Tunable luminescence and energy transfer in Ca3SiO4Cl2:Ce3+,Li+,Mn2+,Eu2+ phosphors

A series of color‐tunable Ca_{3–2x‐y‐z}SiO₄Cl₂ (CSC):xCe³⁺,xLi⁺,yMn²⁺,zEu²⁺ phosphors with low temperature phase structure was synthesized via the sol–gel method. An energy transfer process from Ce³⁺ to Mn²⁺ in CSC:0.01Ce³⁺,0.01Li⁺,yMn²⁺ (y = 0.03–0.09) and the mechanism was verified to be an electric dipole–dipole interaction. The Ce³⁺ and Mn²⁺ emission intensities were greatly enhanced by co‐doping Eu²⁺ ions into CSC:0.01Ce³⁺,0.01Li⁺,0.07Mn²⁺ phosphors due to competitive energy transfers from Eu²⁺/Ce³⁺ to Mn²⁺, and Ce³⁺ to Eu²⁺. Under 332 nm excitation, CSC:0.01Ce³⁺,0.01Li+,0.07Mn²⁺,zEu²⁺ (z = 0.0005–0.002) exhibited tunable emission colors from green to white with coexisting orange, green and violet‐blue emissions. These phosphors could have potential application in white light‐emitting diodes.     

Luminescent properties of Ca3SiO4Cl2 co‐doped with Ce3+ and Eu2+ for near‐ultraviolet light‐emitting diodes

Ca₃SiO₄Cl₂ co‐doped with Ce³⁺,Eu²⁺ was prepared by high temperature reaction. The structure, luminescent properties and the energy transfer process of Ca₃SiO₄Cl₂: Ce³⁺,Eu²⁺ were investigated. Eu²⁺ ions can give enhanced green emission through Ce³⁺ → Eu²⁺ energy transfer in these phosphors. The green phosphor Ca_2.9775SiO₄Cl₂:0.0045Ce³⁺,0.018Eu²⁺ showed intense green emission with broader excitation in the near‐ultraviolet light range. A green light‐emitting diode (LED) based on this phosphor was made, and bright green light from this green LED could be observed by the naked eye under 20 mA current excitation. Hence it is considered to be a good candidate for the green component of a three‐band white LED. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and luminescent properties of novel BaGd2O4:Eu3+ scintillating phosphor

BaGd_2‐xO₄:xEu³⁺ and Ba_1‐yGd_1.79‐2yEu_0.21Na_3yO₄ phosphors were synthesized at 1300°C in air by conventional solid‐state reaction method. Phosphors were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence excitation (PLE) spectra, photoluminescence (PL) spectra and thermoluminescence (TL) spectra. Optimal PL intensity for BaGd_2‐xO₄:xEu³⁺ and Ba_1‐yGd_1.79‐2yEu_0.21Na_3yO₄ phosphors at 276 nm excitation were found to be x = 0.24 and y = 0.125, respectively. The PL intensity of Eu³⁺ emission could only be enhanced by 1.3 times with incorporation of Na⁺ into the BaGd₂O₄ host. Enhanced luminescence was attributed to the flux effect of Na⁺ ions. However, when BaGd₂O₄:Eu³⁺ phosphors were codoped with Na⁺ ions, the induced defects confirmed by TL spectra impaired the emission intensity of Eu³⁺ ions. Copyright © 2012 John Wiley & Sons, Ltd.     

Photoluminescence properties of a novel phosphor CaB2O4:Eu3+ under NUV excitation

The new borate phosphor CaB₂O₄:Eu³⁺ was synthesized by solid‐state method and their photoluminescence properties were investigated. The results show that the pure phase of CaB₂O₄ could be available at 900°C, CaB₂O₄:Eu³⁺ phosphor could be effectively excited by the near ultraviolet light (NUV) (392 nm), and the luminescent intensity of CaB₂O₄:Eu³⁺ phosphor reached to the highest when the doped‐Eu³⁺ content was 4 mol%. The emission spectra of CaB₂O₄:Eu³⁺ phosphor could exhibit red emission at 612 nm and orange emission at 588 nm, which are ascribed to the ⁵D₀–⁷F₂ and ⁵D₀–⁷F₁ transitions of Eu³⁺ ions. Copyright © 2009 John Wiley & Sons, Ltd.     

