Luminescent properties of Ca2SiO4:Eu3+ red phosphor for trichromatic white light emitting diodes

The luminescent properties of Eu3 doped Ca2SiO4 red phosphors synthesized by the flux fusion reaction method were investigated. It was found that the excitation spectrum included two regions: the weak excitation band below 325 nm and strong narrow peaks above 325 nm. The main peak of the excitation band was located at 400 nm. The peaks located at 290 nm were assigned to the combination of the charge transfer transition of O-Eu, peaks above 325 nm (325, 385, 400, 470, 511, and 539 nm) were assigned to the f–f transitions of Eu3 . The emission spectrum was dominated by the red peak located at 612 nm due to the electric dipole transition of 5D0–7F2. In addition, the ef- fects of the Eu3 content and charge compensators of Li , Na , K , and Cl– ions on the emission intensity were investigated. The experiment results suggested that the strongest emission was obtained when the concentration of the Eu3 ions was 0.3 mol–1, and Li ions gave the best improvement to enhance the emission intensity. Ca2SiO4:Eu3 , Li was thus suitable for low-cost trichromatic white light emitting diodes (WLED) based on UV InGaN chip.     

Luminescent characteristics of Ba3Y2（BO3）4：Eu^3＋ phosphor for white LED

The Ba3Y2（BO3）4：Eu^3＋ phosphor was synthesized using a high temperature solid-state reaction method and the luminescent characteristics were investigated. The emission spectrum exhibited one strong red emission at 613 nm, corresponding to the electric dipole 5D0-TF2 transition of Eu^3＋, under 365 nm excitation. The excitation spectrum of 613 nm indicated that the Ba3Y2（BO3）n：Eu^3＋ phosphor was effectively excited by ultraviolet （UV） （254, 365 and 400 nm） and blue （470 nm） light. The effect of Eu^3＋ concentration on the 613 nm emission of the Ba3Y2（BO3）n：Eu^3＋ phosphor was measured. The results showed that the emission intensity increased with increasing Eu^3＋ concentration, and then decreased. The CIE color coordinates of Ba3Y2（BO3）4：Eu^3＋ phosphor were x=0.641 and y=0.359 at 15 mol.% Eu^3＋.     

A blue luminescence glass-ceramics of Eu^2＋ ions activated Li2O-BaO-B2O3

New blue luminescence glass-ceramic samples were prepared in air by annealing of the Eu^3＋-doped Li2O-BaO-B2O3 glass. The as-made glass samples only showed the sharp emission peaks assigned to the transitions of 5^D0-7^Fj （J=0, 1, 2, 3, 4） of Eu^3＋ ions. The glass-ceramic samples gave a strong and broad emission band peaking at about 382 nm ascribed to the 5d-4f transition of Eu^2＋ ions. The optical properties such as excitation and emission spectra, and the decay time of the Eu^2＋ ions were investigated in the glasses or the glass-ceramics samples. The X-ray diffraction pattern showed that LiBan9O15 might be demonstrated to be the crystallites in the glass-ceramic, which contributed to the blue luminescence. SEM micrograph was investigated on the glass-ceramic samples obtained by crystallization of the glass matrix resulting in a mixture of poly-crystals.     

Luminescence properties of YAl3（BO3）4 phosphors doped with Eu^3＋ ions

YAl3 （BO3）4： Eu^3＋ phosphors were prepared by the conventional solid state reaction. The phase structure and morphology were investigated by X-ray diffraction （XRD） and scanning electron microscope （SEM）. Doping YAl3（BO3）4： Eu^3＋ phosphors with concentration of Eu^3＋ ions of 0, 2, 5, 8 and 10 mol% were studied and their luminescent properties at room temperature were discussed. The excitation spectrum of Y0.95Eu0.05Al3（BO3）4 was composed of a broad band centered at about 252 nm and a group of lines in the longer wavelength region. In the emission spectra, the peak wavelength was about 614 nm under a 252 nm UV excitation. The optimal doping concentration of Eu^3＋ ions in YAl3（BO3）4： Eu^3＋ phosphors was 8 mol%.     

