Development of a new blue CaMgSi2O6:Eu2+ phosphor for PDPs

Abstract— A blue‐light‐emitting Eu²⁺‐doped CaMgSi₂O₆ phosphor having a long lifetime for a plasma‐display panel (PDP) was developed. The CaMgSi₂O₆:Eu²⁺(CMS:Eu) phosphors show no luminance degradation during the baking process, and an equivalent photoluminescence peak intensity compared to that of the conventional blue‐phosphor BaMgAl₁₀O₁₇:Eu²⁺ (BAM) after baking. CMS: Eu shows a poor luminescent characteristic for the Xe excimer band excitation due to the lack of absorption. To introduce the absorption center for the Xe excimer band, we performed Gd‐codoping of CMS: Eu as a sensitizer and found a new excitation band around 172 nm, which originated from Gd³⁺. The test PDPs panels using synthesized CMS: Eu phosphor and CMS: Eu, Gd phosphor were examined to investigate the luminescent and aging characteristics of a Xe‐discharge excitation source. The CMS: Eu panel shows an emission peak intensity comparable to that of the BAM panel (i.e., a comparable stimuli L/CIEy, 93% of BAM), while the CMS: Eu, Gd panel shows poorer blue emission intensity compared to the BAM panel (up to 53% of total stimuli of BAM). The CMS: Eu panel and the CMS: Eu, Gd panel show less luminance degradation than the BAM panel under the aging test, and the panel retains 90% of its luminance after 300 hours of driving. It was found that CMS: Eu appears to be a candidate for a new blue PDP phosphor because of its longevity in a Xe‐discharge plasma environment.     

Enhanced PL and VUV absorption of BaZr(BO3)2:Eu3+ by Al3+ incorporation

Abstract— The photoluminescence (PL) and vacuum‐ultraviolet excitation (VUV) properties of BaZr(BO₃)₂ doped with the Eu³⁺ activator ion were studied as a new red phosphor for PDP applications. The excitation spectrum shows strong absorption in the VUV region with an absorption band edge at 200 nm. The charge‐transfer excitation band of Eu³⁺ was enhanced by co‐doping with an Al³⁺ ion into the BaZr(BO₃)₂ lattices. The PL spectrum shows the strongest emission at 615 nm, corresponding to the electric dipole ⁵D₀ → ⁷F₂ transition of Eu³⁺ in BaZr(BO₃)₂, which results in good red‐color purity.     

Rare‐earth materials for use in the dark

Abstract— Recently, it was found that some materials doped with rare‐earth ions show bright and long‐lasting phosphorescence. They do not include radioactive elements and can be safely used as luminous paints for use in the dark. Some of them are better than the traditional zinc sulfide doped with copper (ZnS:Cu). The most important rare‐earth materials with long‐lasting phosphorescence are aluminates such as alkaline‐earth aluminates MAl₂O₄:Eu²⁺, Dy³⁺ (M = Sr, Ca) and garnets Y₃Ga₅O₁₂:Tb³⁺, Gd₃Ga₅O₁₂:Tb³⁺, Cd₃Al₂Ge₃O₁₂:Tb³⁺, Cd₃M₂Ge₃O₁₂:Pr³⁺ (M = Al, Ge), Y₃Al_5?xGa_xO₁₂:Ce³⁺ (x = 3, 3.5). Some oxides such as InBO₃:Tb³⁺, Ba₂SiO₄:Dy³⁺ also show long‐lasting phosphorescence properties. Other sulfide materials include ZnS:Eu, Ca_xSr_1?x S:Bi, Tm, Cu or Ca_xSr_1?xS:Eu. Alkaline‐earth aluminates MAl₂O₄:Eu²⁺ (M = Mg, Ca, Sr, Ba) codoped with RE³⁺ (RE = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were synthesized by using homogeneous precipitation method.     

