples are enhanced significantly by Li⁺ ions doping as charge compensator. Results indicate that as-prepared Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) could be the potential red phosphors used in white light-emitting diodes.     

A novel pure red phosphor Ca8MgLu(PO4)7:Eu3+ for near ultraviolet white light-emitting diodes

A novel red-emitting phosphor Ca₈MgLu(PO₄)₇:Eu³⁺ was synthesized by a high-temperature solid-state reaction method. Its crystal structure, photoluminescence emission and excitation spectra, and decay time were investigated in detail. X-ray diffraction (XRD) results indicate that Ca₈MgLu(PO₄)₇ crystallizes in single-phase component with a whitlockite-like structure and the space group R3c of β-Ca₃(PO₄)₂. The emission spectrum shows a dominant peak at 612 nm due to the dipole ⁵D₀→⁷F₂ transition of Eu³⁺, and the luminescence intensity keeps increasing with increasing the content of Eu³⁺ to 100%. The excitation spectrum is coupled well with the emission of near ultraviolet (NUV) LED (380–410 nm). The CIE coordinates of Ca₈MgLu(PO₄)₇:Eu³⁺ phosphor is (0.654, 0.346), being close to the standard value of National Television Standard Committee (NTSC) for red phosphor, (0.670, 0.330). The internal quantum efficiency of the phosphor is 69% under the excitation of 394 nm. The results show that Ca₈MgLu(PO₄)₇:Eu³⁺ is a very appropriate red-emitting phosphor with a high ratio of red and orange for NUV-based white LEDs.     

Synthesis and photoluminescence properties of CaGd2(MoO4)4:Eu3+ red phosphors

The novel red-emitting Eu³⁺ ions activated CaGd₂(MoO₄)₄ phosphors were prepared by a citrate sol–gel method. The X-ray diffraction patterns confirmed their tetragonal structure when the samples were annealed above 600 °C. The photoluminescence excitation spectra of CaGd₂(MoO₄)₄:Eu³⁺ phosphors exhibited the charge transfer band (CTB) and intense f–f transitions of Eu³⁺ ion. The optimized annealing temperature and Eu³⁺ ion concentration were analyzed for CaGd₂(MoO₄)₄:Eu³⁺ phosphors based on the dominant red (⁵D₀→⁷F₂) emission intensity under NUV (394 nm) excitation. All decay curves were well fitted by the single exponential function. These luminescent powders are expected to find potential applications such as WLEDs and optical display systems.     

Red,green and blue-violet emission coexistence in white-light-emitting Ca3SiO4Cl2:Bi3+, Li+, Eu2+, Eu3+ phosphor

A series of emission-tunable Ca₃SiO₄Cl₂:Bi³⁺, Li⁺, Euⁿ⁺(n =2, 3) (CSC:Bi³⁺, Li⁺, Euⁿ⁺) phosphors have been synthesized via sol-gel method. The X-ray diffraction results indicate that the as-synthesized phosphors crystallize in a low temperature phase with the space group of P21/c. Energy transfer from Bi³⁺ to Eu³⁺/Eu²⁺ exists in CSC:Bi³⁺, Li⁺, Euⁿ⁺ phosphors. Under the excitation of 327 or 365 nm, the Ca_2.98−ySiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, yEuⁿ⁺(y=0.0001–0.002) phosphors show an intense green emission band around 505 nm, while under the excitation of 264 nm, three emission bands centered around 396 nm (Bi³⁺), 505 nm (Eu²⁺) and 614 nm (Eu³⁺) are observed and tunable colors from blue-violet to green or white are achieved in these phosphors by varying the content of Eu. White-light emission with the color coordinate (0.312, 0.328) is obtained in Ca_2.978SiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, 0.002Euⁿ⁺(n =2, 3). Based on these results, the as-prepared CSC:Bi³⁺, Li⁺, Eu²⁺, Eu³⁺ phosphors can act as color-tunable and single-phase white emission phosphors for potential applications in UV-excited white LEDs.     

Crystal structure and luminescence properties of novel Sr10−x(SiO4)3(SO4)3O:xEu2+ phosphor with apatite structure

In this paper, a series of novel luminescent Sr_10−x(SiO₄)₃(SO₄)₃O:xEu²⁺ phosphors with apatite structure were synthesized by a high temperature solid-state reaction. The phase structure, photoluminescence (PL) properties, as well as the PL thermal stability were investigated. Sr_9.92(SiO₄)₃(SO₄)₃O:0.08Eu²⁺ phosphor exhibits better thermal quenching resistance, retaining the luminance of 66.55% at 150 °C compared with that at 25 °C. The quenching concentration of Eu²⁺ in Sr₁₀(SiO₄)₃(SO₄)₃O was about 0.08 (mol) with the dipole–quadrupole interaction. The Sr_10−x(SiO₄)₃(SO₄)₃O:xEu²⁺ phosphors exhibited a broad-band green emission at 538 nm upon excitation at 396 nm. The results indicate that Sr_10−x(SiO₄)₃(SO₄)₃O:xEu²⁺ phosphors have potential applications as near UV-convertible phosphors for white-light UV LEDs.     

