White light emission from novel host-sensitized single-phase Y2WO6: Ln3+ (Ln3+=Eu3+, Dy3+) phosphors

A series of Eu³⁺- or Dy³⁺-doped and Eu³⁺/Dy³⁺ co-doped Y₂WO₆ in pure phase was synthesized via high-temperature solid-state reaction. X-ray diffraction, diffuse reflection spectra, photoluminescence excitation and emission spectra, the CIE chromaticity coordinates and temperature-dependent emission spectra were exploited to investigate the phosphors. Upon UV excitation at 310 nm, efficient energy transfer from the host Y₂WO₆ to dopant ions in Eu³⁺ or Dy³⁺ single-doped samples was demonstrated and those phosphors were suitable for the UV LED excitation. The intense red emission was observed in Y₂WO₆: Eu³⁺, and blue and yellow ones were observed in Y₂WO₆: Dy³⁺. Concentration quenching in Y₂WO₆: Dy³⁺ phosphors could be attributed to the electric dipole-dipole interaction. In Eu³⁺/Dy³⁺ co-doped Y₂WO₆ phosphors energy transfer process only took place from the host to Eu³⁺/Dy³⁺ ions and warm white-light emission can be obtained by adjusting the dopant concentrations. The temperature-dependent luminescence indicated Eu³⁺/Dy³⁺ co-doped Y₂WO₆ was thermally stable. Our overall results suggested that Y₂WO₆: Ln³⁺ (Ln³⁺=Eu³⁺, Dy³⁺) as warm white-light emitting host-sensitized phosphor might be potentially applied in WLEDs.     

White light emission from Eu co-activated Ca2Gd8Si6O26:Dy nanophosphors by solvothermalsynthesis

Ca₂Gd₈(SiO₄)₆O₂ (CGS) nanophosphors with different concentrations of single-doped Dy³⁺ ions and co-doped Dy³⁺/Eu³⁺ ions were prepared by a solvothermal synthesis. Very fine particles in the nanometer range could be achieved by this method, as evidenced by transmission electron microscope measurements. The hexagonal phase of the oxyapatite structure was confirmed by X-ray diffraction patterns. The energy transfer between Eu³⁺ and Dy³⁺ ions was investigated by photoluminescence excitation and emission properties. These phosphors had absorption bands in the UV and NUV region, which are suitable for the emission wavelength of UV or NUV light-emitting diodes (LEDs). With increasing the Eu³⁺ ion concentration, the emission peak intensity corresponding to the ⁵D₀→⁷F₂ transition increased and the yellow (⁴F_9/2→⁶H_13/2) emission intensity also increased compared to the blue (⁴F_9/2→⁶H_15/2) emission intensity due to the increased energy transfer between Dy³⁺ to Eu³⁺ ions. Thus, the Eu³⁺ ions compensated the red emission component of the Dy³⁺ doped CGS nanophosphors. Such phosphors are expected to have potential applications for NUV based white LEDs.     

Structure and Luminescence Characteristics of Eu3+‐Activated Trigonal Layered Perovskite Ba2La2ZnW2O12

Eu³⁺‐doped tungstate Ba₂La₂ZnW₂O₁₂ phosphors with perovskite‐structure were prepared by the high temperature solid‐state reaction. The X‐ray powder diffraction (XRD) patterns and structure refinements indicate that the phosphors crystalized in the trigonal layer‐perovskite. The luminescence properties of the phosphors were investigated such as photoluminescence (PL) excitation and emission spectra, decay lifetimes, and color coordinates. It was found that the pure host shows self‐activated emission excited by the UV light. Moreover, Ba₂La₂ZnW₂O₁₂ also shows scintillation characteristics under the X‐ray irradiation. The near‐UV and blue light can efficiently excite Eu³⁺‐doped Ba₂La₂ZnW₂O₁₂ phosphors inducing the strong orange–red luminescence. The optimal Eu³⁺ doping concentration in this host is 40 mol%. The luminescence spectra and the luminescence color of the phosphors strongly depend on the doping levels and excitation wavelength. The different luminescence features were discussed on the base of crystal structure. Eu³⁺ ions have two possible substitutions on A or B sites in this trigonal layered perovskite. The phosphor could act as a candidate for the potential application in near‐UV excited white‐LEDs lighting.     

