Double emitting phosphor NaSr4(BO3)3:Ce, Tb for near-UV light-emitting diodes

Blue and green double emitting phosphor, Ce³⁺ and Tb³⁺ co-doped NaSr₄(BO₃)₃, was synthesized in a weak reducing atmosphere by a conventional high temperature solid-state reaction technique. For comparison, Ce³⁺ or Tb³⁺ singly doped NaSr₄(BO₃)₃ was also prepared. The emission and excitation spectra of all samples have been investigated. NaSr₄(BO₃)₃:Tb³⁺ excitation includes a strong absorption at about 240 nm and some weak sharp lines in near-ultraviolet (n-UV) spectral region. The excitation of Ce³⁺ and Tb³⁺ co-doped NaSr₄(BO₃)₃ shows a strong broad band absorption in the n-UV region from the contribution of Ce³⁺, which makes it suitable for excitation by a n-UV LED chip. The emission of NaSr₄(BO₃)₃:Ce³⁺,Tb³⁺ consists of a blue emission band from Ce³⁺ and a green emission from Tb³⁺ under the excitation of n-UV light. Energy transfer between Ce³⁺ and Tb³⁺ is also discussed, and the relative intensity of blue emission and green emission could be tuned by adjusting the concentration of Ce³⁺ and Tb³⁺. The phosphor NaSr₄(BO₃)₃:Ce³⁺,Tb³⁺ could be considered as a double emission phosphor for n-UV excited white light-emitting diodes.     

Synthesis and luminescence properties of Eu, Ce and Tb-activated Sr3La2(BO3)4 under UV excitation

The spectroscopic properties in UV-excitable range for the phosphors of Sr₃La₂(BO₃)₄:RE³⁺ (RE³⁺=Eu³⁺, Ce³⁺, Tb³⁺) were investigated. The phosphors were synthesized by conventional solid-state reactions. The photoluminescence (PL) spectra and commission international de I'Eclairage (CIE) coordinates of Sr₃La₂(BO₃)₄:RE³⁺ were investigated. The f-d transitions of Eu³⁺, Ce³⁺ and Tb³⁺ in the host lattices are assumed and corroborated. The PL and PL excitation (PLE) spectra indicate that the main emission wavelength of Sr₃La₂(BO₃)₄:Eu³⁺ is 611 nm, and Sr₃La₂(BO₃)₄:Ce³⁺ shows dominating emission peak at 425 nm, while Sr₃La₂(BO₃)₄:Tb³⁺ displays green emission at 487, 542, 582 and 620 nm. These phosphors were prepared by simple solid-state reaction at 1000 °C. There are lower reactive temperature and more convenient than commercial phosphors. The Sr₃La₂(BO₃)₄:Tb³⁺ applied to cold cathode fluorescent lamp was found to emit green light and have a major peak wavelength at around 542 nm. These phosphors may provide a new kind of luminescent materials under ultraviolet excitation.     

Characterization of the VUV excitation spectrum of BaZr(BO3)2:Eu

The excitation spectra of M (M=Si⁴⁺, Ti⁴⁺) and Eu³⁺ co-doped BaZr(BO₃)₂, BaZrO₃:Eu and La₂Zr₂O₇:Eu in the vacuum ultraviolet (VUV) regions of 110-300 nm are investigated and the host-lattice absorption are characterized. The result indicated that BaZr(BO₃)₂:Eu³⁺ phosphor has a strong absorption under the VUV excitation, and in the host-lattice excitation, the strong band at 130-160 nm could be due to the BO₃ atomic groups; the band at 160-180 nm is related to the excitation of Ba-O; 180-200 nm corresponds to the charge transfer (CT) transition of Zr-O. The band at 200-235 nm due to the CT band of Eu³⁺-O²⁻ and a bond valence study explained the observed weak CT band of Eu³⁺-O²⁻ in the excitation spectra of BaZr(BO₃)₂:Eu³⁺. The emission results show that Si⁴⁺ can sensitize luminescence in the host of BaZr(BO₃)₂:Eu but Ti⁴⁺ has no improvement effect on luminescence.     