Synthesis of Bi and Gd doped ZnB2O4 for evaluation as potential materials in luminescent display applications

A series of Bi³⁺ and Gd³⁺ doped ZnB₂O₄ phosphors were synthesized with solid state reaction technique. X-ray diffraction technique was employed to study the structure of prepared samples. Excitation and emission spectra were recorded to investigate the luminescence properties of phosphors. The doping of Bi³⁺ or Gd³⁺ with a small amount (no more than 3 mol%) does not change the structure of prepared samples remarkably. Bi³⁺ in ZnB₂O₄ can emit intense broad-band purplish blue light peaking at 428 nm under the excitation of a broad-band peaking at 329 nm. The optimal doping concentration of Bi³⁺ is experimentally ascertained to be 0.5 mol%. The decay time of Bi³⁺ in ZnB₂O₄ changes from 0.88 to 1.69 ms. Gd³⁺ in ZnB₂O₄ can be excited with 254 nm ultraviolet light and yield intense 312 nm emission. The optimal doping concentration of Gd³⁺ is experimentally ascertained to be 5 mol%. The decay time of Gd³⁺ in ZnB₂O₄ changes from 0.42 to 1.36 ms.     

High‐efficiency luminescent sources fabricated in mesoporous anodic alumina by sol‐gel synthesis

Abstract— This paper summarizes our recent results on the synthesis and investigation of photoluminescence (PL) from lanthanide‐doped microporous xerogel solids mesoscopically confined in porous anodic alumina (PAA). It was demonstrated, for Tb‐doped samples, that the PL intensity is strongly enhanced in comparison to thin xerogel films processed onto flat surfaces and increased with the thickness of the PAA layer. It was revealed for both Tb‐ and Eu‐doped PAA‐based structures that maximum emission is achieved at a excitation wavelength near 285 nm for the employed TiO₂ and Al2O₃ xerogels. Strong Eu‐ and Tb‐related PL visible to the naked eye was demonstrated, and a method for the fabrication of luminescent images based on anodizing, photolithography, and sol‐gel processes is proposed.     

Eu2+‐doped AlN—SiC solid‐solution phosphors: Synthesis and cathodoluminescence properties

Abstract— Eu and Si co‐doped AlN was reported to be an interesting blue phosphor for field‐emission displays (FEDs). In this paper, SiC instead of Si³N⁴ was used as the Si source. Eu²⁺‐doped AlN—SiC phosphors were prepared by firing the powder mixtures of AlN, SiC, and Eu²O³ at 2050°C for 2 hours under 1‐MPa N². Solid solutions between AlN and SiC were formed in a wide range, promoting the solution of Eu²⁺ in AlN. The phosphors showed intense blue emissions under electron‐beam excitation, indicative of potential phosphors for FEDs.     

White LEDs using the sharp β‐sialon: Eu phosphor and Mn‐doped red phosphor for wide‐color gamut display applications

The sharp β‐sialon (Si_6‐zAl_zO_zN_8‐z : 0 < z < 0.1):Eu green phosphor, combining with a blue LED and CaAlSiN₃:Eu red phosphor, is suitable for the wide‐color gamut white LEDs backlighting system, because of its sharp and asymmetric emission spectrum shape. However, the color gamut and the brightness of the aforementioned display is restricted because of the wide emission band of the CaAlSiN₃:Eu red phosphor. In this work, we used K₂SiF₆:Mn as an alternate red phosphor, which has a sharp emission spectrum. The display with the white LED using sharp β‐sialon:Eu and K₂SiF₆:Mn shows a wide‐color gamut, which covers the hole NTSC triangle. The use of K₂SiF₆:Mn enables to realize not only a wider color gamut but also a higher brightness of displays, compared with the use of CaAlSiN₃:Eu. Furthermore, it is confirmed that the white LED using sharp β‐sialon:Eu and K₂SiF₆:Mn is stable against temperature and also durable under the accelerated drive conditions.     