Synthesis and luminescence properties of single‐component Ca5(PO4)3F:Dy3+, Eu3+ white‐emitting phosphors

A series of Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ phosphors was synthesized by a solid‐state reaction method. The XRD results show that all as‐prepared Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ samples match well with the standard Ca₅(PO₄)₃F structure and the doped Dy³⁺ and Eu³⁺ ions have no effect on the crystal structure. Under near‐ultraviolet excitation, Dy³⁺ doped Ca₅(PO₄)₃F phosphor shows blue (486 nm) and yellow (579 nm) emissions, which correspond to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions respectively. Eu³⁺ co‐doped Ca₅(PO₄)₃F:Dy³⁺ phosphor shows the additional red emission of Eu³⁺ at 631 nm, and an improved color rendering index. The chromaticity coordinates of Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ phosphors also indicate the excellent warm white emission characteristics and low correlated color temperature. Overall, these results suggest that the Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ phosphors have potential applications in warm white light‐emitting diodes as single‐component phosphor.     

Dy and Eu activated Ca3B2O6 phosphors for near ultraviolet‐based light‐emitting diodes

The Dy‐ and Eu‐activated Ca₃B₂O₆ phosphors were synthesized by a high‐temperature solid‐state reaction technique and their structural and luminescent properties were investigated. The phosphors are characterized by X‐ray diffraction, photoluminescence spectra, and Commission International de I'Eclairage (CIE) chromaticity coordinates. It is found that the charge compensator Na⁺ plays an important role in modifying the emission spectral profiles of Dy and Eu ions in the phosphors. The ratio of the emission located at the yellow wavelength portion to that located at the blue wavelength region of the Dy³⁺ ions can be apparently tuned by changing the Na⁺ content. The luminescence intensity of the phosphors can be enhanced with introducing Na⁺ ions as well. The emission colors of Dy/Eu codoped phosphors change from blue to white and successfully acquire the superior white light emission (x = 0.330, y = 0.329) by appropriately tuning the Na⁺/Dy³⁺ content and the excitation wavelength. The energy transfer process from Eu²⁺ to Dy³⁺ and Eu³⁺ occurs in the Dy/Eu codoped phosphors, providing a further approach to modify the emission spectral profile of the examined phosphors. The phosphors presented here have promising applications in the fields of light‐emitting diodes.     

Tunable white light and energy transfer of Dy3+ and Eu3+ doped Y2Mo4O15 phosphors

A series of Dy³⁺ or/and Eu³⁺ doped Y₂Mo₄O₁₅ phosphors were successfully synthesized at a low temperature of 600 °C via solid state reaction. The as-prepared phosphors were characterized by X-ray powder diffraction (XRD), scanning electronic microscope (SEM), photoluminescence (PL) excitation, emission spectra and PL decay curves. XRD results demonstrate that Y₂Mo₄O₁₅: Dy³⁺, Eu³⁺ has the monoclinic structure with the space group of p21/C(14). Under the excitation of ultraviolet (UV) or near-UV light, the Dy³⁺ and Eu³⁺ ions activated Y₂Mo₄O₁₅ phosphors exhibit their characteristic emissions in the blue, yellow and red regions. The emitting light color of the Y₂Mo₄O₁₅: 0.08Dy³⁺, yEu³⁺ phosphors can be adjusted by varying the concentration ratio of Dy³⁺ to Eu³⁺ ions and a white light is achieved when the doping concentration of Eu³⁺ is 5%. In addition, the energy transfer from Dy³⁺ to Eu³⁺ is also confirmed based on the luminescence spectra and decay curves.     