Luminescence of Ce and Pr doped Sr2Mg(BO3)2 under VUV-UV and X-ray excitation

This report presents the luminescence properties of Ce³⁺ and Pr³⁺ activated Sr₂Mg(BO₃)₂ under VUV-UV and X-ray excitation. The five excitation bands of crystal field split 5d states are observed at about 46 729, 44 643, 41 667, 38 314 and 29 762 cm⁻¹ (i.e. 214, 224, 240, 261 and 336 nm) for Ce³⁺ in the host lattice. The doublet Ce³⁺ 5d→4f emission bands were found at about 25 840 and 24 096 cm⁻¹ (387 and 415 nm). The influence of doping concentration and temperature on the emission characteristics and the decay time of Ce³⁺ in Sr₂Mg(BO₃)₂ were investigated. For Pr³⁺ doped samples, the lowest 5d excitation band was observed at about 42017 cm⁻¹ (238 nm), a dominant band at around 35714 cm⁻¹ (280 nm) and two shoulder bands were seen in the emission spectra. The excitation and emission spectra of Ce³⁺ and Pr³⁺ were compared and discussed. The X-ray excited luminescence studies show that the light yields are ∼3200±230 and ∼1400±100 photons/MeV of absorbed X-ray energy for the samples Sr_1.86Ce_0.07Na_0.07Mg(BO₃)₂ and Sr_1.82Pr_0.09Na_0.09Mg(BO₃)₂ at RT, respectively.     

Photoluminescence properties of Eu in Y(PO3)3 under VUV excitation

The photoluminescence properties of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) are investigated. The excitation spectrum of Y_0.85(PO₃)₃:0.15Eu₃⁺ shows that both the (PO₃)₃³⁻ groups and the CT bands of O²⁻-Y³⁺ can efficiently absorb the excitation energy in the region of 120-250 nm. Under 147 nm excitation, the optimal emissive intensity of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) is about 36% of the commercial phosphor (Y,Gd)BO₃:Eu³⁺, which hints that the absorbed energy by the host matrix could be efficiently transferred to Eu³⁺. We try to study the concentration quenching mechanism of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) under 147 and 172 nm excitation.     

New red phosphors BaZr(BO3)2 and SrAl2B2O7 doped with Eu for PDP applications

Vacuum ultraviolet (VUV) excitation and photoluminescence (PL) characteristics of Eu³⁺ ion doped borate phosphors; BaZr(BO₃)₂:Eu³⁺ and SrAl₂B₂O₇:Eu³⁺ are studied. The excitation spectra show strong absorption in the VUV region with the absorption band edge at ca. 200 nm for BaZr(BO₃)₂:Eu³⁺ and 183 nm for SrAl₂B₂O₇:Eu³⁺, respectively, which ensures the efficient absorption of the Xe plasma emission lines. In BaZr(BO₃)₂:Eu³⁺, the charge transfer band of Eu³⁺ does not appear strongly in the excitation spectrum, which can be enhanced by co-doping Al³⁺ ion into the BaZr(BO₃)₂ lattices. The luminescence intensity of BaZr(BO₃)₂:Eu³⁺ is also increased by Al³⁺ incorporation into the lattices. The PL spectra show the strongest emission at 615 nm corresponding to the electric dipole ⁵D₀→⁷F₂ transition of Eu³⁺ in both BaZr(BO₃)₂ and SrAl₂B₂O₇, similar to that in YAl₃(BO₃)₄, which results in a good color purity for display applications.     

