Novel red phosphors LaBSiO5 co-doped with Eu3+, Al3+ for near-UV light-emitting diodes

Red-emitting phosphors LaBSiO₅:Eu³⁺ and LaBSiO₅:Eu³⁺, Al³⁺ were synthesized by the conventional solid state method at 1100 °C. The structure and luminescent properties of these phosphors are investigated. LaBSiO₅:Eu³⁺ and LaBSiO₅:Eu³⁺, Al³⁺ could be efficiently excited by near ultraviolet light with the strongest excitation peak at 395 nm. The main emission peak is located at around 616 nm, which corresponds to the transition of ⁵D₀ → ⁷F₂ of Eu³⁺ ions. The emission intensity of LaBSiO₅:Eu³⁺ was enhanced by introducing Al³⁺ ions. Compared with Y₂O₂S:0.05Eu³⁺, the sample La_0.70B_0.75SiO₅:0.30Eu³⁺, 0.25Al³⁺ shares the intense red emission, and its emission intensity is about 3.8 times as strong as that of Y₂O₂S:0.05Eu³⁺ under 395 nm light excitation. Bright red light can be observed from the red LED based on La_0.70B_0.75SiO₅:0.30Eu³⁺, 0.25Al³⁺, hence La_0.70B_0.75SiO₅:0.30Eu³⁺, 0.25Al³⁺ maybe find application on near-UV InGaN-based white LEDs.     

VUV–UV luminescence of Ce3+, Tb3+, Eu3+, and Dy3+ doped GdOCl

The vacuum ultraviolet spectroscopic properties of GdOCl:Re³⁺ (Re³⁺ = Ce³⁺, Tb³⁺, Eu³⁺, and Dy³⁺) are investigated in detail for the first time. The host absorption band is determined to be around 179 nm, and the f–d transition bands as well as the charge transfer bands are assigned. Upon 179 nm excitation, Re³⁺ (Re³⁺ = Ce³⁺, Tb³⁺, Eu³⁺, Dy³⁺) ions shown their characteristic emissions. Energy transfers from Gd³⁺ to Re³⁺ ion were observed. A broad band ranging from 350 to 400 nm corresponding to the d–f transition of Ce³⁺ is observed. Eu³⁺ has typical red emission with the strongest peak at 620 nm; Tb³⁺ shows characteristic transition of ⁵D_3,4 → ⁷F_j, and its spin-forbidden and spin-allowed f–d transitions in VUV region are calculated with Dorenbos’ equations, these calculated values agree well with the experimental results. Dy³⁺ presents yellow emission (⁴F_9/2 → ⁶H_13/2) with the strongest peak at 573 nm.     

Synthesis and two-color emission properties of BaGd2(MoO4)4:Eu3+,Er3+,Yb3+ phosphors

Eu³⁺, Er³⁺ and Yb³⁺ co-doped BaGd₂(MoO₄)₄ two-color emission phosphor was synthesized by the high temperature solid-state method. The structure of the sample was characterized by XRD, and its luminescence properties were investigated in detail. Under the excitation of 395 nm ultraviolet light, the BaGd₂(MoO₄)₄:Eu³⁺,Er³⁺,Yb³⁺ phosphor emitted an intense red light at 595 and 614 nm, which can be attributed to ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂ transitions of Eu³⁺, respectively. The phosphor will also show bright green light under 980 nm infrared light excitation. The green emission peaks centred at 529 and 552 nm, were attributed to ⁴H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions of Er³⁺, respectively. It indicated that the two-color emission can be achieved from the same BaGd₂(MoO₄)₄:Eu³⁺,Er³⁺,Yb³⁺ host system based on the different pumping source, 395 nm UV light and 980 nm infrared light, respectively. The obtained results showed that this kind of phosphor may be potential in the field of multi-color fluorescence imaging and anti-counterfeiting.     