Orange‐red upconversion luminescence of Sm3+‐doped ZnO‐B2O3‐SiO2 glass by infrared femtosecond laser irradiation

Abstract— Near‐infrared‐to‐visible upconversion luminescence was observed in Sm³⁺‐doped ZnO‐B₂O₃‐SiO₂ glass under femtosecond laser irradiation. The luminescence spectra show that the upconversion luminescence originates from ⁴G^5/2 to ⁶H^j/2 (j = 5, 7, 9) transition of Sm³⁺. The dependence of the fluorescence intensity of Sm³⁺ on the pump power indicates that a two‐photon absorption process is dominant in the conversion of infrared radiation to the visible luminescence. The analysis of the upconversion mechanism reveals that the simultaneous absorption of two infrared photons produces the population of upper excited states, which leads to the characteristic orange‐red emission of Sm³⁺. A three‐dimensional display is demonstrated based on the multiphoton absorption upconversion luminescence.     

Near‐infrared‐emitting ZnS: Er and ZnS(Se): Cr TFEL devices

Abstract— Electroluminescent near‐infrared (NIR) emitters are of interest in creating special displays for applications such as communications, chemical sensoring, friend‐and‐foe identification, aligning and checking systems that detect NIR radiation, medicine, etc. By performing this research, known NIR emitters (thermal sources, semiconductor diodes and lasers, and solid‐state lasers) were supplemented by NIR‐emitting TFEL devices based on ZnS: Er(F) and ZnS(Se): Cr electron‐beam‐evaporated films. Some characteristics of these devices as NIR emitters are given. There are two narrow intensive bands at ^～980 and ～1530 nm in the emission spectrum of ZnS: Er(F) TFEL devices. The broadband emission is the range of from 1.8 μm up to 2.7 μm takes place in the ZnS(Se): Cr devices. The wavelength of the peak emission can be varied owing to interference. The mechanism of electroluminescence in the ZnS: Er(F) and ZnS(Se): Cr devices is the direct impact excitation of Er³⁺ and Cr²⁺ ions, respectively.     

Synthesis, characteristics and luminescent properties of a new europium(III) organic complex applied in near UV LED

A novel indane based β-diketone with trifluorobutane in the contraposition, 5-acetylindane-4,4,4-trifluorobutane-1,3-dione (HAITFBD) and its europium(III) ternary complex, Eu(AITFBD)₃phen, were designed and synthesized, where phen was 1,10-phenanthroline. The complex was characterized by IR, UV-visible, thermogravimetric analysis (TGA) and photoluminescence (PL) spectroscopy in details. The results show that the Eu(III) complex exhibits high thermal stability, wide and strong excitation bands from 300 nm to 425 nm when monitored at 611 nm, which matches well with the 380 nm-emitting InGaN chips. The complex exhibits intense red emission under excitation of near UV light due to the f-f transitions of the central Eu³⁺ ion. Based on the emission spectrum, the CIE chromaticity coordinates of the LED are calculated as x = 0.63 and y = 0.34, which is suitable to be used as an efficient red phosphor in fabrication of white LEDs. The fluorescence lifetime and the luminescence quantum yield were also measured. The lowest triplet state energy of the primary ligand AITFBD was measured to be 17,730 cm⁻¹, higher than that of the lowest excitation state energy level of the central Eu³⁺ ion, ⁵D₀, and this suggests that the photoluminescence of the complex is a ligand-sensitized luminescence process (antenna effect). Finally, a bright red light-emitting diode was fabricated by coating the Eu(AITFBD)₃phen complex onto a 380 nm-emitting InGaN chip. All the results indicate that Eu(AITFBD)₃phen can be applied as a red component for fabrication of near ultraviolet-based white light-emitting diodes.     

A study on the chromaticity shifts of blue phosphor for color plasma displays

The dependency of the chromaticity shifts on the concentration of Eu²⁺ doped in BaMgAl₁₀O₁₇ (BAM) was investigated under heat‐treatment and vacuum ultraviolet (VUV) irradiation. The Eu²⁺ ions in BAM show an asymmetrical broad emission band with a maximum at ～452 nm under excitation of VUV light at room temperature, showing that multiple crystalline cationic sites exist in the host. It was found that the chromaticity shifts greatly decrease with increasing heat‐treatment temperature. Regardless of the Eu²⁺ concentration, the chromaticity shifts caused by heat‐treatment are greater than that caused by VUV irradiation. Compared with conventional BAM, a solid solution of BAM with barium aluminate as a powder and film was also studied, and very few chromacity shifts were observed. It is suggested that the distribution of Eu²⁺ ions in different sites in a BAM lattice results in different chromaticity coordinates. By increasing the Eu²⁺ concentration in BAM, or under heat‐treatment and VUV irradiation, the emission band shifts towards longer wavelengths.     