Effective energy transfer between Ceand Eu in CaAl2Si2O8 host under vacuum ultraviolet illumination

We presented the energy transfer from Ce³⁺ to Eu²⁺ in CaAl₂Si₂O₈ host. The Ce³⁺-doped CaAl₂Si₂O₈ phosphor had a strong emission band at 378 nm under the vacuum ultraviolet (VUV) light. This emission spectrum of Ce³⁺ well overlapped with the excitation spectrum of Eu²⁺ under the UV illumination. As a result, the energy transfer from Ce³⁺ to Eu²⁺ in CaAl₂Si₂O₈ matrix was observed under VUV excitation, which resulted in a significant enhancement of the emission peak intensity at 446 nm. More details about the luminescent properties were presented.     

Luminescence optimization of Eu-doped LnAl3(BO3)4 (Ln=Y, Gd) red phosphor using spray pyrolysis

LnAl₃(BO₃)₄:Eu³⁺ (Ln=Y, Gd) red phosphor particles were prepared by spray pyrolysis and the luminescent intensity under vacuum ultraviolet (VUV) excitation was investigated by changing Eu³⁺ content, Y/Gd molar ratio, and boron content. The concentration quenching for Eu³⁺ activator was observed at 5 at%. The highest luminescent intensity at 615 nm due to the ⁵D₀→⁷F₂ transitions of Eu³⁺ was achieved when the ratio of Gd to Y was 0.55. The R/O ratio (obtained by dividing the red emission intensity at 615 nm with the orange one at 592 nm), however, was not influenced by the G/Y ratio. Using excess boron, up to 135% of the stoichiometric quantity, improved the emission intensity of LnAl₃(BO₃)₄:Eu³⁺ red phosphor. According to XRD analysis, the sample prepared using boron of a stoichiometric quantity had YBO₃ phase as a minor phase. Such YBO₃ phase progressively disappeared with an increase in the excess quantity of boron, which was responsible for the enhancement of emission intensity. In addition, the R/O ratio became larger and larger by increasing the excess content of boron due to a reduction in the symmetry of Y site. Consequently, both the emission intensity and the color coordinate of LnAl₃(BO₃)₄:Eu³⁺ red phosphors were successfully optimized in terms of the Y/Gd ratio and the excess quantity of boron in spray pyrolysis.     

Synthesis and luminescence properties of red-emitting phosphors NaY0.87Eu0.13(WO4)1.2(MoO4)0.8

A series of NaY_1−yEu_y(WO₄)_2−x(MoO₄)_x (x=0−2 and y=0.06−0.15) phosphors have been prepared by a combustion route. X-ray powder diffraction, photoluminescence excitation and emission spectra were used to characterize the resulting samples. The excitation spectra of these phosphors show the strongest absorption at about 396 nm, which matches well with the commercially available n-UV-emitting GaN-based LED chip. Their emission spectra show an intense red emission at 616 nm due to the ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺. As the Mo content increases, the intensity of the ⁵D₀→⁷F₂ emission of Eu³⁺ activated at wavelength of 396 nm increases and reaches a maximum when the relative ratio of Mo/W is 2:3. The intense red-emission of the tungstomolybdate phosphors at near-UV excitation suggests that the material is a potential candidate for white light emitting diode (WLEDs).     

Ca2BO3Cl:Ce,Eu: A potential tunable yellow-white-blue-emitting phosphors for white light-emitting diodes

Polycrystalline Ca₂BO₃Cl:Ce³⁺,Eu²⁺ phosphors were synthesized by a solid-state reaction and which could display tunable color emission from blue to yellow under an ultraviolet (UV) source by adjusting the ratio of Ce³⁺ and Eu²⁺ appropriately. The mechanism of resonance-type energy transfer from Ce³⁺ to Eu²⁺ was established to be electric dipole-dipole natured, and the critical distance was estimated to be 31 Å based on the spectral overlap and concentration quenching model. A white light was obtained from Ca₂BO₃Cl:0.06Ce³⁺,0.01Eu²⁺ phosphor with chromaticity coordinates (x=0.31, y=0.29) and relative color temperature of 7330 K upon excitation with 360 nm, which is potentially a good candidate as an UV-convertible phosphor for white light-emitting diodes (LEDs).     

