Modification of luminescence spectra of CaF2: Eu2+

CaF₂:Eu²⁺ is a well known phosphor having efficient excitation in the near ultraviolet (NUV) range. Phosphors with NUV excitation are required in newly emerging applications such as photoluminescence liquid crystal displays (PLLCD), solid‐state lighting (SSL), and down‐conversion for solar cells. However, emission of CaF₂:Eu²⁺ is around 424 nm. Eye sensitivity drops considerably at these wavelengths. It is thus not useful for display applications for which emission in one of the primary colours (blue – 450 nm, green – 540 nm or red – 610 nm) is required. Efforts were made to modify the Photoluminescence (PL) spectra of CaF₂:Eu²⁺ to meet these requirements using co‐dopants. A Ca_0.49Sr_0.50Eu_0.01F₂ phosphor showing better colour coordinates and having an emission maximum around 440 nm was discovered during these studies. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and photoluminescence of EuII in barium zinc orthosilicate: a novel green color emitting phosphor for white‐LEDs

A series of Eu²⁺‐activated barium orthosilicates (BaZnSiO₄) were synthesized using a high‐temperature solid‐state reaction. A photoluminescence excitation study of Eu²⁺ shows a broad absorption band in the range of 270–450 nm, with multiple absorption peak maxima (310, 350 and 400 nm) due to 4f–5d electronic transition. The emission spectra of all the compositions show green color emission (in the spectral region 450–550 nm with a peak maximum at 502 nm and a shoulder at ~ 490 nm) with appropriate Comission Internationale de l'Eclairage (CIE) color coordinates. The two emission peaks are due to the presence of Eu²⁺ in two different Ba sites in the BaZnSiO₄ host lattice. The energy transfers between the Eu²⁺ ions in BaZnSiO₄ host are elucidated from the critical concentration quenching data based on the electronic multipolar interaction. All Eu²⁺‐activated BaZnSiO₄ phosphor materials can be efficiently excited in the ultraviolet (UV) to near UV‐region (270–420 nm), making them attractive candidate as a green phosphor for solid state lighting–white light‐emitting diodes.     

Investigation on luminescence properties of Eu2+‐doped Ba3Al2O5Cl2 phosphor for near‐UV‐excited white LEDs

Ba₃Al₂O₅Cl₂:Eu²⁺ phosphor was prepared by combustion synthesis (CS). The prepared phosphor was excited at 329 nm; the phosphors shows an efficient bluish‐green wide‐band emission centred at 490 nm, which originates from the 4f⁶d¹ → 4f⁷ transition of Eu²⁺ ions. The excitation spectra of the phosphors have a band centred at 329 nm. It was also characterized by XRD, FT–IR for confirmation of phase purity, and FT–IR analysis indicated the vibrations of metal–oxygen (M–O) groups. SEM shows the morphology of the phosphor at the submicron scale. The results indicate that Ba₃Al₂O₅Cl₂:Eu²⁺ phosphor may be applicable for solid‐state lighting purposes. Copyright © 2012 John Wiley & Sons, Ltd.     

Novel blue‐emitting SrMg2Al16O27:Eu2+ phosphor for solid‐state lighting

Eu²⁺‐activated SrMg₂Al₁₆O₂₇ novel phosphor was synthesized by a combustion method (550°C furnace). The prepared phosphor was first characterized by X‐ray diffraction (XRD) for confirmation of phase purity. SEM analysis showed the morphology of the phosphor. The photoluminescence characteristics showed broad‐band excitation at 324 nm, which was monitored at 465 nm emission wavelength. The SrMg₂Al₁₆O₂₇:Eu²⁺ phosphor shows broad blue emission centred at 465 nm, emitting a blue light corresponding to 4f⁶5d¹ → 4f⁷ transition. Here we report the photoluminescence characteristics of the prepared phosphor and compare it with commercial BAM:Eu²⁺ phosphor. Copyright © 2011 John Wiley & Sons, Ltd.     

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.     