Luminescence enhancement of BaMgSiO4：Eu^2＋ by adding borate as flux

The luminescence of EU^2＋ in BaMgSiO4 with BaB2O4 as flux was studied. The emission spectrum of the phosphor consisted of two bands, peaking at about 398 nm and 515 nm, which were attributed to the emissions from different Eu^2＋ sites in the lattice. When the BaB2O4 flux was applied, the intensity of the 398 nm emission was not clearly affected, but the intensity of the 515 nm emission was enhanced by about ten times. Gaussian fitting showed that the emission band at around 515 nm could actually be resolved into two bands with peak wavelengths of 499 nm and 521 nm, respectively. The assignments of the emission bands to the cation sites were carried out according to the values of bond valence. The overlapping of the 398 nm emission band on the excitation band of 515 nm emission implied that energy transfer could occur from the luminescent center related to the 398 nm emission to the center related to the 515 nm emission, and the energy transfer process remarkably enhanced the intensity of the 515 nm emission band. The phosphor had strong excitation at around 350-400 nm and emitted a bright green luminescence. Thus it could have applications as a green component in solid-state lighting devices assembled by near-UV Light Emitting Diodes （LED） combined with tricolor phosphors.     

Study on Luminescence Properties of High-Density Phosphors BiTaO4：Pr^3＋ and BiTaO4

The photoluminescence properties of BiTaO4:Pr^3 and BiTaO4 at room temperature were studied, and the infrared transmission and diffusion reflection spectra of BiTaO4 were measured. The photoluminescence spectrum of BiTaO4 peaks at about 420, 440 and 465nm. There has an obvious excitation band from 330 to 370nm. The photoluminescence spectrum of BiTaO4:Pr^3 consists of the characteristic emission of Pr^3 , and its main peak is at 606 nm from ^3P0→^3H6 transition of Pr^3 . Its excitation spectrum consists of the wide band with maximum at 325nm, the wide band in the range of 375-430nm, and the characteristic excitation of Pr^3 .The bands at 325nm and 375-430nm may be from the absorption of the charge transfer transition of the tantalate group and defect energy levels in its forbidden band, respectively.There is energy transfer from host to Pr^3 . Because both the host density and photoluminescence peak intensity of BiTaO4:Pr^3 are superior to PbWO4, BiTaO4:Pr^3 may be a potential heavy scintillator.     

Luminescent properties of Eu³⁺-doped BaZrO₃ phosphor for UV white light emitting diode

A novel orange phosphor Eu3+ doped barium zirconate(BaZrO3) was synthesized by conventional solid state reaction method and its crystal structure and luminescent properties were investigated in this paper.The X-ray diffraction patterns(XRD) showed that simple BaZrO3 phase was obtained.Monitoring at 596 nm,the excitation spectrum consisted of a broad band and a series of narrow bands and the stronger excitation peaks located at 275 and 393 nm,respectively.The emission spectrum excited by 393 nm UV light was composed of four narrow bands.The strongest emission was located at 596 nm.The appropriate concentration of Eu3+ was 0.025(molar fraction) for the highest emission intensity at 596 nm.The H3BO3 and ammonium were added as flux and the results showed that 2 wt.% NH4F ions was the optimal flux for BaZrO3:Eu3+.     