Synthesis and luminescence properties of europium doped YBa3B9O18

Europium (Eu³⁺) doped YBa₃B₉O₁₈ were synthesized by conventional solid state solidification methods. (Y_1−xEu_x)Ba₃B₉O₁₈ formed solid solutions in the range of x=0–1.0. The luminescence property measurements upon excitation in ultraviolet–visible range show well-known Eu³⁺ excitation and emission. The charge transfer excitation band of Eu³⁺ dominates the excitation spectra. The emission spectrum of Eu³⁺ ions consists mainly of several groups of lines in the 550–720 nm region, due to the transitions from the ⁵D₀ level to the levels ⁷F_J (J=0, 1, 2, 3, 4) of Eu³⁺ ions. The dependence of luminescence intensity on Eu³⁺ concentration shows no concentration quenching for fully concentrated EuBa₃B₉O₁₈. Eu³⁺ doped YBa₃B₉O₁₈ are promising phosphors for applications in displays and optical devices.     

Eu-activated Ba2Mg(BO3)2 yellow-emitting phosphors for near ultraviolet-based light-emitting diodes

A series of Eu²⁺-activated Ba₂Mg(BO₃)₂ yellow phosphors were prepared by a high temperature solid-state reaction. The phosphor emits intense yellow light under near ultraviolet excitation. Large Stokes shift can be attributed to the asymmetric nature of the Eu site and the lack of rigidity in the host. The concentration self-quenching mechanism of Ba₂Mg(BO₃)₂:Eu²⁺ is d-d interaction and the critical transfer distance is calculated to be about 12.29 Å. Prototype light-emitting diodes were fabricated by coating the Ba₂Mg(BO₃)₂:0.07Eu²⁺ phosphor onto ∼370 nm-emitting InGaN chips. The LEDs exhibit intense yellow-emitting under a forward bias of 20 mA. The results indicate that Eu²⁺-activated Ba₂Mg(BO₃)₂ is a candidate as a yellow component for fabrication of near-UV white light-emitting diodes.     

Excitation energy dependent chromaticity of BaZr(BO3)2:Eu

The luminescence properties of BaZr(BO₃)₂:5% Eu were investigated under ultraviolet (UV) and vacuum ultraviolet (VUV) excitation and different luminescence behaviors were observed by different excitation energies. After the analyses of the luminescence spectra, the result indicates that Eu³⁺ occupying non-centrosymmetric sites Ba²⁺ can be excited preferentially under 254 nm excitation, while Eu³⁺ occupying centrosymmetric sites Zr⁴⁺ can be excited preferentially under 147 nm excitation.     

Energy transfer in Y3Al5O12:Ce, Pr and CaMoO4:Sm, Eu phosphors

Non-radiative energy transfers (ET) from Ce³⁺ to Pr³⁺ in Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and from Sm³⁺ to Eu³⁺ in CaMoO₄:Sm³⁺, Eu³⁺ are studied based on photoluminescence spectroscopy and fluorescence decay patterns. The result indicates an electric dipole-dipole interaction that governs ET in the LED phosphors. For Ce³⁺ concentration of 0.01 in YAG:Ce³⁺, Pr³⁺, the rate constant and critical distance are evaluated to be 4.5×10⁻³⁶ cm⁶ s⁻¹ and 0.81 nm, respectively. An increase in the red emission line of Pr³⁺ relative to the yellow emission band of Ce³⁺, on increasing Ce³⁺ concentration is observed. This behavior is attributed to the increase of spectral overlap integrals between Ce³⁺ emission and Pr³⁺ excitation due to the fact that the yellow band shifts to the red spectral side with increasing Ce³⁺ concentration. In CaMoO₄:Sm³⁺, Eu³⁺, Sm³⁺-Eu³⁺ transfer occurs from ⁴G_5/2 of Sm³⁺ to ⁵D₀ of Eu³⁺. The rate constant of 8.5×10⁻⁴⁰ cm⁶ s⁻¹ and the critical transfer distance of 0.89 nm are evaluated.     