Investigation on the luminescence of RE3+ (RE = Ce,Tb, Eu and Tm) in KMGd(PO4)2 (M = Ca,Sr) phosphates

The VUV excited luminescent properties of Ce³⁺, Tb³⁺, Eu³⁺ and Tm³⁺ in the matrices of KMGd(PO₄)₂ (M = Ca, Sr) were investigated. The bands at about 165 nm and 155 nm in the VUV excitation spectra are attributed to host lattice absorptions of the two matrices. For Ce³⁺-doped samples, the Ce³⁺ 5d levels can be identified. As for Tb³⁺-doped samples, typical 4f–5d absorption bands in the region of 175–250 nm were observed. For Eu³⁺ and Tm³⁺-doped samples, the O²⁻–Eu³⁺ and O²–Tm³⁺ CTBs are observed to be at about 229 nm and 177 nm, respectively. From the standpoints of color purity and luminescent efficiency, KCaGd(PO₄)₂:Tb³⁺ is an attractive candidate of green light PDP phosphor.     

Photoluminescence properties of Y0.95 − xMxBO3:Eu3+ (M = Ca,Sr, Ba,Zn, Al, 0 ≤ x ≤ 0.1) in 100–450 nm regions

The single phases of Y_0.95 − xM_xBO₃:5%Eu³⁺ (M = Ca, Sr, Ba, Zn, Al, 0 ≤ x ≤ 0.1) were synthesized successfully by solid-state reaction. Their luminescent properties were studied under UV and VUV excitation. The results indicated that with the incorporation of Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺ or Al³⁺ into the host lattice of YBO₃:Eu³⁺, the high symmetry around Eu³⁺ was destroyed and the ratio of red emission(⁵D₀–⁷F₂) to orange one (⁵D₀–⁷F₁) increased, leading to a better chromaticity. Furthermore, the co-doping ions such as Ca²⁺, Zn²⁺ and Al³⁺ were beneficial to enhance the luminescent intensity of Eu³⁺. These phenomena were evaluated, and possible explanations were proposed.     

Photoluminescence properties of Sr3(PO4)2: Eu2+, Dy3+ double-emitting blue phosphor for white LEDs

Double-emitting blue phosphor Sr₃(PO₄)₂: Eu²⁺, Dy³⁺ was synthesized by solid state reaction under H₂ atmosphere. XRD exhibited the pure hexagonal phase of the prepared phosphor. The photoluminescence results showed that all samples had intense broad absorption band between 250 and 450 nm, which matched well with the near-UV (350–420 nm) emission band of InGaN-based chips. The emission spectrum of Sr₃(PO₄)₂: Eu²⁺, Dy³⁺ consisted of two broad bands, peaked at 485 nm and 410 nm, which originated from two luminescent centers, related to 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ in six-coordinated Sr(I) and ten-coordinated Sr(II) sites respectively. The intensity ratio of two emission bands could be easily tuned by adjusting Dy³⁺ co-doping content, which resulted in color-tunable luminescence in bluish green region to purplish blue region.     

Microwave-assisted synthesis and characterization of LaPO4:Re (Re = Ce3+, Eu3+, Tb3+) nanorods

LaPO₄:Re (Re = Ce³⁺, Eu³⁺ and Tb³⁺) nanorods have been successfully synthesized on a large scale by a facile and rapid microwave heating method. The structure, morphology and physical properties of the as-prepared products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence spectroscopy (PL). XRD patterns showed that the as-prepared products had hexagonal structure and high crystallinity and purity. TEM images showed that these LaPO₄:Re nanorods have a high yield and an obvious one-dimensional structure with diameter from 6 nm to 30 nm and length up to 400 nm. The luminescence spectra of the products indicated that different rare-earth ions had been successfully doped in LaPO₄ matrix via the microwave heating method and the actual doping amounts of Re ions were determined by the inductively coupled plasma (ICP).     