A novel red phosphor Ca2YNbO6:Eu3+ for WLEDs

Due to the advantages of good physicochemical properties, thermal stability, and optical properties, double perovskite compounds have received extensive attention. On this basis, a new type of red phosphor, Ca₂YNbO₆:xEu³⁺, was synthesized using a high-temperature solid-phase method. Its phase purity, morphology, elemental composition, absorption spectrum, photoluminescence, thermal stability, and Commission Internationale de l'éclairage (CIE) chromaticity coordinates were thoroughly investigated. The results display that there is no impurity phase in the samples and the convergence factor R_wp = 14.2%; the microscopic particles are uniform and full, and the distribution of each element is uniform. The energy band gap ΔE is between 3.71 eV and 3.65 eV. The luminescence intensity is the best when the doped Eu³⁺ concentration x reaches 0.4, and emits 612 nm red light (⁵D₀→⁷F₂) under 465 nm excitation, and the concentration quenching is attributed to a d–d interaction. The luminescence intensity at 425 K was still 75% of the room temperature luminescence intensity, which indicates that the thermal stability is extremely superior. The CIE chromaticity coordinates (0.6534, 0.3455) of the Ca2YNbO6:0.4Eu³⁺ phosphors are very close to National Television Standards Committee (0.670, 0.330), and the samples have low correlated colour temperature (2656 K) and high colour purity (99.90%). All findings suggest that Ca₂YNbO₆:Eu³⁺ can serve as a substitute for red phosphor in WLEDs.     

Ca3(PO4)2:Eu3+ phosphor preparation with different morphologies and their fluorescence properties

Ca₃(PO₄)₂:Eu³⁺ phosphor was prepared using a facile chemistry method in the presence of surfactants. The effects of surfactants on the morphology and photoluminescence properties of Ca₃(PO₄)₂:Eu³⁺ phosphor were investigated. The morphology of the phosphor was significantly influenced by the surfactants employed. When nonionic surfactant glyceryl monostearate and anionic surfactant sodium dodecylbenzene sulfonate were employed, the phospor powders are composed of a large number of homogeneous spherical particles with sizes of 0.3–0.6 µm and 2–3 µm, respectively. By contrast, when cationic surfactant cetyltrimethylammonium bromide was used, the morphology of the phosphor is completely different. The product is an excellent cuboid, and the phosphor prepared with 2.5 mmol cetyltrimethylammonium bromide showed higher luminescent intensity than phosphors prepared with the other two types of surfactants. Copyright © 2013 John Wiley & Sons, Ltd.     

Luminescence properties of Ce3+ in orthosilicate oxyapatite NaY9(SiO4)6O2

Ce³⁺‐doped orthosilicate oxyapatite NaY₉(SiO₄)₆O₂ phosphors NaY_9–x(SiO₄)₆O₂:xCe³⁺ were prepared by a conventional high‐temperature solid‐state reaction method, and their spectroscopic characteristics were systematically investigated. The occupancies of Ce³⁺ ions at two different sites (Wyckoff 6 h and 4f sites) in NaY₉(SiO₄)₆O₂ were determined. The influence of doping concentration on the emission intensity of Ce³⁺ was investigated and the critical distance Rc was estimated in terms of the concentration quenching data.     