A vertex‐fed hexa‐band frequency reconfigurable antenna for wireless applications

Present article embodies the design and analysis of an octagonal shaped split ring resonator based multiband antenna fed at vertex for wireless applications with frequency‐band reconfigurable characteristics. The proposed antenna is printed on FR4 substrate with electrical dimension of 0.4884 λ × 0.4329 λ × 0.0178 λ (44 × 39 × 1.6 mm³), at lower frequency of 3.33 GHz. The antenna consists of SRR based vertex fed octagonal ring as the radiation element and switchable reclined L‐shaped slotted ground plane. Antenna achieves six bands for wireless standards viz: upper WLAN (5.0/5.8 GHz), lower WiMAX (3.3 GHz), super extended C‐band (6.6 GHz), middle X band (9.9 GHz—for space communication), and lower K_U band (15.9 GHz—for satellite communication systems operating band). Stable radiation patterns are observed for the operating bands with low cross polarization. The proposed design achieves hexa band characteristics during switching ON state of PIN diode located at reclined L‐shaped slot in the ground plane. Experimental characteristic of antenna shows close agreement with those obtained by simulation of the proposed antenna.     

Investigation on luminescence of Na3Ca6(PO4)5:Eu2+ phosphor for LEDs

In this paper, a series of Na₃Ca_6(1−x)(PO₄)₅:xEu²⁺ (NCP:xEu²⁺, 0 ≤ x ≤ 4%) phosphors were prepared by conventional solid-state reaction method, and their photoluminescence properties were studied. Upon 365 nm excitation, the typical NCP:2%Eu²⁺ phosphor shows an asymmetric bluish green emission band with the dominant peak at 498 nm which could be attributed to the 4f⁶5d¹-4f⁷ transition of Eu²⁺. By measuring the time-resolved photoluminescence spectra, it reveals more than one Eu²⁺ emission center in the Eu²⁺-activated NCP phosphors. By monitoring 498 nm, the excitation spectrum of NCP:2%Eu²⁺ demonstrates a broad excitation band ranging from 240 to 450 nm, which can match well with the emission wavelength of the NUV LED chip. The SEM image shows that the average particle size of NCP:2%Eu²⁺ is about 19.4 µm. The above results imply that the NCP:Eu²⁺ phosphor could have potential application in LEDs.     

Eu2+‐doped barium thioaluminate EL devices prepared by two‐target pulsed‐electron‐beam evaporation

Abstract— New blue‐emitting thin‐film‐electroluminescent (TFEL) devices that satisfy the requirements for full‐color TFEL displays were developed. Eu²⁺‐doped BaAl²S⁴ thin films were used for the emission layer. BaAl²S⁴:Eu thin films were prepared by two‐target pulsed‐electron‐beam evaporation suitable for the deposition of multinary compounds that have difficulty in obtaining stoichiometoric thin films. The EL spectrum only had a peak at around 470 nm. The Commission Interantionale de l'Eclairge (CIE) color coordinates were x = 0.12 and y = 0.10. The luminance level from a 50‐Hz pulses voltage was 65 cd/m².     

Highly efficient blue organic light‐emitting diode with high color purity using 4,4′‐N,N′‐dicarbazole‐biphyenyl (CBP) doped with 1,4‐bis[2‐(3‐N‐ethylcarbazoryl) vinyl]benzene (BCzVB)