Combustion synthesis and luminescence properties of yellow-emitting phosphors Ca2BO3Cl:Eu2+

Yellow-emitting phosphor Ca₂BO₃Cl:Eu²⁺ was synthesized by a solution-combustion method. The phase structure and microstructure were determined by the X-ray diffraction (XRD) and scanning electron microscope (SEM) analysis, respectively. The as-prepared Ca₂BO₃Cl:Eu²⁺ phosphor absorbed near ultraviolet and blue light of 320–500 nm, and showed an intense yellow emission band centered at 569 nm with the CIE coordinate of (0.453, 0.526). The lifetime of Eu²⁺ ions in Ca₂BO₃Cl:Eu²⁺ phosphor was measured, furthermore the temperature dependent luminescence property and mechanism were studied, which also testified that the present phosphor had a promising potential for white light-emitting diodes.     

Formation and spectral probing of transparent oxyfluoride glass-ceramics containing (Eu2+, Eu3+:BaGdF5) nano-crystals

In the present study, we report the formation of transparent glass-ceramics containing BaGdF₅ nanocrystals under optimum ceramization of SiO₂–BaF₂–K₂O–Sb₂O₃–GdF₃–Eu₂O₃ based oxyfluoride glass and the energy transfer mechanisms in Eu²⁺ → Eu³⁺ and Gd³⁺ → Eu³⁺ has been interpreted through luminescence study. The modification of local environment surrounding dopant ion in glass and glass ceramics has been studied using Eu³⁺ ion as spectral probe. The optimum ceramization temperature was determined from the differential scanning calorimetry (DSC) thermogram which revealed that the glass transition temperature (T_g), the crystallization onset temperature (T_x), and crystallization peak temperature (T_p) are 563 °C, 607 °C and 641 °C, respectively. X-ray diffraction pattern of the glass-ceramics sample displayed the presence of cubic BaGdF₅ phase (JCPDS code: 24-0098). Transmission electron microscopy image of the glass-ceramics samples revealed homogeneous distribution of spherical fluoride nanocrystals ranging 5–15 nm in size. The emission transitions from the higher excited sates (⁵D_J, J = 1, 2, and 3) as well as lowered asymmetry ratio of the ⁵D₀ → ⁷F₂ transition (forced electric dipole transition) to that of the ⁵D₀ → ⁷F₁ transition (magnetic dipole) of Eu³⁺ in the glass-ceramics when compared to glass sample demonstrated the incorporation of dopant Eu³⁺ ions into the cubic BaGdF₅ nanocrystals with higher local symmetry with enhanced ionic nature. The presence of absorption bands of Eu²⁺ ions and Gd³⁺ ions present in the glass matrix or fluoride nanocrystals in the excitation spectra of Eu³⁺ by monitoring emission at 614 nm indicated energy transfer from (Eu²⁺ → Eu³⁺) and (Gd³⁺ → Eu³⁺) in both glass and glass-ceramics samples.     

Optical studies on X and γ irradiated vacuum grown CsBrI:Eu2+ crystals

CsBr_0.9I_0.1:Eu²⁺ crystals were grown by Bridgman technique. Optical absorption spectrum of the unirradiated CsBr_0.9I_0.1:Eu²⁺ crystals show absorption bands at 270 nm and 340 nm. Irradiated CsBr_0.9I_0.1:Eu²⁺ shows single F band for F(Br⁻) and F(I⁻) centers at 730 nm. Conversion of Eu²⁺ to Eu³⁺ after irradiation is confirmed by optical absorption technique. Sharp and single Photoluminescence (PL) emission band is observed at 440 nm for CsBr_0.9I_0.1:Eu²⁺ crystals. Photostimulated Luminescence (PSL) emission band observed for CsBr_0.9I_0.1:Eu²⁺ crystals at 442 nm due to excitation at 730 nm shows that the F centers are photostimulable. PSL emission intensity increases linearly with irradiation dose up to 2.5 Krad.     