Microwave‐assisted sintering synthesis of greenish‐yellow emitting Sr2SiO4:Eu2+ phosphors

Europium ion (Eu²⁺) doped Sr₂SiO₄ phosphors with greenish‐yellow emission were synthesized using microwave‐assisted sintering. The phase structure and photoluminescence (PL) properties of the obtained phosphor samples were investigated. The PL excitation spectra of the Sr₂SiO₄:Eu²⁺ phosphors exhibited a broad band in the range of 260 nm to 485 nm with a maximum at 361 nm attributed to the 5f‐4d allowed transition of the Eu²⁺ ions. Under an excitation at 361 nm, the Sr₂SiO₄:Eu²⁺ phosphor exhibited a greenish‐yellow emission peak at 541 nm with an International‐Commission‐on‐Illumination (CIE) chromaticity of (0.3064, 0.4772). The results suggest that the microwave‐assisted sintering method is promising for the synthesis of phosphors owing to the decreased sintering time without the use of additional reductive agents.     

Combustion synthesis and luminescence properties of SrAl2O4:Eu2+, Dy3+, Tb3+ phosphor.

Eu(2+), Dy(3+) and Tb(3+) co-doped strontium aluminate phosphor with high brightness and long afterglow was synthesized by a combustion method, using urea as a reducer. The properties of SrAl(2)O(4):Eu(2+),Dy(3+),Tb(3+) phosphor with a series of initiating combustion temperatures, urea concentrations and boric acid molar fractions were investigated. The sample at initiating combustion temperature of 600 degrees C exhibited an intense emission peak at 513 nm, in which the phosphor existed as a single-phase monoclinic structure. The experimental results showed that the optimum ratio of urea is 2.0 times higher than theoretical quantities and that the suitable molar fraction of H(3)BO(3) is 0.08. The average particle size of the phosphor was 50-80 nm and its luminescence properties were studied systematically. Compared with SrAl(2)O(4):Eu(2+),Dy(3+) phosphor, the initial luminescence brightness improved from 2.50 candela (cd)/m(2) to 3.55 cd/m(2) and the long afterglow time was prolonged from 1290 s to 2743 s.     

Luminescence and energy‐transfer properties of color‐tunable Ca2Mg0.25Al1.5Si1.25O7:Ce3+/Eu2+/Tb3+ phosphors for ultraviolet light‐emitting diodes

A series of Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺/Eu²⁺/Tb³⁺ phosphors was been prepared via a conventional high temperature solid‐state reaction and their luminescence properties were studied. The emission spectra of Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺,Eu²⁺ and Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺,Tb³⁺ phosphors show not only a band due to Ce³⁺ ions (409 nm) but also as a band due to Eu²⁺ (520 nm) and Tb³⁺ (542 nm) ions. More importantly, the effective energy transfer from Ce³⁺ to Eu²⁺ and Tb³⁺ ions was confirmed and investigated by emission/excitation spectra and luminescent decay behaviors. Furthermore, the energy level scheme and energy transfer mechanism were investigated and were demonstrated to be of resonant type via dipole–dipole (Ce³⁺ to Eu²⁺) and dipole–quadrupole (Ce³⁺ to Tb³⁺) reactions, respectively. Under excitation at 350 nm, the emitting color could be changed from blue to green by adjusting the relative doping concentration of Ce³⁺ and Eu²⁺ ions as well as Ce³⁺ and Tb³⁺ ions. The above results indicate that Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺,Eu²⁺/Tb³⁺ are promising single‐phase blue‐to‐green phosphors for application in phosphor conversion white‐light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Novel red colour emitting Ca0.995Mg2(SO4)3:0.5Eu2+ phosphor under ultraviolet,blue, and green excitation for plant growth LEDs