VUV Spectroscopy of GdPO4： Eu^3＋ and GdBO3： Eu^3＋

The emission and the excitation spectra of GdPO4 ： Eu^3＋ and GdBO3： Eu^3 ＋ prepared by solid state reaction method were investigated using the synchrotron radiation source of SUPERLUMI station of HASYLAB. The energy transfer between Gd^3＋ and Eu^3＋ was discussed with the probability of quantum cutting process. In the excitation spectra monitoring the red emission from Eu^3＋ , the distinct lines corresponding to the intraconfigurational 4f-4f transitions from Gd^3＋ were observed for both samples, indicating an efficient energy transfer from host Gd^3＋ ions to the doped Eu^3＋ ions. The efficient energy transfer is necessary for the quantum cutting process based on the two-step energy transfer from Gd^3＋ to Eu^3＋ . However, the overlapping of the lines corresponding to Gd^3＋ ：^8S7/2→^6GJ and the broad excitation band （180 - 270 nm） due to Eu^3＋- O^2- charge transfer states （CTS） around 200 nm cause excitation energy on ^6GJ levels to dissipate into CTS by direct energy transfer, unfavorable to the cross relaxation energy transfer between Gd^3＋ and Eu^3＋, thus unfavorable to the quantum cutting process. With the help of the general rules governing the energy positions of Eu^3＋-O^2- ：CTS, the suggestions concerning searching suitable oxide hosts for Gd^3＋-Eu^3＋ quantum cutting were made.     

Synthesis and Luminescence of SrZnO2：Eu^3＋, Li^＋ Phosphor by Long Wavelength UV Excitation

SrZnO2 ： Eu^3 ＋ , Li^＋ phosphor powder by long wavelength UV excitation was synthesized by conventional solid-state reaction method. XRD and PL were employed to characterize their properties. The resuits show that Eu^3＋ ions preferentially occupy Sr^2＋ asymmetry cationic sites, thus emitting 612 nm red light originated from ^5D0 to ^7F2 transition. The luminescent intensity can be greatly enhanced with incorporation of Li^＋ ions. The excitation efficiency in range of 350 - 400 nm also increases greatly due to incorporating Li ^＋ ions. SrZnO2 ： Eu^3 ＋ , Li^＋ is a promising redemitting phosphor by long wavelength UV excitation.     

Role of monovalent co-dopants on the PL emission properties of YAI3（BO3）4：Ce3＋ phosphor

The cerium （Ce3＋） doped yttrium aluminium borate （YAB） phosphor was synthesized by modified solid state reaction. The phosphor＇s phase purity and its emission properties were studied using powder X-ray diffraction pattern and photoluminescence spectroscopy. The synthesized YAB had rhomobohedral crystal structure. The phosphor had two different excitation and emission spectra. By 325 nm excitation, the phosphor had emission at 373 nm and with 363 nm excitation; the phosphor gave violet-blue emission at 418 nm. The UV emission of the phosphor originated due to Ce3＋ ions at the yttrium site and violet-blue emission owing to Ce3＋ ions at non-regular sites viz., A13＋ and interstitial sites. The emission intensity of the phosphor was enhanced when monovalent ions （K＋, Na＋, and F） were added as co-dopants. The crucial role of ionic radii of monovalent co-dopants on the emission enhancement of the YAB：Ce3＋ phosphor was reported. Thermogravimetric study showed that the YAB possessed high thermal stability at up to 900 ℃.     

Vacuum ultraviolet excited photoluminescence properties of Gd2O2CO3：Eu^3＋ phosphor

The Gd2O2CO3：Eu^3＋ with type-Ⅱ structure phosphor was successfully synthesized via flux method at 400 ℃ and their photoluminescence properties in vacuum ultraviolet （VUV） region were examined. The broad and strong excitation bands in the range of 153-205 nm owing to the CO3^2- host absorption and charge transfer （CT） of Gd^3＋-O2^- were observed for Gd2O2CO3：Eu^3＋. Under 172 nm excitation, Gd2O2CO3：Eu^3＋ exhibited strong red emission with good color purity, indicating Eu^3＋ ions located at low symmetry sites and the chromaticity coordination of luminescence for Gd2O2CO3：Eu^3＋ was （x=0.652, y=0.345）. The photoluminescence quenching concentration of Eu^3＋ excited by 172 nm for Gd2O2CO3：Eu^3＋ was about 5%. Gd2O2CO3：Eu^3＋ would be a potential VUV-excited red phosphor applied in mercury-free fluorescent lamps.     