Luminescence of Eu3+ and Pr3+ in the weberite,Ca2La3Sb3O14

The spectroscopic properties of the Eu³⁺ and Pr³⁺ ions in the weberite, Ca₂La₃Sb₃O₁₄ are examined in this paper. The Eu³⁺ is used as a structural probe ion to elucidate the local site symmetry of the La³⁺ ion in Ca₂La₃Sb₃O₁₄. The interpretation of the Eu³⁺ emission spectrum is not consistent with the C_2h and S₂ (C_i) point symmetry that are prescribed for the La³⁺ sites by the I2/m11 space group of Ca₂La₃Sb₃O₁₄. The emission spectrum of Ca₂La₃Sb₃O₁₄:Pr³⁺ is dominated by emission transitions emanating from the ¹D₂ state. The low energy of the Pr³⁺4f² → 4f¹5d¹ interconfiguration excitation transition in Ca₂La₃Sb₃O₁₄ (3.83 eV or 32 258 cm⁻¹) is attributed to the high covalence which is induced by short Pr³⁺O²⁻ bond distances within the coordination polyhedral units in the lattice. The high covalence of chemical bonding appears to be the hallmark of the weberite structure. A study that compares the optical properties of Eu³⁺ and Pr³⁺ in the weberites, Ca₂La₃Sb₃O₁₄ and NaGdSb₂O₇ is presented.     

Synthesis,characterization and luminescence of Sr3Al2O6 phosphor with trivalent rare earth dopant

The luminescent properties of Sr₃Al₂O₆ doped and co-doped with the rare earths (Ln³⁺ = Eu³⁺, Dy³⁺, Eu³⁺ and Dy³⁺) have been studied. The material was synthesized by reflux method and fired up to 900 °C for 16 h. The X-ray diffraction pattern confirms that the synthesized material consists of Sr₃Al₂O₆ as main phase. The photoluminescence study gives a clear evidence of europium stabilizing in trivalent form and surprisingly with no presence of europium in the divalent state. The addition of Dy³⁺ as co-dopant in the Sr₃Al₂O₆:Eu³⁺ matrix shows the quenching effect in the photoluminescence (PL) spectra. The photoluminescence intensity of Eu³⁺ falls gradually on increasing the concentration of the co-dopant in the range from 0.1 mole% to 2.0 mole%. The significantly intense thermoluminescence (TL) glow peak was obtained for Sr₃Al₂O₆:Eu³⁺, Dy³⁺ (1% and 0.1%) at around 194 °C when irradiated with 10 kGy dose from Sr-90 β source.     

Synthesis and luminescent properties of SrZnO2:Eu3+,M+ (M = Li,Na, K) phosphor

In this paper, a series of novel luminescent materials, SrZnO₂:Eu³⁺,M⁺ (M = Li, Na, K) have been synthesized by conventional solid-state reaction. X-ray diffraction (XRD) patterns and photoluminescence (PL) spectra were carried out to characterize their structural and luminescent properties. It was found that under ultraviolet excitation with a wavelength of 301 nm, SrZnO₂:Eu³⁺ gives a red luminescence that was attributed to the transitions from ⁵D₀ excited states to ⁷F_J (J = 0–4) ground states of Eu³⁺ ions. The feature and the high intensity of hypersensitive transition ⁵D₀ → ⁷F₂ indicate that Eu³⁺ prefers to occupy a low symmetry site. The incorporation of alkali metal ions greatly enhanced the luminescence intensity and slightly changed the excitation and emission peak position, probably due to the influence of the coordination conditions for Eu³⁺ ions.     

Preparation and luminescence properties of yellow long-lasting phosphor Ca2ZnSi2O7:Eu2+, Dy3+

Long-lasting phosphors Ca₂ZnSi₂O₇:Eu²⁺, Dy³⁺ are prepared by solid-state reaction method assisted with different fluxes. Broadband emission, peaked at 580 nm and originating from 4f to 5d transition of Eu²⁺, is observed. The emission intensities of the phosphors can be enhanced by 4.84 and 7.73 times with the introduction of H₃BO₃ and CaF₂, respectively. Moreover, their afterglow times are also respectively prolonged to 11 h and 12 h. The yellow afterglow can be excited by both ultraviolet and visible light, thus permitting its application in both room and outdoor environment. In terms of the crystal structure and trap feature of the phosphors added with different fluxes, the mechanism for the improved luminescence and afterglow properties is discussed.     