Luminescence in Li3Al2(PO4)3:Eu2+

A series of efficient Li₃Al₂(PO₄)₃:Eu²⁺ novel phosphors were synthesized by the facile combustion method. The effects of dopant on the luminescence behavior of Li₃Al₂(PO₄)₃ phosphor were also investigated. The phosphors were characterized by X‐ray diffraction, field emission scanning electron microscope and photoluminescence techniques. The result shows that all samples can be excited efficiently by near‐ultraviolet excitation under 310 nm. The emission was observed for Li₃Al₂(PO₄)₃:Eu²⁺ phosphor at 425 nm, which corresponded to the d → f transition. The concentration quenching of Eu²⁺ was observed in Li₃Al₂(PO₄)₃:Eu²⁺ when the Eu concentration was at 0.5 mol%. The prepared powders exhibited intense blue emission at the 425 nm owing to the Eu²⁺ ion by Hg‐free excitation at 310 nm (i.e., solid‐state lighting excitation). Consequently, the availability of such a phosphor will significantly help in the development of blue‐emitting solid‐state lighting applications. 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.     

Synthesis of AlN: Eu2+ green phosphors by a simple direct nitridation method

Eu‐doped aluminum nitride phosphors were successfully prepared using simple direct nitridation of a metallic aluminum and Eu₂O₃ powder mixture in flowing ammonia. AlN formed at reaction temperatures >900°C, and Eu³⁺ transformed into the secondary oxide phase EuAl₂O₄ in the nitridation condition. Phase pure AlN was obtained by post‐heat treatment of the nitridated product at 1600°C for 3 h in a nitrogen atmosphere, with an Eu²⁺ doping concentration < 0.5%. The phosphors exhibited broad green emission centered at 521 nm under 363 nm excitation. The luminescence of the phosphor was significantly influenced by the post‐heat treatment temperature, which affected the dissolution of Eu²⁺, phase purity, crystallinity, and particle size of the AlN host.     

Synthesis and luminescence properties of blue‐emitting phosphor Ca12Al14O32F2:Eu2+ for white light‐emitting diode

A blue‐emitting phosphor Ca₁₂Al₁₄O₃₂F₂:Eu²⁺ was synthesized using a high‐temperature solid‐state reaction under a reductive atmosphere. The X‐ray diffraction measurements indicate that a pure phase Ca₁₂Al₁₄O₃₂F₂:Eu²⁺ can be obtained for low doping concentration of Eu²⁺. The phosphor has a strong absorption in the range 270–420 nm with a maximum at ~340 nm and blue emission in the range 400–500 nm with chromatic coordination of (0.152, 0.045). The optimal doping concentration is ~0.24. In addition, the luminescence properties of the as‐synthesized phosphor were evaluated by comparison with those of Ca₁₂Al₁₄O₃₂Cl₂:Eu²⁺ and the commercially available phosphor BaMgAl₁₀O₁₇:Eu²⁺. The emission intensity of Ca₁₂Al₁₄O₃₂F₂:Eu²⁺ was ~72% that of BaMgAl₁₀O₁₇:Eu²⁺ under excitation at λ = 375 nm. The results indicate that Ca₁₂Al₁₄O₃₂F₂:Eu²⁺ has potential application as a near‐UV‐convertible blue phosphor for white light‐emitting diodes.     

ZnWO4:Eu3+ phosphor with intense blue LED excitation: photoluminescence and electron density distribution analysis

A high intensity 464 nm excitable ZnWO₄:Eu³⁺ red‐emitting phosphor for warm white lighting applications was prepared using a solid‐state reaction method by varying the dopant Eu³⁺ concentration. Crystalline purity and phase identification was confirmed and revealed using powder X‐ray diffraction and Rietveld refinement analysis. The surface morphology of Zn_1‐xEu_xWO₄ (x = 0, 0.01, 0.02, 0.03, 0.04 and 0.05) was examined using scanning electron microscopy (SEM) techniques. From SEM analysis, the ZnWO₄:Eu³⁺ phosphor prepared at 1–3% molar Eu³⁺ concentrations exhibited a small pebble‐like morphology with a smooth surface. On increasing the molar concentration of Eu³⁺ to >3%, the pebble stone morphology disappeared and a large, smooth irregular polygon‐shaped granular‐like morphology was obtained. Of the higher mol% Eu³⁺, the 4% Eu³⁺‐doped ZnWO₄ showed the best photoluminescence properties with high intensity and sharp excitation at 395 and 464 nm, followed by red emission centred at 615 nm with excellent CIE coordinates (x = 0.58 and y = 0.41) in the core red region. Elemental composition and chemical state analysis were carried out for the 4% Eu³⁺‐doped ZnWO₄ phosphor using X‐ray photoelectron spectroscopy and energy dispersive X‐ray spectroscopy studies. Based on all the above analyses, the Eu³⁺‐doped ZnWO₄ phosphor was found to be a very efficient red‐emitting phosphor under near‐UV light as well as under visible light excitation and could be used for white LED and field emissive displays applications.     

