Experimental and theoretical luminous efficacies of phosphors used in combination with blue‐emitting LEDs for lighting and backlighting

Abstract— Phosphors that absorb blue light and emit in the green, yellow, and red have been synthesized, and their experimental and theoretical luminous efficacies are compared. It is proposed that a blue‐emitting LED in combination with red‐emitting Sr₂Si₅N₈: Eu²⁺ and green‐emitting SrGa₂S₄: Eu²⁺ phosphors is used as an energy‐efficient white‐light source for display backlighting applications.     

Quantum chemistry and QSPR study on relationship between crystal structure and emission wavelength of Eu2+‐doped phosphors

Abstract— The relationship between crystal structures and emission properties has been computationally investigated for Eu²⁺‐doped phosphors. The electronic structure of the Eu²⁺‐doped BaMgAl¹⁰O¹⁷ phosphor was analyzed by using the quantum chemistry method. The different effects of O and Ba atoms on the Eu 5d states were determined. The presence of O and Ba atoms increases and decreases the energy level of the Eu 5d orbital by forming anti‐bonding and bonding interactions, respectively. According to the electronic‐structure analysis, the structure index that represents the local geometrical information of the Eu atom was defined. The relationship between the crystal structures and the emission wavelengths of the 1 6 Eu²⁺‐doped oxide phosphors were studied by using the quantitative structure‐property relationship (QSPR). The QSPR model suggested that the both O and alkaline‐earth atoms around the Eu atom are of importance in the determination of the emission wavelength. The interaction between the Eu and the nearest O atoms make the Eu²⁺ emission wavelength short. On the other hand, the interaction from the alkaline‐earth atoms around the Eu atom lengthens the Eu²⁺emission wavelength. This evaluation method is useful in selecting the host material that indicates a desirable emission wavelength of the Eu²⁺‐doped phosphors.     

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.     

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.     

Red shift of the PSL spectra by Al3+ doping in BaFBr:Eu2+

Abstract— Photostimulated luminescent (PSL) materials are currently used for digital storage and display in radiography. The phosphor BaFBr:Eu²⁺ doped with Al³⁺ is shown to have a very high PSL intensity, and the peak of the PSL spectrum shifts to a longer wavelength. Compared with BaFBr:Eu²⁺ doped with Ca²⁺, Sr²⁺, or Mg²⁺, BaAlFBr:Eu²⁺ is better suited to the stimulated light wavelength emitted by a semiconductor laser. The red‐shift mechanism is considered to be a FAcenter for BaFBr:Eu²⁺ doped with Ca²⁺, Sr²⁺, or Mg²⁺ and a F^Z1 center for BaFBr:Eu²⁺ doped with Al³⁺.     

Development of field‐emission displays

Abstract— FEDs are one of the attractive flat‐panel displays that realize high‐quality motion images and low power consumption. FEDs are constructed by using three elemental technologies: micro‐ or nano‐fabrication technology of emitters, opto‐electronic semiconductor technology of anode patterns, and vacuum packaging technology. Each of the three elemental technologies is essential to realize FEDs. The present status of each three technologies, especially the improvement of Spindt‐type field emitters, the trend of flat vacuum packages, and development of phosphors for FEDs is described in this paper.     

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.     

New oxide phosphors for FEDs: Ruddlesden—Popper phases synthesized with IIIB‐group elements

Abstract— A red‐emitting phosphor, SrTiO³:Pr³⁺, for low‐voltage‐type FEDs and VFDs was developed by Futaba Corporation in 1996. The addition of Al or Ga is essential in the preparation of this phosphor because it improves the luminescence efficiency dramatically. For this impurity effect, Futaba Corporation proposed a charge‐compensation mechanism, which was supported by a recent observation of emission lines due to Al³⁺‐Pr³⁺ pairs. In addition, it was found that Al also works as a scavenger of planar defects, presumably SrO thin layers interleaved in the SrTiO³ lattice, by forming strontium aluminates. The latter mechanism suggests the possibility that a similar impurity effect can be found in materials with crystal structures, including alkaline‐earth oxide layers (Ruddlesden‐Popper phases).     

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.     