Synthesis and photoluminescence properties of a cyan-emitting phosphor Ca3(PO4)2:Eu2+ for white light-emitting diodes

In this paper, a cyan-emitting phosphor Ca₃(PO₄)₂:Eu²⁺ (TCP:Eu²⁺) was synthesized and evaluated as a candidate for white light emitting diodes (WLEDs). This phosphor shows strong and broad absorption in 250–450 nm region, but the emission spectrum is prominent at around 480 nm. The emission intensity of the TCP:Eu²⁺ was found to be 60% and 82% of that of the commercial BaMgAl₁₀O₁₇:Eu²⁺ (BAM) under excitation at 340 nm and 370 nm, respectively. Upon excitation at 370 nm, the absolute internal and external quantum efficiencies of the Ca₃(PO₄)₂:1.5%Eu²⁺ are 60% and 42%, respectively. Moreover, a white LED lamp was fabricated by coating TCP:Eu²⁺ with a blue-emitting BAM and a red-emitting CaAlSiN₃:Eu²⁺ on a near-ultraviolet (375 nm) LED chip, driven by a 350 mA forward bias current, and it produces an intense white light with a color rendering index of 75.     

Luminescence properties and energy transfer of a novel bluish-green tunable NaBa4(BO3)3:Ce3+, Tb3+ phosphor

A series of single-phased emission tunable NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ phosphors were synthesized by solid-state reaction. The crystal structure, photoluminescence properties, concentration quenching and energy transfer of NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ were systematically investigated. The wavelength-tunable bluish-green light can be realized by coupling the emission bands centered at 425 and 543 nm ascribed to the contribution from Ce³⁺ and Tb³⁺, respectively. The energy transfer from Ce³⁺ to Tb³⁺ in NaBa₄(BO₃)₃ host was studied and demonstrated to be a resonant type via a dipole–dipole interaction mechanism. The energy transfer efficiency (Ce³⁺ → Tb³⁺) obtained by decay curves was consistent with the result calculated by the emission intensity, which gradually increased from 0% to 84.5% by increasing the Tb³⁺ doping content from 0 to 0.45. The results indicate that the NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ phosphors have potential applications as an ultraviolet-convertible phosphor due to its effective excitation in the ultraviolet rang.     

Crystal growth and photoluminescence characteristics of Ca2MgSi2O7:Eu3+ thin films grown by pulsed laser deposition

Ca₂MgSi₂O₇:Eu³⁺ films were deposited on Al₂O₃ (0 0 0 1) substrates by pulsed laser deposition. The films were grown at various oxygen pressures ranging from 100 to 400 mTorr. The crystallinity and surface morphology of the films were examined by X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. XRD and AFM respectively showed that the Ca₂MgSi₂O₇:Eu³⁺ films had a zircon structure and consisted of homogeneous grains ranging from 100 to 400 nm depending on the deposition conditions. The radiation emitted was dominated by a red emission peak at 620 nm. The maximum PL intensity of the Ca₂MgSi₂O₇:Eu³⁺ films grown at 300 mTorr was increased by a factor of 1.3 compared to that of Ca₂MgSi₂O₇:Eu³⁺ films grown at 100 mTorr. The crystallinity, surface roughness and photoluminescence of the thin-film phosphors were strongly dependent on the deposition conditions, in particular, the oxygen partial pressure.     