Luminescence characteristics of Eu3+ activated borate phosphor for white light emitting diode

In this paper, the Sr₃Y₂ (BO₃)₄:Eu³⁺ phosphor was synthesized by high temperature solid-state reaction method and the luminescence characteristics were investigated. The emission spectrum exhibits one strong red emission at 613nm corresponding to the electric dipole ⁵D₀--⁷F₂ transition of Eu³⁺ under 365nm excitation, this is because Eu³⁺ substituted for Y³⁺ occupied the non-centrosymmetric position in the crystal structure of Sr₃Y₂ (BO₃)₄. The excitation spectrum indicates that the phosphor can be effectively excited by ultraviolet (254nm, 365nm and 400nm) and blue (470nm) light. The effect of Eu³⁺ concentration on the red emission of Sr₃Y₂ (BO₃)₄:Eu³⁺ was measured, the result shows that the emission intensities increase with increasing Eu³⁺ concentration, then decrease. The Commission Internationale del'Eclairage chromaticity (x, y) of Sr₃Y₂(BO₃)₄:Eu³⁺ phosphor is (0.640,0.355) at 15 mol% Eu³⁺.     

On the Luminescence of Ce<Superscript>3+</Superscript>, Eu<Superscript>3+</Superscript>, and Tb<Superscript>3+</Superscript> in Novel Borate LiSr<Subscript>4</Subscript>(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>

This paper reports on the photoluminescence (PL) and time-resolved properties of Ce³⁺, Eu³⁺, and Tb³⁺ in novel LiSr₄(BO₃)₃ powder phosphors. Ce³⁺ shows an emission band peaking at 420 nm under 350-nm UV excitation. Energy transfer from Ce³⁺ to Mn²⁺ takes place in the co-doped samples. Eu³⁺ shows red emission under near UV excitation. LiSr₄(BO₃)₃:Eu³⁺ phosphor could be a suitable candidate for phosphor-converted solid state lighting. The luminescence lifetime is 2.13 ms for Eu³⁺ in LiSr₄(BO₃)₃:0.001Eu³⁺. As Eu³⁺ concentration increasing, the decay curves deviate from exponential behavior. Tb³⁺ shows the strongest ⁵D₄→⁷ F₅ emission line at 540 nm. Decay curves of ⁵D₄→⁷ F₅ and ⁵D₃→⁷ F₅ emission with different Tb³⁺ concentrations were also measured. Cross-relaxation process is discussed based on the decay curves.     

Low-temperature high-resolution VUV spectroscopy of Ce doped LiYF4, LiLuF4 and LuF3 crystals

For LiYF₄:Ce³⁺, LiLuF₄:Ce³⁺ and LuF₃:Ce³⁺ crystals UV/visible emission and time-resolved VUV/UV excitation spectra were recorded at liquid helium temperature with spectral resolution of 0.1 nm for excitation spectra and better than 0.3 nm for emission spectra. Well resolved fine structures due to zero-phonon lines were clearly observed in both excitation and emission spectra for LiYF₄:Ce³⁺ and LiLuF₄:Ce³⁺. For LuF₃:Ce³⁺ crystal no fine structure was detected in the spectra even at the highest spectral resolution. Under the host excitation, the fine structure for high-energy emission band of Ce³⁺ (5d-²F_5/2) in LiLuF₄:Ce³⁺ becomes well pronounced because of weaker reabsorption effect, as compared to Ce³⁺ 4f-5d absorption, due to small penetration depth for exciting radiation. As a result the crystal-field splitting for ²F_7/2 and ²F_5/2 levels of Ce³⁺ in LiLuF₄ crystal was measured. First observation of zero-phonon lines at ∼81,550 and ∼82,900 cm⁻¹ as well as vibronic side bands due to interconfigurational 4f¹⁴-4f¹³5d transitions in Lu³⁺ is reported for excitation spectrum of LiLuF₄:Ce³⁺.     