Optical properties of Eu2+/Eu3+ mixed valence phosphor Ca2SiO2F2:Eu2+/Eu3+

The Eu²⁺/Eu³⁺ mixed valence phosphor Ca₂SiO₂F₂:Eu²⁺/Eu³⁺ was prepared using a solid‐state reaction synthesis method in a CO atmosphere, and the optical properties were investigated. The spectroscopic properties revealed that Ca²⁺ ions were occupied by both Eu²⁺ and Eu³⁺ ions in Ca₂SiO₂F₂, and both ions were able to generate their characteristic emissions. A broad 5d → 4f Eu²⁺ band at ~470 nm and narrow 4f → 4f Eu³⁺ peaks upon excitation with n‐UV light were observed. The ratio between Eu²⁺ and Eu³⁺ emissions changed regularly, and the relative intensity of the red component from Eu³⁺ became systematically stronger with increasing overall Eu content. As a result, the emission color of these phosphors can be tunable from blue to pink under n‐UV light excitation.     

Synthesis and luminescence study of Eu3+‐doped SrYAl3O7 phosphor

Rare‐earth ions play an important role in eco‐friendly solid‐state lighting for the lighting industry. In the present study we were interested in Eu³⁺ ion‐doped inorganic phosphors for near ultraviolet (UV) excited light‐emitting diode (LED) applications. Eu³⁺ ion‐activated SrYAl₃O₇ phosphors were prepared using a solution combustion route at 550°C. Photoluminescence characterization of SrYAl₃O₇:Eu³⁺ phosphors showed a 612 nm emission peak in the red region of the spectrum due to the ⁵D₀→⁷F₂ transition of Eu³⁺ ions under excitation at 395 nm in the near‐UV region and at the 466 nm blue excitation wavelength. These red and blue emissions are supported for white light generation for LED lighting. Structure, bonding between each element of the sample and morphology of the sample were analysed using X‐ray diffraction (XRD) and scanning electron microscopy (SEM), which showed that the samples were crystallized in a well known structure. The phosphor was irradiated with a ⁶⁰Co‐γ (gamma) source at a dose rate of 7.2 kGy/h. Thermoluminescence (TL) studies of these Eu³⁺‐doped SrYAl₃O₇ phosphors were performed using a Nucleonix TL 1009I TL reader. Trapping parameters of this phosphor such as activation energy (E), order of kinetics (b) and frequency factor (s) were calculated using Chen's peak shape method, the initial rise method and Ilich's method.     

Combustion synthesis of blue‐emitting submicron CaAl4O7:Eu2+, Dy3+ persistence phosphor

Long persistence phosphor CaAl₄O₇: Eu²⁺, Dy³⁺ were prepared by a combustion method. The phosphors were characterized by means of X‐ray diffraction (XRD), scanning electron microscopy (SEM), decay time measurement techniques and photoluminescence spectra (PL). The CaAl₄O₇: Eu²⁺, Dy³⁺ phosphor showed a broad blue emission, peaking at 445 nm when excited at 341 nm. Such a blue emission can be attributed to the intrinsic 4f → 5d transitions of Eu²⁺ in the host lattices. The lifetime decay curve of the Dy³⁺ co‐doped CaAl₄O₇: Eu²⁺ phosphor contains a fast decay component and another slow decay one. Surface morphology also has been studied by SEM. The calculated CIE colour chromaticity coordinates was (0.227, 043). We have also discussed a possible long‐persistent mechanism of CaAl₄O₇:Eu²⁺, Dy³⁺ phosphor. All the results indicate that this phosphor has promising potential for practical applications in the field of long‐lasting phosphors for the purposes of sign boards and defence. Copyright © 2011 John Wiley & Sons, Ltd.     