Synthesis and luminescence properties of red long-lasting phosphor Y2O2S:Eu3+, Mg2+, Ti4+ nanoparticles

We report an effective method to synthesize Y₂O₂S:Eu³⁺, Mg²⁺, Ti⁴⁺ nanoparticles. Tube-like Y(OH)₃ were firstly synthesized by hydrothermal method to serve as the precursor. Nanocrystalline long-lasting phosphor Y₂O₂S:Eu³⁺, Mg²⁺, Ti⁴⁺ was obtained by calcinating the precursor with co-activators and S powder. XRD investigation shows a pure phase of Y₂O₂S, indicating no other impurity phase appeared. SEM and TEM observation reveals that the precursor synthesized via a hydrothermal routine has tube-like structure and the final phosphor reveals a hexagonal shape. The fine nanoparticles which have the particle size ranging from 30 to 50 nm show uniform size and well-dispersed distribution. From the spectrum, the main emission peaks are ascribed to Eu³⁺ ions transition from ⁵D_J (J = 0, 1, 2) to ⁷F_J (J = 0, 1, 2, 3, 4). After irradiation by 325 nm for 10 min, the Y₂O₂S:Eu³⁺, Mg²⁺, Ti⁴⁺ long-lasting phosphor shows very bright red afterglow and the longest could last for more than 1 h even after the irradiation source had been removed. It is considered that the long-lasting phosphorescence is due to the contribution from the electron traps with suitable trap depth.     

Photoluminescence of CaAlSiN3:Eu2+-based fine red-emitting phosphors synthesized by carbothermal reduction and nitridation method

In this research, we have presented the synthesis and characterization of the various Ca_1−xEu_xAl_0.76Si_1.18N₃ (x = 0.01 ∼ 0.1) red-emitting phosphors, which were successfully prepared by carbothermal reduction and nitridation (CTRN) method without the strict needs of high pressure. Here, raw materials were CaCO₃, AlN, Si₃N₄, Eu₂O₃, and C. In particular, C was considered as efficient and robust reducing agent. The influences of reaction temperature, holding time, C content, and Eu²⁺ concentration were investigated in the crystal phase compositions and photoluminescence properties of the as-prepared phosphors. Importantly, CaAlSiN₃:Eu²⁺-based red phosphors with interesting properties were obtained with reaction temperature at 1600 °C for 4 h by atmospheric N₂–10%H₂ pressure, and the C/O ratio of 1.5:1, respectively. The emission peak positions of as-prepared phosphors were red-shifted from 607 nm to 654 nm with Eu²⁺ concentration from 1 mol% to 10 mol%. Meanwhile the highest luminescence intensity was achieved with 2 mol% of Eu²⁺ concentration, which showed high external quantum efficiency up to 71%. Combining the phosphor blend of green-emitting β-sialon:Eu²⁺, yellow-emitting Ca-α-sialon:Eu²⁺, and red-emitting Ca_0.98Eu_0.02Al_0.76Si_1.18N₃ with a blue LED (light emitting diodes), warm white LED can be generated, yielding the color rendering index (Ra) of 93 at correlated color temperature (CCT) of 3295 K. These results indicate that CaAlSiN₃:Eu²⁺-based red-emitting phosphors prepared by facile CTRN are highly promising candidates for warm white LEDs.     

Synthesis and luminescence properties of Ca8NaGd(PO4)6F2: Eu2+, Mn2+ for white LEDs

A series of luminescent emission-tunable phosphors Ca₈NaGd(PO₄)₆F₂: Eu²⁺, Mn²⁺ have been prepared by a combustion-assisted synthesis method. The X-ray diffraction measurement results indicate that the crystal structure of the phosphor is a single phase of Ca₈NaGd(PO₄)₆F₂. The photoluminescence (PL) properties of Eu²⁺ and Mn²⁺-codoped Ca₈NaGd(PO₄)₆F₂ phosphors were also investigated. The phosphors can be efficiently excited by ultraviolet (UV) light and show a blue emission band at about 450 nm and a yellow emission band at about 574 nm, which originated from the Eu²⁺ ions and the Mn²⁺ ions, respectively. The efficient energy transfer from the Eu²⁺ ions to the Mn²⁺ ions was observed and its mechanism should be a resonant type via a nonradiative dipole–quadrupole interaction. A color-tunable emission in Ca₈NaGd(PO₄)₆F₂ phosphors can be realized by Eu²⁺ → Mn²⁺ energy transfer. Our results indicate that the developed phosphor may be used as a potential white emitting phosphor for UV based white LEDs.