The luminescent properties of CaYBO4:Ln(Ln=Eu, Tb) under UV-VUV range

The luminescent properties of CaYBO₄:Ln(Ln=Eu³⁺, Tb³⁺) were investigated under ultraviolet (UV) and vacuum ultraviolet (VUV) region. The CT band of Eu³⁺ at about 245 nm blue-shifted to 230 nm in VUV excitation spectrum; the band with the maximum at 183 nm was considered as the host lattice absorption. For the sample of CaYBO₄:0.08Tb³⁺, the bands at about 235 and 263 nm were assigned to the f-d transitions of Tb³⁺ and the CT band of Tb³⁺ was calculated according to Jφrgensen's theory. Under UV and VUV excitation, the main emission of Eu³⁺ corresponding to the ⁵D₀-⁷F₂ transition located at about 610 nm and two intense emission of Tb³⁺ from the ⁵D₄-⁷F₅ transition had been observed at about 542 and 552 nm, respectively. With the incorporation of Gd³⁺ into the host lattice of CaYBO₄, the luminescence of Tb³⁺ was enhanced while that of Eu³⁺ was decreased because of their different excitation mechanism.     

Synthesis and luminescence investigation of RE (Eu, Tb and Ce)-doped lithium silicate (Li2SiO3)

Synthesis and photoluminescence (PL) investigations of lithium metasilicate doped with Eu³⁺, Tb³⁺ and Ce³⁺ were carried out. PL spectra of Eu-doped sample showed peaks corresponding to the ⁵D₀→⁷F_j (j=1, 2, 3 and 4) transitions under ultraviolet excitation. Strong red emission coming from the hypersensitive ⁵D₀→⁷F₂ transition of Eu³⁺ ion suggested the presence of the dopant ion in structurally disordered environment. Tb³⁺-doped silicate sample showed blue-green emission corresponding to the ⁵D₄→⁷F_j (j=6, 5 and 4) transitions. Ce-doped sample under excitation from UV, showed a broad emission band in the region 350-370 nm with shoulders around 410 nm. The fluorescence lifetimes of Eu³⁺ and Tb³⁺ ions were found out to be 790 and 600 μs, respectively. For Ce³⁺, the lifetime was of the order of 45 ns. PL spectra of the europium- and terbium-doped samples were compared with commercial red (Y₂O₃:Eu³⁺) and green (LaPO₄:Tb³⁺) phosphors, respectively. It was found that the emission from the doped silicate sample was 37% of the commercial phosphor in case of the Tb-doped sample and 8% of the commercial phosphor in case of the Eu-doped sample.     

Synthesis and photoluminescence properties of MZr2(PO4)3:Eu3+; Bi3+ (M=Na; K) phosphors

A series of new red phosphors, MZr₂(PO₄)₃:Eu³⁺; Bi³⁺ (M=Na; K), were synthesized using the solidstate reaction method, and their photoluminescence spectra were measured. The MZr₂(PO₄)₃:Eu³⁺; Bi³⁺ (M=Na; K) phosphors were efficiently excited by an ultraviolet (UV; 395 nm) source, and showed intense orange-red emission at 595 nm. Further investigation of the concentration-dependent emission spectra indicated that the MZr₂(PO₄)₃:Eu³⁺; Bi³⁺ (M=Na; K) phosphors exhibit the strongest luminescence intensity when y = 0.01 in NaZr_2(0:95−y)(PO₄)₃:Eu_0.10³⁺, Bi_2y ³⁺ and y = 0.09 in NaZr_2(0.95−y)(PO₄)₃:Eu_0.10³⁺, Bi_2y ³⁺, whereas the relative PL intensity decreases with increasing Bi³⁺ concentration due to concentration quenching. The addition of Bi³⁺ widens the excitation band of NaZr_2(0.95−y)(PO₄)₃:Eu_0.10³⁺, Bi_2y ³⁺ around 320 nm, which provides the useful idea of broadening the excitation band around 300–350 nm to fit the ultraviolet chip.