TWI261613B - Phosphor formulations for low voltage and manufacturing methods thereof - Google Patents

Abstract

This invention provides phosphor formulations for operating at low voltage and their manufacturing methods. The phosphor materials have the compositions BaMgAl10O17 doped with europium ions or europium and manganese ions. Excited by electron beam, the phosphors emit blue or bluish green light, respectively. Furthermore, the phosphor formulations of the invention produce single phase phosphors by many synthetic methods, such as solid state reaction, co-precipitation, sol gel, and micro-emulsion. The phosphor formulation manufacturing methods of the invention are simple and also suitable for mass production so as to make valuable products.

Description

1261613 V. INSTRUCTION DESCRIPTION α) Technical Field of the Invention The present invention relates to a fluorescent powder formulation suitable for low operating voltage electron beam excitation and a preparation method thereof, and particularly to a field emission display (field emission display; FED), various phosphor powder formulations by means of electrons, plasma-excited phototubes and light sources, and a preparation method thereof. [Prior Art]

The importance of displays in today's life is increasing. In addition to computers or the Internet, televisions, mobile phones, personal digital assistants (P D A) and vehicle information systems must control or transmit messages through the display. For the reasons of weight, volume and health, the ratio of flat displays is increasing for each product. In 1999, the global flat panel display market was approximately $18.5 billion. This huge growth was due to the increased functionality and price decline of liquid crystal displays (L C D). And other flat panel displays;

F P D) is in the stage of active development. Its uses include large-scale home audio and video equipment such as plasma and projection, as well as a wide range of mobile phones and digital cameras. Technology that is expected to surpass and replace liquid crystal displays in terms of price and performance is attracting a lot of money for research and development. In the future, the characteristics of the display need to be small, power-saving, high-resolution, and responsive; while the production requires high yield and mass production. Among the many display technologies, the field emission display (FED) is known as the new technology that has the greatest chance to replace LCD. The technical principle of F E D is very similar to that of a conventional cathode ray tube (c a t h o d e - r a y

Page 6 1261613 ————————— V. Invention Description (2) tube; CRT), in fact, FED is a thin cathode ray tube (CRT). Considering the structural aspect, the CRT is to emit an electron beam from a single electron gun to strike the phosphor panel, and use the deflecting plate to control the direction of the electron beam, but the FED has no deflecting plate, and each pixel is completed by an emitting tip, and the entire FED is counted. 100,000 active cold emitters. Although the appearance of F E D is like a thin C R T, the operating voltage (SlkV) of F E D is much smaller than the operating voltage (15 to 30 kV) required by the CRT. The first proposed field emission principle is called S p i n d t t y p e micro-scale array, and each unit in the array includes a tiny circular hole and a metal cone therein. However, the lithography technique required to make a circular hole on a substrate and the size limitation of the evaporation technique for making a metal cone limit the size of the finished product (400 mm per side) and the manufacturing cost is high. In addition, Spindt's tip of the field emitter is also prone to loss due to loss. In addition to the Spindt type field emitters, the industry is looking for alternative technologies that are exceptionally good, easy to mass produce, and inexpensive. Early literature showed that the carbon of the diamond structure was used as the field emission electron, and the required starting voltage was extremely small. Later, it was found that the graphite or carbon nanotubes of the nanostructure are also good field emission materials, among which the carbon nanotubes (carb〇rl) The characteristics of nano tube; CNT) are particularly significant' and also have the best chance of commercialization. Another important part of the carbon nanotube field emitter (CNT-FED) is the layer of phosphor material. The characteristics of this layer of phosphor material will determine the light color and light-emitting efficiency of the field emitter, and have considerable R&D value. And the current research on phosphor powder in this area is still in its infancy. In terms of related patents, South Korea's Samsung (Samsung) has applied for more than a dozen articles since 1998.

Page 7 1261613 V. Description of the Invention (3) Patent for operating voltage phosphors, and discloses various phosphor formulations in the patents and claims that these phosphors have the advantages of high efficiency for FED, including ZnS, Zn, Cd)S, ZnS·· Zn, ZnS: Ag, (Zn, Cd)S: Ag,

Cl, ZnGa2 04, ZnGa2 04: B i, SrTi03: RE (RE is a rare earth element) and a phosphor such as Y2Si05 (such as U.S. Patent No. 5 0 6 8 1 5 7 , 6 1 5 2 9 6 5, 6 3 2 2 7 2 5 ^ 6 4 1 6 6 8 8 ^ 6 4 4 0 3 2 9 , 6 6 4 1 7 5 6 and 2 0 0 3 1 9 7 4 6 0, European Patent No. 0 8 8 2 7 7 6 and 1 0 5 2 2 7 6, and French Patent No. 2800509). In addition, Futaba Denshi Koggo has applied for several patents on low operating voltage phosphors. The phosphors are SrTi03: pr, ZnGa2 04: Li, p, (Zn, Cd)S: Ag, C1. versus

La^S: RE (RE is a rare earth element) phosphor (such as U.S. Patent No. 5 6 1^ 0 9 8 , 2 0 0 2 0 5 7 2 2 9 and Republic of China Patent No. 4 6 4 9 〇 2 ). Currently, the phosphor used in the commercial FED is roughly a P22 series phosphor, wherein the blue phosphor is ZnS: Ag, C1, and the green phosphor is ... u, u' Al, and red light The light body is ns: Eu. The phosphors of these ί : 3 ί cathode ray tubes (C!T), these phosphors are not used in crt to make the FED have a low-day spoon. =: Causes the deterioration of the working body, the source of the pollution field, and the reduction: the qualitative difference between the two climates is better than that of the oxides, and it is easy to make... Π = shortened life. In addition, these CRTs have poor luminous efficiency when they are hit by electrons in the luminescent moon. - $ # ΐ 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述