In the recent few years, Eu²⁺- and Mn⁴⁺-activated phosphors are widely used as potential colour converters for indoor plant cultivation lighting application due to their marvellous luminescence characteristics as well as low cost. In this investigation, we synthesized novel red colour-emitting Ca_(2−x)Mg₂(SO₄)₃:xmol% Eu²⁺ (x = 0–1.0 mol%) phosphors via a solid-state reaction method in a reducing atmosphere. The photoluminescence (PL) excitation spectra of synthesized phosphors exhibited a broad excitation band with three excitation bands peaking at 349 nm, 494 nm, and 554 nm. Under these excitations, emission spectra exhibited a broad band in the red colour region at ~634 nm. The PL emission intensity was measured for different concentrations of Eu²⁺. The maximum Eu²⁺ doping concentration in the Ca₂Mg₂(SO₄)₃ host was observed for 0.5 mol%. According to Dexter theory, it was determined that dipole–dipole interaction was responsible for the concentration quenching. The luminous red colour emission of the sample was confirmed using Commission international de l'eclairage colour coordinates. The results of PL excitation and emission spectra of the prepared phosphors were well matched with excitation and emission wavelengths of phytochrome P_R. Therefore, from the entire investigation and obtained results it was concluded that the synthesized Ca_0.995Mg₂(SO₄)₃:0.5mol%Eu²⁺ phosphor has huge potential for plant cultivation application.     

Influence of rare earth elements (Y,Gd and Lu) on the luminescent properties of green phosphor ZnMoO4:Tb3+

(Zn,Ln_x)MoO₄:Tb³⁺ (Ln = Y³⁺, Gd³⁺ and Lu³⁺) were prepared using the co‐precipitation method. Phase impurity, morphology and composition were investigated by power X‐ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The experimental results show that crystal structure is not destroyed after doping an appropriate amount of Y³⁺, Gd³⁺ and Lu³⁺. EDS analysis reveals that Y, Gd and Lu have been successfully doped into ZnMoO₄. In addition, the morphology of the phosphors is notably improved, exhibiting homogeneous dispersion morphology and irregular shapes of particle size ~ 0.5–1 µm. The luminescent intensity of (Zn,Ln_x)MoO₄:Tb³⁺ (Ln = Y³⁺, Gd³⁺ and Lu³⁺) phosphor is obviously higher than that of ZnMoO₄:Tb³⁺ phosphor. The energy transfer process between trivalent rare earth ions indicates that the inert earth ions can act as an energy bridge from MoO₄^2‐ to Tb³⁺. Copyright © 2013 John Wiley & Sons, Ltd.     

Optical properties and energy transfer of Eu2+/Ce3+ co‐activated Na3Ca6(PO4)5 phosphor

Ce³⁺/Eu²⁺ co‐doped Na₃Ca₆(PO₄)₅ phosphors were prepared using a combustion‐assisted synthesis method. X‐Ray powder diffraction (XRD) analysis confirmed the formation of a Na₃Ca₆(PO₄)₅ crystal phase. Na₃Ca₆(PO₄)₅:Eu²⁺ phosphors have an efficient bluish‐green emission band that peaks at 489 nm, whereas Ce³⁺‐doped Na₃Ca₆(PO₄)₅ showed a bright emission band at 391 nm. Analysis of the experimental results suggests that enhancement of the Eu²⁺ emission intensity in co‐doped Na₃Ca₆(PO₄)₅:Eu²⁺,Ce³⁺ phosphors is due to a resonance‐type energy transfer from Ce³⁺ to Eu²⁺ ions, which is predominantly governed by an exchange interaction mechanism. These results indicate that Ce³⁺/Eu²⁺ co‐doped Na₃Ca₆(PO₄)₅ is potentially useful as a highly efficient, bluish‐green emitting, UV‐convertible phosphor for white‐light‐emitting diodes. Copyright © 2014 John Wiley & Sons, Ltd.     