Abstract— An efficient pure blue multilayer organic light‐emitting diode employing 1,4‐bis[2‐(3‐N‐ethylcarbazoryl)vinyl]benzene (BCzVB) doped into 4,4′‐N,N′‐dicarbazole‐biphyenyl (CBP) is reported. The device structure is ITO (indium tin oxide)/TPD (N,N′‐diphenyl‐N,N′‐bis (3‐methylphenyl)‐1,1′biphenyl‐4,4′diamine)/CBP:BCzVB/Alq₃ (tris‐(8‐hydroxy‐quinolinato) aluminum)/Liq (8‐hydroxy‐quinolinato lithium)/Al; here TPD was used as the hole‐transporting layer, CBP as the blue‐emitting host, BCzVB as the blue dopant, Alq₃ as the electron‐transporting layer, Liq as the electron‐injection layer, and Al as the cathode, respectively. A maximum luminance of 8500 cd/m² and a device efficiency of 3.5 cd/A were achieved. The CIE co‐ordinates were x = 0.15, y = 0.16. The electroluminescent spectra reveal a dominant peak at 448 nm and additional peaks at 476 nm with a full width at half maximum of 60 nm. The Föster energy transfer and, especially, carrier trapping models were considered to be the main mechanism for exciton formation on BCzVB molecules under electrical excitation.     

A dual‐band dual‐polarized cubical DRA coupled with new modified cross‐shaped slot for ISM (2.4 GHz) and Wi‐MAX (3.3‐3.6 GHz) band applications

In this article, a new modified cross‐shaped coupled cubical dielectric resonator antenna (DRA) has been investigated for dual‐band dual‐polarized applications. The linearly polarized (LP) fields in DRA has been generated by using a single slot in the ground plane and kept at either 45° (S_L1) or ?45° (S_L2) from the microstrip feed line. Combining these two slots (S_L1 and S_L2) in the modified ground plane, the proposed structure able to generate circularly polarized (CP) field in DRA. But the generated CP field is not enough to cover ISM 2400 band. To achieve CP in ISM 2400 band, an extra slot (S_L3) to the existing slots and an extra strip (S_T) in the circular ring feed line have been included. This modified final antenna arrangement has been able to produce LP (due to loading effect, ie, slot and DRA) and CP fields (orthogonal modes have been generated, ie, TE ^x₁₁₁ and TE ^y₁₁₁), simultaneously. The measured CP and LP, ?10 dB impedance bandwidths are 11.85% (2.38‐2.68 GHz) and 9.11% (3.25‐3.56 GHz) in combination with the 3‐dB axial ratio bandwidth of 4.11% (2.38‐2.48 GHz). The generated CP and LP fields are used for different wireless communication bands such as ISM 2400 and Wi‐MAX (3.3‐3.7 GHz) bands.     

Dysprosium doped di-strontium magnesium di-silicate white light emitting phosphor by solid state reaction method

Dysprosium doped di-strontium magnesium di-silicate namely Sr₂MgSi₂O₇:Dy³⁺ phosphor was prepared by the solid state reaction method. The phase structure, surface morphology, particle size, elemental analysis was analyzed by using XRD, TEM, EDX and FTIR techniques. The EDX and FTIR spectra confirm the present elements in Sr₂MgSi₂O₇:Dy³⁺ phosphor. The optical properties of Sr₂MgSi₂O₇:Dy³⁺ phosphor was investigated utilizing thermoluminescence (TL), photoluminescence (PL), long lasting phosphorescence and mechanoluminescence (ML). Under the ultraviolet excitation, the emission spectra of Sr₂MgSi₂O₇:Dy³⁺ phosphor are composed of a broad band and the characteristic emission of Dy³⁺ peaking at 470 nm (blue), 575 nm (yellow) and 678 nm (red), originating from the transitions of ⁴F_9/2 → ⁶H_15/2, ⁴F_9/2 → ⁶H_13/2 and ⁴F_9/2 → ⁶H_11/2. CIE color coordinates of Sr₂MgSi₂O₇:Dy³⁺ are suitable as white light emitting phosphor. Decay graph indicate that this phosphor also contains fast decay and slow decay process. The peak of ML intensity increases linearly with increasing impact velocity of the moving piston. The possible mechanism of this white light emitting long lasting phosphor is also investigated.     