Identification of charge‐transfer transition between Gd3+ to O2− in gadolinium‐containing oxide phosphors in VUV region

Abstract— The broad bands at around 155 nm for GdAl₃(BO₃)₄:Eu, at 184 nm for Ca₄GdO(BO₃)₃:Eu, at 183 nm for Gd₂SiO₅:Eu, and at 170 nm for GdAlO₃:Eu were observed. These bands were assigned to the charge‐transfer (CT) transition of Gd³⁺‐O^2?. In the excitation spectrum of (Gd,Y)BO₃:Eu, a broadened excitation band was observed in VUV region. It could be considered that this band was composed of two bands at about 160 and 166 nm. The preceding band was assigned to the BO₃ group absorption. The later one at about 166 nm could be assigned to the CT transition of Gd³⁺‐O^2?, according to the result of GdAl₃(BO₃)₄:Eu, Ca₄GdO(BO₃)₃:Eu, Gd₂SiO₅:Eu, and GdAlO₃:Eu. The excitation spectra overlapped between the CT transition of Gd³⁺‐O^2? and BO₃ groups absorption. It caused the emission of Eu³⁺ to take place effectively in the trivalent europium‐doped (Gd,Y)BO₃ host lattice under 147‐nm excitation.     

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.     

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.     

Characterization of a SAG‐InGaN/AlGaN LED by mixed‐source HVPE with a multi‐sliding boat system

Abstract— The selective area growth (SAG) of a InGaN/AlGaN light‐emitting diode (LED) is performed by using mixed‐source hydride vapor‐phase epitaxy (HVPE) with a multi‐sliding boat system. The SAG‐InGaN/AlGaN LED consists of a Si‐doped AlGaN cladding layer, an InGaN active layer, a Mg‐doped AlGaN cladding layer, and a Mg‐doped GaN capping layer. The carrier concentration of the n‐type Al_xGa_1?xN (x ～ 16%) cladding layer depends on the amount of poly‐Si placed in the Al‐Ga source. The carrier concentration is varied from 2.0 × 10¹⁶ to 1.1 × 10¹⁷ cm^?3. Electroluminescence (EL) characteristics show an emission peak wavelength at 426 nm with a full width at half‐maximum (FWHM) of approximately 0.47 eV at 20 mA. It was found that the mixed‐source HVPE method with a multi‐sliding boat system is a candidate growth method for III‐nitride LEDs.     

Energy‐transfer dynamics of blue‐phosphorescent iridium and rhodium complexes doped in fluorescent molecules

Abstract— The temperature‐dependent photoluminescence features of polycarbonate thin films doped with blue‐phosphorescent molecules, either bis[(4,6‐difluorophenyl)‐pyridinato‐N,C^2′] (picolinate) iridium (Flrpic) or bis(2‐phenylpyridinato‐N,C^2′) (acetylacetonate) rhodium [(ppy)²Rh(acac)], which have an equivalent triplet energy of 2.64 eV, have been studied. The photoluminescence intensity of the Flrpic‐doped polycarbonate thin film did not show any dependence on temperature. On the other hand, as for the (ppy)²Rh(acac)‐doped polycarbonate thin film, decreasing photoluminescence intensity with increasing temperature (especially above 100K) was clearly visible. These results reflect that the internal heavy‐atom effect of (ppy)²Rh(acac) is weaker than that of Flrpic. Furthermore, the steady‐state and time‐resolved photoluminescence spectra of tris(8‐hydroxyquinoline) aluminum (Alq₃) thin films heavily doped with Flrpic or (ppy)²Rh(acac) (50 wt.%) at 8K was studied. It was found that the enhanced phosphorescence from Alq₃ is mainly due not to the external heavy‐atom effect by doping with the phosphorescent molecule but to the exothermic triplet energy transfer from the phosphorescent molecule to Alq₃.     