Strong green fluorescent hydrogels with Ba2MgSi2O7:Eu2+ phosphor embedded in cellulose

Non‐cytotoxic and green‐emitting fluorescent hydrogels were constructed from a cellulose solution containing Ba₂MgSi₂O₇:Eu²⁺ green phosphor in a NaOH/urea aqueous system. The structure, optical properties and cytotoxicity of these hydrogels were studied. The Ba₂MgSi₂O₇:Eu²⁺ phosphor particles were dispersed evenly in the cellulose hydrogel matrix. Good luminescent properties of Ba₂MgSi₂O₇:Eu²⁺ phosphor were maintained in the hydrogels, leading to strong green emission under ultraviolet excitation. Fluorescent hydrogels have no obvious cytotoxicity in a 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) proliferation test, and have potential use in in vivo applications like optical imaging and drug delivery.     

Insights into the discrepant luminescence for BaSiO3:Eu2+ phosphors prepared by solid‐state reaction and precipitation reaction methods

Two synthesis routes, solid‐state reaction and precipitation reaction, were employed to prepare BaSiO₃:Eu²⁺ phosphors in this study. Discrepancies in the luminescence green emission at 505 nm for the solid‐state reaction method sample and in the yellow emission at 570 nm for the sample prepared by the precipitation reaction method, were observed respectively. A detail investigation about the discrepant luminescence of BaSiO₃:Eu²⁺ phosphors was performed by evaluation of X‐ray diffraction (XRD), photoluminescence (PL)/photoluminescence excitation (PLE), decay time and thermal quenching properties. The results showed that the yellow emission was generated from the BaSiO₃:Eu²⁺ phosphor, while the green emission was ascribed to a small amount of Ba₂SiO₄:Eu²⁺ compound that was present in the solid‐state reaction sample. This work clarifies the luminescence properties of Eu²⁺ ions in BaSiO₃ and Ba₂SiO₄ hosts.     

Structural characterization and optical properties of Ca2MgSi2O7:Eu2+,Dy3+ phosphor by solid‐state reaction method

Ca₂MgSi₂O₇:Eu²⁺,Dy³⁺ phosphor was prepared by the solid‐state reaction method under a weak reducing atmosphere. The obtained phosphor was characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), energy dispersive X‐ray spectroscopy (EDX) and Fourier transform infrared (FT‐IR) techniques. The phase structure of the Ca₂MgSi₂O₇:Eu²⁺,Dy³⁺ phosphor was akermanite type, which is a member of the melilite group. The surface morphology of the sintered phosphor was not uniform and phosphors aggregated tightly. EDX and FT‐IR spectra confirm the elements present in the Ca₂MgSi₂O₇:Eu²⁺,Dy³⁺ phosphor. Under UV excitation, a broadband emission spectrum was found. The emission spectra observed in the green region centered at 535 nm, which is due to the 4f–5d transition. The mechanoluminescence (ML) intensity of the prepared phosphor increased linearly with increases in the mechanical load. The ML spectra were similar to the photoluminescence (PL), which indicates that ML is emitted from the same emitting center of Eu²⁺ ions as PL. Copyright © 2014 John Wiley & Sons, Ltd.     

ZnAl2O4:Eu novel phosphor: SEM and mechanoluminescence characterization synthesized by solution combustion technique

Eu doped ZnAl₂O₄ phosphors were synthesized by the solution combustion technique using carbohydrazide as a fuel. Mechanoluminescence (ML) was excited impulsively by dropping a piston of 0.7 kg onto the phosphors. Two distinct peaks were observed in the ML glow curve of the γ‐ray irradiated ZnAl₂O₄:Eu phosphors. Dependence of ML on various parameters as impact velocity of the piston dropped on to it, mass of the sample, gamma ray doses given to the sample and ML spectra have been studied. ML emission spectrum showed the characteristic emission of Eu³⁺ ion in this system. ML is observed to be optimum for the sample having 0.2 mol% of Eu in the ZnAl₂O₄ phosphor. XRD result confirms formation of the phosphors. SEM characterization shows its surface morphology. This novel phosphor may be a potential candidate for dosimetric use due to its linear dose response. Copyright © 2014 John Wiley & Sons, Ltd.     