Photoluminescence properties of Ca2Al2O5:RE3+ (RE = Eu,Dy and Tb) phosphors for solid state lighting

Ca₂Al₂O₅:Eu³⁺, Ca₂Al₂O₅:Dy³⁺ and Ca₂Al₂O₅:Tb³⁺ phosphors were synthesized using a combustion synthesis method. The prepared phosphors were characterized by X‐ray powder diffraction for phase purity, by scanning electron microscopy for morphology, and by photoluminescence for emission and excitation measurements. The Ca₂Al₂O₅:Eu³⁺ phosphors could be efficiently excited at 396 nm and showed red emission at 594 nm and 616 nm due to ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂ transitions. Dy³⁺‐doped phosphors showed blue emission at 482 nm and yellow emission at 573 nm. Ca₂Al₂O₅:Tb³⁺ phosphors showed emission at 545 nm when excited at 352 nm. Concentration quenching occurred in both Eu³⁺ and Dy³⁺phosphors at 0.5 mol%. Photoluminescence results suggested that the aluminate‐based phosphor could be a potential candidate for application in environmentally friendly based lighting technologies.     

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.     

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.     

Luminescence properties of red‐emission Mg4Nb2O9:Eu3+ phosphor

Red‐emitting Mg₄Nb₂O₉:Eu³⁺ phosphor is synthesized via a solid‐state reaction method in air, and its crystal structure and luminescence are investigated. The phosphor can be excited efficiently by ~ 395 nm light, coupled well with a ~ 395 nm near‐ultraviolet chip and emits red light at ~ 613 nm with sharp spectra due to ⁵D₀ → ⁷ F₂ transition of the Eu³⁺ ion. Mg₄Nb₂O₉:Eu³⁺ phosphor sintered at 1350 ºC shows Commission international de I'Eclairage (CIE) chromaticity coordinates of x = 0.6354, y = 0.3592, and is a potential red‐emitting phosphor candidate for white light‐emitting diodes (W‐LEDs) under ~ 395 nm near‐ultraviolet LED chip excitation. Copyright © 2014 John Wiley & Sons, Ltd.     

Characterization and luminescence properties of CaMgSi2O6:Eu2+ blue phosphor

A blue CaMgSi₂O₆:Eu²⁺ phosphor was prepared by the solid‐state reaction method and the phosphor characterized in terms of crystal structure, particle size, photoluminescence (PL), thermoluminescence (TL) and mechanoluminescence (ML) properties using X‐ray diffraction (XRD), transmission electron microscopy (TEM), PL spectroscopy, TLD reader and ML impact technique. The XRD result shows that phosphor is formed in a single phase and has a monoclinic structure with the space group C2/c. Furthermore, the PL excitation spectra of Eu²⁺‐doped CaMgSi₂O₆ phosphor showed a strong band peak at 356 nm and the PL emission spectrum has a peak at 450 nm. The depths and frequency factors of trap centers were calculated using the TL glow curve by deconvolution method in which the trap depths were found to be 0.48 and 0.61 eV. The formation of CaMgSi₂O₆:Eu²⁺ phosphor was confirmed by Fourier transform infrared spectroscopy. The ML intensity increased linearly with the impact velocity of the piston used to deform the phosphor. It was shown that the local piezoelectricity‐induced electron bombardment model is responsible for the ML emission. Finally, the optical properties of CaMgSi₂O₆:Eu²⁺ phosphors are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and photoluminescence characteristics of (Y,Gd)BO3:RE (RE = Eu3+, Ce3+, Dy3+ and Tb3+) phosphors for blue chip and near‐UV white LEDs

A series of Eu³⁺‐, Ce³⁺‐, Dy³⁺‐ and Tb³⁺‐doped (Y,Gd)BO₃ phosphors was synthesized by a solid‐state diffusion method. X‐Ray diffraction confirmed their hexagonal structure and the scanning electron microscopy results showed crystalline particles. The excitation spectra revealed that (Y,Gd)BO₃ phosphors doped with Eu³⁺, Ce³⁺ , Dy³⁺ and Tb³⁺ are effectively excited with near UV‐light of 395 nm/blue light, 364, 351 and 314 nm, respectively. Photoluminescence spectra of Eu³⁺‐, Ce³⁺‐ and Tb³⁺/Dy³⁺‐doped phosphor showed intense emission of reddish orange, blue and white light, respectively. The phosphor Y_0.60Gd_0.38BO₃:Ce_0.02 showed CIE 1931 color coordinates of (0.158, 0.031) and better color purity compared with commercially available blue BAM:Eu²⁺ phosphor. The phosphor (Y,Gd)BO₃ doped with Eu³⁺, Dy³⁺ and Tb³⁺ showed CIE 1931 color coordinates of (0.667, 0.332), (0.251, 0.299) and (0.333, 0.391) respectively. Significant photoluminescence characteristics of the prepared phosphors indicate that they might serve as potential candidates for blue chip and near‐UV white light‐emitting diode applications. 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.