Characterization of Y2O2S： Eu^3＋, Mg^2＋, Ti^4＋ Long-Lasting Phosphor Synthesized by Flux Method

Long-lasting phosphor Y₂O₂S: Eu³⁺, Mg²⁺, Ti⁴⁺ was synthesized by a flux method and their luminescence properties were investigated. The result indicates that the unit cell parameter c is linearly increased with the increase of Eu₂O₃ content in Y₂O₂S: Eu_x³⁺ (0.01 ≤ x ≤ 0.10). On the other hand, the change of unit cell parameter a is not linear dependence. In the Y₂O₂S: Eu³⁺ crystal structure, Eu³⁺ ions only replaced Y³⁺ ions' places in which it posited center position of c axis. With the increase of Eu₂O₃ content, the position of the strongest emission peak changed from 540 nm (⁵D₁→⁷F₂ transition) to 626 nm (⁵D₀→⁷F₂ transition), and the maximum intensity was obtained when x = 0.09 in Y₂O₂S: Eu_x³⁺ (0.01 ≤ x ≤ 0.10). This is due to the environment of trivalent europium in the crystal structure of Y₂O₂S. Doping with Mg²⁺ or Ti⁴⁺ ions alone cannot get the good long-lasting afterglow effect, whereas co-doping with Mg²⁺ and Ti⁴⁺ ions and excited with 365 nm ultraviolet light, a strong thermoluminesence peak appeared, red and orange long-lasting phosphorescence (LLP) was also observed and the phosphorescence lasted nearly 3 h in the light perception of the dark-adapted human eye (0.32 mcd · m⁻²). Thus the LLP mechanism was analyzed.     

Preparation and Characterization of Red Luminescent Ca0.8 Zn0.2 TiO3 ： Pr3 ＋ , Na^＋ Nanophosphor

Nanophosphor with the nominal composition of Ca0.8 Zn0.2 TiO3 ： Pr3 ＋ , Na^＋ （CZTOPN） was synthesized at relatively low temperature by the sol-gel method. Metal ions were dispersed by citric acid in ethylene glycol solvent and then react with Ti（OC4H9）4 to form sol and gel. The decomposition process of the precursor, and crystallization and particle size of CZTOPN were examined by thermal analysis （TG-DSC）, powder X-ray diffraction （XRD）, and scan election microscopy （SEM）. Results of TG-DSC and XRD reveal that the composition of Ca0.8 Zn0.2 TiO3 ： Pr3 ＋ , Na^＋ changes with the sintering temperature. SEM data indicate that the diameter of particles is under 50 nm even if the sintering temperature increases to 1000 ℃. In contrast to a solid state reaction, the excitation spectra of samples synthesized by the sol-gel method shift blue about 10 nm and the emission intensity at 617 nm increases significantly.     

Luminescence investigation of Eu~（3＋）-Bi~（3＋） co-doped CaMoO_4 phosphor

A series of Eu³⁺-Bi³⁺ co-doped CaMoO₄ red phosphors were synthesized via the solid-sate reaction method. The crystal structures of the obtained samples were identified by X-ray powder diffraction (XRD). The photoluminescence property was investigated, and the results showed that the intensity of excitation spectra and emission spectra could be changed with different doping ratios of Bi³⁺/Eu³⁺. The proposed explanation of these changes was from the energy transfer between Bi³⁺ and Eu³⁺ and the unbalanced charge from the substitution of Eu³⁺ and Bi³⁺ for Ca²⁺ in CaMoO₄. The obtained samples are a promising red light emitting phosphor for the needs of different excitation sources with near-UV and blue GaN-based chips.     

Effects of crystal field on photoluminescence properties of Ca2Al2SiO7:Eu2+ phosphors

A series of single-phased Ca₂Al₂SiO₇:Eu²⁺ phosphors were synthesized by the solid-state reaction. Their structure and photolumi-nescence properties were investigated by the X-ray powder diffraction （XRD） and excitation and emission spectra in detail. The emission spectra of Ca₂Al₂SiO₇:Eu²⁺ phosphors consisted of blue and green band located at419 and542 nm, respectively. The relative intensities of the blue and green emission changed with Eu²⁺ concentration and were sensitive to the excitation wavelength. The unique photoluminescence property originated from the 4f⁷→4f⁶5d transition of Eu²+ at different energy levels, on which the effect of the crystal field strength was con-sidered to be tailed by adjusting the host composition.     