Thermal quenching of luminescence of LiSr4(BO3)3:Eu2+ orange‐emitting phosphor

An orange‐emitting phosphor, Eu²⁺‐activated LiSr₄(BO₃)₃, was synthesized using the conventional solid‐state reaction. The photoluminescence excitation and emission spectra, and temperature dependence of the luminescence intensity of the phosphor were investigated. The results showed that LiSr₄(BO₃)₃:Eu²⁺ could be efficiently excited by incident light of 250–450 nm, and emits a strong orange light. With increasing temperature, the emission bands of LiSr₄(BO₃)₃:Eu²⁺ show an abnormal blue‐shift with broadening bandwidth and decreasing emission intensity. Copyright © 2013 John Wiley & Sons, Ltd.     

Persistent luminescence of CaMgSi2O6:Eu2+,Dy3+ and CaMgSi2O6:Eu2+,Ce3+ phosphors prepared using the solid‐state reaction method

CaMgSi₂O₆:Eu²⁺,Dy³⁺ and CaMgSi₂O₆:Eu²⁺,Ce³⁺ phosphors were synthesized using the solid‐state reaction method. X‐Ray diffraction (XRD) and photoluminescence (PL) analyses were used to characterize the phosphors. The XRD results revealed that the synthesized CaMgSi₂O₆:Eu²⁺,Dy³⁺ and CaMgSi₂O₆:Eu²⁺,Ce³⁺ phosphors were crystalline and are assigned to the monoclinic structure with a space group C2/c. The calculated crystal sizes of CaMgSi₂O₆:Eu²⁺,Dy³⁺ and CaMgSi₂O₆:Eu²⁺,Ce³⁺ phosphors with a main (221) diffraction peak were 44.87 and 53.51 nm, respectively. Energy‐dispersive X‐ray spectroscopy (EDX) confirmed the proper preparation of the sample. The PL emission spectra of CaMgSi₂O₆:Eu²⁺,Dy³⁺ and CaMgSi₂O₆:Eu²⁺,Ce³⁺ phosphors have a broad band peak at 444.5 and 466 nm, respectively, which is due to electronic transition from 4f⁶5d¹ to 4f⁷. The afterglow results indicate that the CaMgSi₂O₆:Eu²⁺,Dy³⁺ phosphor has better persistence luminescence than the CaMgSi₂O₆:Eu²⁺,Ce³⁺ phosphor. Copyright © 2015 John Wiley & Sons, Ltd.     

Tunable emission from LiBaBO3:Eu3+;Bi3+ phosphor for solid‐state lighting

Europium (Eu³⁺) and bismuth (Bi³⁺) co‐activated LiBaBO₃ powder phosphors were synthesized by a solid‐state reaction and the structure, particle morphology, optical and photoluminescent properties were investigated. X‐Ray diffraction patterns of the LiBaBO₃ phosphors crystallized in a pure monoclinic phase, i.e. there were no secondary phases due to either incidental impurities or undecomposed starting materials. Scanning electron microscopy images showed that the powders were made up of fluffy needle‐like particles that were randomly aligned. The band‐gap of the LiBaBO₃ host was estimated to be 3.33 eV from the UV/vis absorption data. Blue emission was observed from the LiBaBO₃ host, which is ascribed to self‐activation of the host matrix. In addition, greenish‐blue (493 nm) and red (613 nm) emissions were observed from europium‐doped samples and were attributed to the emissions of Eu²⁺ and Eu³⁺, respectively. Furthermore, after codoping with Bi³⁺, the emission intensity of Eu³⁺ located at 613 nm was significantly enhanced. From the Commission Internationale de I′Eclairage (CIE) color coordinates, white emission was observed from LiBa_1–xBO₃:xEu³⁺ (x = 0.020 and 0.025) phosphor powders with color coordinates of x = 0.368, y = 0.378 and x = 0.376, y = 0.366, respectively.