Spectroscopic investigations on high efficiency deep red-emitting Ca2SiO4:Eu3+ phosphors synthesized from agricultural waste

Europium doped calcium orthosilicate (Ca₂SiO₄) phosphors have been synthesized by the conventional high temperature solid-state reaction method in various concentrations from agricultural waste (egg shell as a CaO and rice husk as a SiO₂). These phosphors structure from X-ray diffraction and morphology from scanning electron microscopy have been examined. Concentration dependent Eu³⁺ ions luminescent properties in Ca₂SiO₄ phosphors have been studied from the excitation, emission and decay curves analysis. The ⁵D₀ → ⁷F_J transitions observed in luminescence spectrum allows to determine the site symmetry of the Eu³⁺ ion. A charge transfer band (CTB) at around 260?nm which is due to the Eu–O interaction in the host along with the 4f – 4f excitation bands due to Eu³⁺ ions in UV and blue regions are observed. The color co-ordinates determined from emission spectra varies with concentrations of Eu³⁺ ions and are found to fall in the red region. The decay curves show single exponential behavior for all concentrations of Eu³⁺ ions (0.01–0.4?mol%) and the lifetimes varied from 2.67 to 2.78?ms. It is worth noting that the present material is found to be far better than many red phosphors synthesized by using agricultural waste as raw materials.     

Synthesis and photoluminescence performance of single-component Ca3YAl3B4O15:Dy3+, Eu3+ white-emitting phosphor for white light-emitting diodes

A single-component Ca₃YAl₃B₄O₁₅ (CYAB):Dy³⁺, Eu³⁺ phosphor was synthesized by the traditional high temperature solid-phase method, Dy³⁺ and Eu³⁺ were codoped in the structure to obtain a warm white emission. The results of XRD and EDS revealed that all samples had the standard Ca₃YAl₃B₄O₁₅ structure, and no impurity phase appeared with codoping. The emission of Dy³⁺ in CYAB consisted of both main peaks at 476 nm and 570 nm, with which a white emission could be observed. Furthermore, a characteristic emission peak of Eu³⁺ appeared at 617 nm in Dy³⁺/Eu³⁺-codoped samples to supplement red component for the white emission of Dy³⁺, due to the energy transfer effect between Dy³⁺ and Eu³⁺. With the amount of Eu³⁺ raised, the correlated colour temperature of CYAB:Dy³⁺, Eu³⁺ phosphor obviously decreased, and a warm white light was successfully realized from the manufactured w-LEDs. Therefore, all results indicated that the single-component Dy³⁺/Eu³⁺ codoped CYAB white-emitting phosphor had a potential application in ultraviolet excited w-LEDs.     

Citrate-based sol–gel synthesis and luminescent properties of Y6WO12:Eu3+, Dy3+ phosphors for solid-state lighting applications

The rare-earth ions (Eu³⁺, Dy³⁺) doped Y₆WO₁₂ phosphors were prepared by a citrate-based sol–gel method. The morphologies and structural properties of the as-prepared and doped samples were analyzed by scanning electron microscope images and X-ray diffraction patterns. The luminescent properties were studied by examining the excitation and emission spectra of the samples. The Eu³⁺ and Dy³⁺ ions doped samples exhibited their characteristic emission bands in the visible region under ultraviolet light excitation. The temperature-dependent photoluminescence (PL) properties of the samples were also investigated. The PL spectra of the synthesized samples by the sol–gel method were compared with those of the bulk sample prepared by a solid-state reaction. Similarly, the Commission International de I’Eclairage chromaticity coordinates and the decay times of Y₆WO₁₂:Eu³⁺ (3 mol%) and Y₆WO₁₂:Dy³⁺ (2 mol%) phosphors were studied.     