Luminescence properties of a single-host phosphor Bal.8-wSrwLi0.4SiO4： cea＋,Eu2＋,Mn2＋ for WLED

In order to obtain a single-host-white-light phosphor,a series of Ba1.8-w-x-y-zSrwLi0.4-xCexEuyMnzSiO4(BSLS:Ce3+,Eu2+,Mn2+)powder samples were synthesized via high temperature solid-state reaction.The structure and photoluminescence properties were investigated.Under ultraviolet excitation,the emission spectra contained three bands:the 370-470 nm blue band,the 470-570 nm green band and the 570-700 nm red band,which arose from the 5d→4f transitions of Ce3+ and Eu2+,and the 4T1→6A1 transition of Mn2+,respectively.The excitation spectra of the emissions of Ce3+ and Mn2+ ions showed the energy transfer from Ce3+ to Mn2+.White light emission was obtained from the tri-doped samples of appropriate doping concentration under 310-360 nm excitation.     

Comparative Study on Photoluminescent Properties of CaGdAlO4：Eu3＋ Phosphors Synthesized with Three Methods

CaGdAlO4 ： Eu^3＋ powder phosphors were prepared using citrate sol-gel （CSG）, haft-dry and half-wet （HDW） and solid state （SS） methods, respectively. X-ray diffraction results confirm the formation of CaGdAlO4：Eu^3＋ at 900 % （CSG）, 1200℃ （HDW） and 1400℃ （SS）, respectively. Field emission scan electron microscopy （FE-SEM） images show that the CaGdAlO4：Eu^3＋ powder prepared by the CSG and HDW method has an elliptical shape and that prepared under the SS method has a flaky shape. Upon excitation with 280 nm UV light, all the CaGdAlO4： Eu^3＋ powders show bright red emission on account of the 4f-4f transitions of the Eu^3＋ ions. Moreover, the size of the phosphor particles and the emission intensity increase with the increase of calcined temperature. At the same calcination temperature of 1400 ℃, the ^5D0→^7F2 emission intensity of the sample prepared by HDW method is the highest. Stark components of the ^5D0→^7FJ emission transitions, both at room temperature and at a low temperature, reveal that the Eu^3＋ ions occupy only one site with non-centrosymmetry in the crystals.     

Upconversion luminescence of Y2O3：Er^3＋ ,Yb^3＋ nanoparticles prepared by a homogeneous precipitation method

Y2O3： Er^3＋, Yb^3＋ nanoparticles were synthesized by a homogeneous precipitation method without and with different concentrations of EDTA 2Na. Upconversion luminescence spectra of the samples were studied under 980 nm laser excitation. The results of XRD showed that the obtained Y2O3：Er^3＋,Yb^3＋ nanoparticles were of a cubic structure. The average crystallite sizes calculated were in the range of 28-40 nm. Green and red upconversion emission were observed, and attributed to ^2H11/2,^4S3/2→^4I15/2 and ^4F9/2→^4I15/2 transitions of the ion, respectively. The ratio of the intensity of green emission to that of red emission drastically changed with a change in the EDTA 2Na concentration. In the sample synthesized without EDTA, the relative intensity of the green emission was weaker than that of the red emission. The relative intensities of green emission increased with the increased amount of EDTA 2Na used. The possible upconversion luminescence mechanisms were discussed.     

Spectroscopic investigations of Gd3Sc2Ga3O12 garnet doped with Cr^3＋ and Nd^3＋ ions

Absorption, excitation and emission spectra as well as decay time measurements at 10, 77, and 300 K were performed for Ga₃Gd₃Sc₂O₁₂ garnet single-crystal doped with Cr³⁺ and Nd³⁺ ions. Strong reabsorption of Cr³⁺ emission by Nd³⁺ absorption lines was observed. The assignments of f–f and d–d transitions were proposed. The broad emission band of chromium ions is an indication that weak/intermediate crystal field strength is present at the Cr³⁺ site.