Numerical analysis of density of energy states for electron‐emission sources in MgO

Abstract— An analytical method to determine the density of energy states of electron‐emission sources (EESs) in chemical‐doped MgO is described using a discharge probability model and a thermal excitation and emission model. The density of energy states for multiple types of EESs is represented by using a linear combination of Gaussian functions of which parameters are determined by the theoretical emission time constant of an exoelectron and statistical delay time ts extracted from experimental stochastic distributions of discharge delay time in plasma‐display panels. When applied to Si‐doped MgO, the effective number of Si EES is calculated to be 1.8 × 10⁶ per cell. The average and standard deviations of activation energy have an energy level of 770 meV and a large value of 55 meV. In Si and H co‐doped MgO, the high peak density of [H^2?]⁰ appears at 550 meV. ts at the short time interval of 1 msec decreases and is independent of temperature due to exoelectron emission from the [H^2?]⁰. The dependence of ts at a time interval of 10 msec on temperature becomes weak because the energy structure of the Si EES broadens significantly attributed to the electrostatic effects of the doped H atoms.     

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.     

Active‐matrix organic light‐emitting diode using inverse‐staggered poly‐Si TFTs with a center‐offset gated structure

Abstract— A low‐cost active‐matrix backplane using non‐laser polycrystalline silicon (poly‐Si) having inverse‐staggered TFTs with amorphous‐silicon (a‐Si) n⁺ contacts has been developed. The thin‐film transistors (TFTs) have a center‐offset gated structure to reduce the leakage current without scarifying the ON‐currents. The leakage current of the center‐offset TFTs at Vg = ?10 V is two orders of magnitude lower than those of the non‐offset TFTs. The center‐offset length of the TFTs was 3 μm for both the switching and driving TFTs. A 2.2‐in. QQVGA (1 60 × 1 20) active‐matrix organic light‐emitting‐diode (AMOLED) display was demonstrated using conventional 2T + 1C pixel circuits.     

Reduction of defects and improvement in the performance of blue phosphor for thick‐dielectric electroluminescent displays using Color‐by‐Blue

Abstract— Defect‐free large‐area inorganic thick‐dielectric EL (TDEL) displays using Color by Blue (CBB) technology have been successfully developed. We have achieved the world's highest blue‐phosphor luminance of 900 cd/m² for a single‐pixel device by using CBB and by optimizing the e‐beam gun configuration and the flow rate of H₂S in the vacuum chamber. By analyzing the defects on panels with triple‐pattern phosphors and CBB panels, we also found that the number of defects on CBB panels can be drastically reduced compared with those on triple‐pattern panels. The defect‐free 17‐in. VGA CBB panels show better characteristics, a high peak luminance of 600 cd/m² and a high contrast ratio of 1000:1, compared with those of triple‐pattern panels.     

Study of the effect of water on thermal and operating degradation of BaMgAl10O17: Eu2+ (BAM) blue phosphor

Abstract— From the adsorption and desorption characteristics of water, we showed that water can intercalate into BaMgAl₁₀O₁₇: Eu²⁺ blue phosphor. ESR, XANES, and XPS analyses confirmed that oxidation by water causes thermal degradation of BAM. We also demonstrated that intercalated water accelerates luminance degradation under VUV irradiation and showed oxidation of Eu²⁺ during panel operation by means of μ‐XPS. We concluded that the cause of thermal and operating degradation of BAM is the oxidation of Eu²⁺ due to water.     

High‐efficiency p‐i‐n organic light‐emitting diodes with long lifetime

Abstract— High‐performance organic light‐emitting diodes (OLEDs) are promoting future applications of solid‐state lighting and flat‐panel displays. We demonstrate here that the performance demands for OLEDs are met by the PIN (p‐doped hole‐transport layer/intrinsically conductive emission layer/n‐doped electron‐transport layer) approach. This approach enables high current efficiency, low driving voltage, as well as long OLED lifetimes. Data on very‐high‐efficiency diodes (power efficiencies exceeding 70 lm/W) incorporating a double‐emission layer, comprised of two bipolar layers doped with tris(phenylpyridine)iridium [Ir(ppy)₃], into the PIN architecture are shown. Lifetimes of more than 220,000 hours at a brightness of 150 cd/m² are reported for a red PIN diode. The PIN approach further allows the integration of highly efficient top‐emitting diodes on a wide range of substrates. This is an important factor, especially for display applications where the compatibility of PIN OLEDs with various kinds of substrates is a key advantage. The PIN concept is very compatible with different backplanes, including passive‐matrix substrates as well as active‐matrix substrates on low‐temperature polysilicon (LTPS) or, in particular, amorphous silicon (a‐Si).