The influence of Mo6+ doping on the luminescence properties of red-emitting phosphor Sr9Eu2W4−xMoxO24 (x = 0–4)

A series of red emitting phosphors Sr₉Eu₂W_4?xMo_xO₂₄ (x = 0–4) have been synthesized by solid-state reactions and their crystal structures, photoluminescence properties were studied. The excitation and emission spectra of Sr₉Eu₂W_4?xMo_xO₂₄ phosphors can be modified by Mo⁶⁺ doping. As the molybdate content increased, the Eu³⁺ emission intensity of Sr₉Eu₂W_4?xMo_xO₂₄ (x = 0–4) under 395 nm excitation was found to increase and reached a maximum at x = 2. The excitation spectra, the emission intensities and the chromaticity coordinates of Sr₉Eu₂W_4?xMo_xO₂₄ (x = 2) were compared to those of the conventional red phosphor Y₂O₂S: Eu³⁺. The intense red-emission under near-UV excitation suggests that Sr₉Eu₂W_4?xMo_xO₂₄ (x = 2) could be a potential candidate for white light generation by using near-UV LEDs. In this study, the effects of Mo⁶⁺ doping on the crystal structure and photoluminescence properties of Sr₉Eu₂W_4?xMo_xO₂₄ were discussed.     

White emitting Dy3+ activated perovskite titanates and energy transfer by Eu3+ codoping

Perovskite type titanate phosphors Sr_0.97−xDy_0.03Li_xTi_1−xNb_xO₃, Sr_0.9−xDy_xLi_0.1Ti_0.9Nb_0.1O₃ and Sr_0.87−yDy_0.03Eu_yLi_0.1Ti_0.9Nb_0.1O₃ were prepared by conventional solid state method. Herein, white light emission from Sr_0.9−xDy_xLi_0.1Ti_0.9Nb_0.1O₃ phosphors and the lowering of its color temperature through codoping with Eu³⁺ ions are reported. Raman measurements have shown that the incorporation of dopants alters the vibrational properties of these phosphors significantly, indicating the reduction of the local symmetry in the crystal lattice. The addition of LiNbO₃ in SrTiO₃:Dy³⁺ phosphor enhances the luminescence intensity and the yellow to blue ratio resulting in emission of high quality white light with color coordinates corresponding to that of standard white. Life time measurements and data fits of Sr_0.9−xDy_xLi_0.1Ti_0.9Nb_0.1O₃ phosphors revealed the biexponential behaviour of luminescence decay profiles. From Judd-Ofelt analysis it is found that the intensity parameter Ω₂ increases with Dy³⁺ concentration and a quantum efficiency of 90.4% was obtained for optimum concentration. In the case of Dy³⁺ and Eu³⁺ codoped phosphors, the color coordinates are found to be sensitive to the Eu³⁺ concentration and the highest energy transfer efficiency of 92% was obtained for the phosphor doped with 10 mol% Eu³⁺. The emission color changes from cold white to reddish orange when the wavelength of excitation alters from 452 to 388 nm, since the energy transfer mechanism alone take place under 452 nm excitation and both direct absorption and the energy transfer mechanism occurs under 388 nm excitation.     

Effect of Sr/Ca substitution on phase structure and photoluminescence properties of micro-SrxCa1−xAlSiN3: Eu2+ phosphor for high CRI white LEDs

Sr_xCa_1−xAlSiN₃: Eu²⁺ phosphors were prepared by using the high temperature solid state reaction in a 1.1 Mpa N₂ atmosphere. The phase structures, photoluminescence (PL) properties, and chromaticity properties of the phosphors affected by Sr/Ca Substitution have been investigated in detail. With increasing Sr content (x value), the crystal grain became bigger and the average grain size increased from 5 µm to 10 µm. PL emission bands of Sr_xCa_1−xAlSiN₃: Eu²⁺ showed a blue-shift from 660 (x=0) to 617 nm (x=0.8), the shoulder of the excitation spectra around 550 nm showed a slightly blue-shift and decay lifetime shortened from 776.96 (x=0.2) to 642.35 ns (x=0.8). Both the emission and excitation intensity of peak position increased with Sr content increased. The ideal white light with high CRI (Ra>88) can be obtained by mixing the Sr_xCa_1−xAlSiN₃: Eu²⁺ phosphors and commercial green phosphors with appropriate proportion of the components.     

Luminescence properties of Eu2+ and Mn2+ doped Sr1.7Mg0.3SiO4 phosphors

Eu²⁺, Mn²⁺ doped Sr_1.7Mg_0.3SiO₄ phosphors were prepared by high temperature solid-state reaction method. Their luminescence properties were studied. The emission spectra of Eu²⁺ singly doped Sr_1.7Mg_0.3SiO₄ consist of a blue band (455 nm) and a green band (550 nm). The relative intensities of two emissions varied with Eu²⁺ concentration. Eu²⁺ and Mn²⁺ co-doped Sr_1.7Mg_0.3SiO₄ phosphors emit three color lights and present whitish color. The blue (455 nm) and green (550 nm) emissions are attributed to the transitions of Eu²⁺, while the red (670 nm) emission is originated from the transition of Mn²⁺ ion. The results indicate the energy transfer from Eu²⁺ to Mn²⁺. The mechanism of the energy transfer is resonance-type energy transfer due to the spectral overlap between the emission of Eu²⁺and the absorption of Mn²⁺.