Tunable full-color emission phosphors: Enhanced security application via a patterned 3-dimensions code

Developing tunable full-color emission photoluminescent materials is always desired in color-on-demand applications and still confronts challenges. Theoretically, full color including white emission can be achieved by the combination of three primary colors (red, green, and blue) based on the additive color theory. Herein, a strategy for the preparation of tunable full-color luminescence is realized by mixing the inorganic rare-earth-doped SrAl₂O₄: Eu²⁺, Dy³⁺ (green emission), Y₂O₂S: Eu³⁺, Mg²⁺, Ti⁴⁺, Ti⁴⁺_0.05 (red emission), and Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ (blue emission) phosphors with different ratios. By adjusting individual phosphors at certain specific ratios, white light (0.332, 0.332) and full-spectra emission are achieved under a single low excitation energy (λ_ex = 365 nm) using a portable ultraviolet (UV) lamp. Based on the facile preparation and effective tunable full-color emission features of the phosphors, a novel encryption way of the luminescent unit as information storage 3 dimensions (3D) codes is developed. The multiplexed encrypting information capacity of the codes is enhanced in a 3D maneuver strategy by simply adjusting the number of light-emitting units with infinite emission colors. The proposed strategy makes the tunable full-color emission phosphors useful in promising applications including full-color display, high-level information encryption and anti-fake.     

Red-shift and improved afterglow of Sr3Al2-xBxO5Cl2:Eu2+, Dy3+ phosphors via a cation substitution strategy

Sr₃Al_2-xB_xO₅Cl₂:Eu²⁺, Dy³⁺ (x = 0, 0.2, 0.4) long persistent phosphors were prepared via solid-state process. The pristine Sr₃Al₂O₅Cl₂:Eu²⁺, Dy³⁺ phosphor exhibits orange/red broad band emission around 609 nm, which can be attributed to the electric radiation transitions 4f⁶5 d¹→4f⁷ of Eu²⁺. Upon the same excitation, the B³⁺-doped Sr₃Al_2-xB_xO₅Cl₂:Eu²⁺, Dy³⁺ phosphors display red-shift from 609 nm to 625 nm with increasing B³⁺ concentrations. The XRD patterns show that Al³⁺ can be replaced by B³⁺ in the host lattice at the tetrahedral site, which causes lattice contraction and crystal field enhancement, and thereafter achieves the red-shift on the emission spectrum. The XPS investigation provides direct evidence of the dominant 2-valent europium in the phosphor, which can be ascribed for the broad band emission of the prepared phosphors. The afterglow of all phosphors show standard double exponential decay behavior, and the afterglow of Sr₃Al₂O₅Cl₂:Eu²⁺, Dy³⁺is rather weak, while the sample co-doped with B³⁺shows longer and stronger afterglow, as confirmed after the curve simulation. The analysis of thermally stimulated luminescence showed that, when B³⁺ is introduced, a much deeper trap is created, and the density of the electron trap is also significantly increased. As a result, B³⁺ ions caused redshift and enhanced afterglow for the Sr₃Al_2-xB_xO₅Cl₂:Eu²⁺, Dy³⁺ phosphor.     

Structural characterization,energy transfer,and Judd–Ofelt analysis of pure and the Eu3+-doped Ca2LiMg2V3O12 phosphors