A dual‐band dual‐mode microstrip Yagi antenna with quasi‐end‐fire radiation

A dual‐band dual‐mode microstrip Yagi antenna with quasi‐end‐fire radiation patterns is proposed in this paper. It consists of five radiating patches driven by a single slot‐loaded patch placed in the middle. Meanwhile, two slot‐loaded parasitic patches are symmetrically located on two sides of the driven patch, respectively. In the lower band, the five patches involved resonate at TM₀₁ mode. While in the upper band, all the patches resonate at TM₀₂ mode. In order to ensure quasi‐end‐fire radiations in the both bands, four slots are symmetrically etched around the strongest surface currents of each patch resonating at TM₀₂ mode. As a result, the resonant frequency of TM₀₂ mode is decreased dramatically, while the resonant frequency of TM₀₁ mode almost remains unchanged. With these arrangements, the separations between any two of the adjacent patches at their centers satisfy the requirements in design of the microstrip Yagi antenna in both bands, so as to realize the dual‐band dual‐mode microstrip Yagi antenna on a single‐layer substrate. Finally, an antenna prototype is fabricated and tested. The measured results reveal that the dual operating bands of 2.76~2.88 and 4.88~5.03 GHz for |S₁₁| < ?10 dB are satisfactorily achieved. Most importantly, the proposed antenna can indeed realize the quasi‐end‐fire radiation patterns in dual operating bands.     

Red emitting MTiO3 (M = Ca or Sr) phosphors doped with Eu3+ or Pr3+ with some cations as co-dopants

Ca (or Sr)TiO₃:Eu³⁺, M (Li⁺ or Na⁺ or K⁺) and CaTiO₃:Pr³⁺, M (Li⁺ or Na⁺ or Ag⁺ or K⁺ or Gd³⁺ or La³⁺) powders were prepared by combustion synthesis method and the samples were further heated to ～1000 °C to improve the crystallinity. The structure and morphology of materials were examined by X-ray diffraction (XRD) and a scanning electron microscopy (SEM). The morphologies of SrTiO₃:Eu³⁺, CaTiO₃:Eu³⁺ or CaTiO₃:Pr³⁺ powders co-doped with other metal ions were very similar. Small and coagulated particles of nearly cubical shapes with small size distribution having smooth and regular surface were formed. Photo-luminescence spectra of CaTiO₃:Pr³⁺ and co-doped either with Li⁺, Na⁺, K⁺, Ag⁺, La³⁺ or Gd³⁺ ions showed red emissions at 613 nm due to the ¹D₂ → ³H₄ transition of Pr³⁺. The variation of intensity of emission peak with different co-doping follows the order: K⁺ > Ag⁺ > Na⁺ > Li⁺ > La³⁺ > Gd³⁺. The characteristic emissions of CaTiO₃:Eu³⁺ lattices had strong emission at 614 and 620 nm for ⁵D₀ → ⁷F₂ with other weak transitions observed at 580, 592, 654, 705 nm for ⁵D₀ → ⁷F_n transitions where n = 0, 1, 3, 4 respectively in all host lattices. Photoluminescence intensity in SrTiO₃:Eu³⁺ is more than CaTiO₃:Eu³⁺ lattices. A remarkable increase of photoluminescence intensity (in ⁵D₀ → ⁷F₂ transition) was observed if co-doped with Li⁺ ions in CaTiO₃:Eu³⁺ and SrTiO3:Eu³⁺.     

Effect of alkali metal ions co-doping on the structure and luminescent properties of phosphor Zn3(BO3)2:Eu3+

A series of the Zn₃(BO₃)₂:Eu³⁺ without or with alkali metal ions doping at a low sintering temperature were synthesized by the solid-state reaction method. The XRD pattern shows that all samples exhibit Zn₃(BO₃)₂ crystalline phase. The samples co-doped with alkali metal ions have better crystallinity compared with the un-compensated ones. The different charge compensation approaches have no influence on the shape and position of the emission and excitation spectra. However, the luminescent intensity of samples has been obviously enhanced with different alkali metal ions co-doping. The introduction of Li⁺ can increase the red emission of Eu³⁺ compared with the others. Thus, the volume compensation and the equilibrium of mole number can be taken into consideration by charge compensated (CC) approaches.