A novel vanadate host Ca₂LiMg₂V₃O₁₂ (CLMV) and the Eu³⁺-doped samples were synthesized via a solid-state reaction method. The phase formation and the morphological analysis were studied in detail. The Rietveld refinement result shows that the host belongs to cubic space group Ia-3d (230) with lattice parameter, a = 12.3948 Å, V = 1904.23 Å³, and Z = 8. The diffuse reflectance spectroscopy measurement estimated the bandgap of the host and the CLMV:0.05Eu³⁺ phosphors. The host exhibits a broad absorption band (peak at 345 nm) ranging from 240 to 380 nm, which is attributed to the charge transfer in the O²⁻–V⁵⁺ complex. Under near UV excitation (λ_exc = 345 nm), the host gives a broad emission band covering the visible region from 400 to 730 nm and the emission is in the bluish–green region of the CIE diagram. When the host is doped with the Eu³⁺ ions and excited at 345 nm, the emission spectrum depicts the superimposition of the characteristic emission bands (red emission) of the Eu³⁺ ions corresponding to the f–f transitions over the broad emission band of the host. The calculated color coordinates (9600 to 2280 K) demonstrated the color tuning ability of the phosphor as the dopant concentration is increased in the host. This is because the VO₄³⁻ group plays the sensitiser role and partially transfers energy with the Eu³⁺ ions. When the same set of phosphors were excited at the dominant characteristic excitation band (λ_exc = 394 nm) of the Eu³⁺, the characteristic emission bands of the Eu³⁺ in the orange–red region were observed. As the electric dipole transition of the Eu³⁺ was found to be dominant, the prepared phosphors possessed high color purity (CP). The energy transfer mechanism and the lifetime values were also presented. The temperature-dependent PL studies showed good thermal stability of the optimum sample. Various radiative transition properties were analyzed by the Judd–Ofelt theory. The photometric results reveal the color tuning ability and CP of the CLMV:xEu³⁺ phosphors.     

Near white light emission from K+ ion compensated CaSO4:Dy3+,Eu3+ phosphors

Dy³⁺:Eu³⁺ doped calcium sulfate (CaSO₄:Dy³⁺,Eu³⁺) phosphors co-doped with various K⁺ compensator concentrations were synthesized by recrystallization method. These orthorhombic phased phosphors showed intense multi-color near white light. The multi-color aspect ratios and the emission life times were strongly dependent on K⁺-concentration. These results suggest that the rare-earth (Re³⁺) ions are situated at the sites of Ca²⁺ and the site occupancy was being compensated by K⁺ ions. The near white light emission and large lifetimes suggest that present phosphor could be potentially applied as a blue excited white light-emitting phosphor for light emitting diodes.     

Warm-white light performance of Dy3+, Eu3+: NaLa(WO4)2 phosphors excited with a 450-nm LED

Dy³⁺, Eu³⁺: NaLa(WO₄)₂ phosphors are successfully synthesized through the solid-state reaction technique. The phase-structure and morphology are measured via X-ray diffraction and energy dispersive spectrometry. The concentrations of Dy³⁺, Eu³⁺, La³⁺, and W⁶⁺ are measured via ICP. The absorption and excited spectra are presented, which indicate that a blue band ranging from 430 to 480 nm is suitable for excitation. Using a commercial blue LED with a wavelength of 450 nm as the excitation light source, emission spectra for samples with varying dopant concentration ratios of Dy³⁺ to Eu³⁺ are obtained, which show good tunable yellow and red emission. For the purpose of investigating white LED performance, CIE spectra and a white light photo are also presented. The results reveal that varying the dopant concentration ratio of Dy³⁺ to Eu³⁺ plays a key role in the warm-white performance. With increasing concentration of Eu³⁺, the correlated color temperature decreases from 4069 to 3172 K, which indicates good warm-white performance.     

Tuning of Bi3+-related excitation and emission positions through crystal field modulation in the perovskite-structured La2(Znx, Mg1-x)TiO6 (0 ≤ x ≤ 1):Bi3+ solid solution for white LEDs

In the past year, emission-tunable crystals based on the rare-earth (RE) ions as luminescent center have been frequently reported for use in UV and blue converted white LEDs, but so far tuning the non-RE Bi³⁺ related emissions through the crystal field modulation is still not discovered in the perovskite crystals. In this work, we design and report a type of Bi³⁺ doped La₂(Zn_x,Mg_1-x)TiO₆ (0 ≤ x ≤ 1) perovskite solid solutions, which enable showing the tunable Bi³⁺ excitation and emission positions. The XRD results show that gradual substitution of smaller Mg²⁺ ions with larger Zn²⁺ ions can lead to the blue-shifting of X-ray diffraction (XRD) position, revealing the expansion of cell lattice. Together with structural analysis, our refined XRD and time-resolved spectral results reveal that there is only one type of La site available for Bi³⁺ substitution. With this regular crystal lattice change, the crystal field strength around Bi³⁺ ions is found to vary regularly, allowing to realization of the excitation and emission spectral tuning, i.e., the Bi³⁺ excitation and emission positions as the Mg ions are replaced by the Zn ions can tune from 348?nm to 392?nm and from 405?nm to 433?nm, respectively. This Bi³⁺ spectral tuning peak after calculated by the dielectric chemical bond theory features a linear relationship with the crystal field strength and, thus, is ascribed to the crystal field modulation. On basis of the La₂(Zn_0.4,Mg_0.6)TiO₆ blue, SrGa₂S₄:Eu²⁺ green and Y₂O₃:Eu³⁺ red phosphors, a UV converted warm white LED device with desirable color rendering index (CRI) of 78, correlated color temperature (CCT) of 3650 K and good luminous efficacy of 118.13?lm/W, is fabricated. This work provides new insights into using the crystal-field modulation to discover more Bi³⁺ emission-tunable crystals for white LEDs in the future.     

Synthesis,energy transfer and multicolor luminescent property of Eu3+-doped LiCa2Mg2V3O12 phosphors for warm white light-emitting diodes

In this study, Eu³⁺-doped LiCa₂Mg₂V₃O₁₂ (LCMVO) phosphors with multicolor luminescent property were prepared by the solid phase reaction. Their structure, morphology and luminescent property were studied systematically by X-ray diffraction, scanning electron microscope and photoluminescence spectra. The LCMVO phosphors showed pure cubic crystal structure with space group ($Ia\overline{3}d$) and irregular spherical morphology. The excitation spectra showed a strong absorption to ultraviolet light. Under the excitation wavelength at 360 nm, they exhibited a cyan emission with a luminescence center at 520 nm. When Eu³⁺ ions were doped into LCMVO system, the Eu³⁺ characteristic emissions were also observed and the emission colors were tuned from cyan to orange via adjusting Eu³⁺ ion concentration. Further, electric dipole-quadrupole interaction and luminescence decay curves were adopted to explain the energy transfer from (VO₄)^3- to Eu³⁺. The emission spectra of as-obtained phosphors at different temperature were measured to evaluate their thermal stability. The quantum efficiency values were measured to be 42.5% for LCMVO host and 38.6% for LCMVO: 0.01Eu³⁺ sample. The final prepared LED lamp showed easeful warm white light with suitable Ra of 89 and CCT of 3847 K, respectively. These results suggest LCMVO phosphors may be applied in near ultraviolet chip-excited white light-emitting diodes.     

Structure evolution and delayed quenching of the double perovskite NaLaMgWO6:Eu3+ phosphor for white LEDs

Eu³⁺ ions activated NaLaMgWO₆ phosphors were successfully synthesized by an improved sol-gel method using citric acid and polyethylene glycol as complexing agents. Crystal structure and doping site were investigated by XRD, Rietveld refinement and Raman spectra. The phosphors had monoclinic double perovskite structure with space group C2/m, as well as layered ordering of A-site and rock-salt ordering of B-site. The blueshift of Raman T_2g(1) mode manifested Eu³⁺ ions had entered into A-site. Thereafter, luminescence properties, such as excitation and emission spectra, CIE coordinates, concentration quenching and thermal quenching were discussed. The quenching concentration for hypersensitive electric dipole transition of Eu³⁺ reached up to 50.0 mol%. The delayed concentration quenching was observed in NaLaMgWO₆: Eu³⁺ phosphor. The theoretical quenching concentration was obtained based on L. Ozawa's theory, and the quenching mechanism on Dexter's theory. Excellent thermal stability of this phosphor shows that it is a potential red phosphor for solid state lighting.     

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.     

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.     

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.