Page 8 1261613 V. Description of invention (4) The luminous intensity of the material can be applied to the FED industry. SUMMARY OF THE INVENTION An object of the present invention is to provide a fluorescent material having a host lattice of BaMgA 11 () 017 oxide, doped with ytterbium ions or simultaneously doped with lanthanum and manganese ions, and excited by an electron beam to obtain blue Or blue-green fluorescent. It has pure light color and high luminous intensity, and has high structural stability compared with sulfide. In addition to fluorescent materials suitable for FED, it can be applied to various electronic and electrical materials due to its pure color and high luminous intensity. Pulp-excited phototube and fluorescent material of the light source. That is, the present invention achieves the above objects by the following technical means; it comprises: consisting of the following inventions: · A phosphor powder formulation based on BaMgA 11Q017 as a host lattice, excited by low voltage Source excitation can produce blue or blue-green fluorescence, and its host lattice material formula is (B a^E ux) Mg A 11Q017 or (Bai-χΕ ux ) ( Mg yMny) Al10O17 (0.0001 S0.5 and 0.0001 Sy S0.5 or 0.05 $ 0 . 2 and 0 . 0 5 $ y $ 0 . 2 ), the host lattice material formulation is synthesized by solid state reaction method, and the preparation method of the phosphor powder formula includes the following Steps: a. Mixing raw materials: the raw materials include lanthanum, cerium, magnesium, manganese and aluminum, which are reduced from their metal oxides or their salts, and then composed of one or more compounds, ruthenium compounds, ruthenium compounds, town compounds, fierce The compound and the compound are subjected to sintering; b. Sintering: pre-sintering is carried out for 6 to 24 hours at a temperature of 14,000 to 1880 °C in a reducing gas atmosphere (mixed gas atmosphere of mixed hydrogen or the like).

1261613 V. INSTRUCTIONS (5) The formulation of the host lattice material can also be formed by a method of coprecipitation, gelation or microemulsion. The low voltage excitation source is selected from the group consisting of a carbon nanotube (CNT ο η η 〇 tube emitter; CNT), a surface conduction electron emitter (SED), and a ballistic electron surface emitter (BSD). And a group of electronic excitation sources such as metal insulator metal emitters (MIMs); the excitation source has a voltage of $ 1 k V, and the excitation source is a plasma excitation source.

[Embodiment] Example 1: 0.6274 g of barium oxide (BaO), 0.800 g of cerium oxide (Eu2 03), 〇·1 8 3 3 g of magnesium oxide (MgO) and 2.173 g of alumina (α12〇) 3) (ie, according to the ratio of (B a 〇9 E u.M ) M g A 1 i 〇0丨7), mix well, grind and mix thoroughly with a spider, and place the homogeneous mixture in the oxidation Then, the alumina crucible is placed in a high-temperature furnace in a reducing atmosphere and pre-sintered at 丨6 5 1 for 12 hours, and the heating and cooling rates of the sintering process are both 5 艽/m丨n. After the sintering is completed, it is ground with a grinding spider to make it a uniform powder of powder. Embodiment 2:

1.8947 grams of barium oxide (BaO), 0.2416 grams of barium oxide (Eu2〇3), 〇·5 0 9 1 gram of magnesium oxide (MgO), 7. gram of alumina (Al2〇3) and 〇·1 2 6 3 g of carbonic acid (MnC03) (that is, according to the ratio of (BauEw.JUg.92Mn/〇8) 3 A 11Q01?), thoroughly mixed, thoroughly mixed with a mortar, and

Page 10 1261613 V. Description of the invention (6) The homogeneous mixture is placed in an alumina crucible, and then the alumina crucible is placed in a high-temperature furnace and pre-sintered at 1 60 50 ° C for 12 hours in a reducing atmosphere. The heating and cooling rates are both 5 °C / mi η. After the sintering is completed, it is ground by a mortar to make it into a powder of uniform particles, that is, a finished product. Samples of (Ba^EuJMgAU? (X = 0.1) and (Ba!-χΕιιχ) (Μ§1ιΜη7)Α11()017 (X = 0.1, y = 0.08) prepared according to an embodiment of the present invention, which are wound by X-ray powder The purity of the crystal phase was identified by the ejector. The results are shown in Fig. 1 (a) and (b). The standard BaMgAlnC^Jb compound (Fig. 1 (c)) (JCPDS η 〇: 2 6 - 0 1 6 3 ) X-ray powder diffraction pattern comparison, it can be seen that the phosphor disclosed in the present invention is a single phase, has a hexagonal structure, and its lattice constant is 8=1)=5.62 A, c = 8.781 A; a = β = 90°, γ = 120° ° "Fig. 2" is prepared according to an embodiment of the present invention (Ba^xEuJ MgAl10O17 (X = 0.1) and (BapxEUxKMg yMny) Al10O17 (X = 0 . 1 , y = 0 . 0 8 ) The light emission spectrum of the sample. It can be seen from the results that the two kinds of phosphors emit blue and blue-green fluorescence through low-voltage electron beam excitation. The data was converted to the form of this luminosity by the formula of the chromaticity diagram set by the Commission Internationale de l'Eclairage (CIE) in 1973. The chromaticity coordinates are shown in Figure 3. This is equivalent to X = 0.1481 and y = 0.0659 blue light and X = 0.1470 and y = 0.2777 blue-green light. The chromaticity coordinate map shows the fixed strontium content. Increasing the content of manganese will make the phosphor color blue

Page 11 1261613 V. INSTRUCTIONS (7) The color shifts to the green range, and the color of the phosphor can be changed by changing the concentration of the doping ions. Page 12 1261613 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1(a) shows an X-ray powder diffraction pattern of a (Ba^EUx) MgAl10O17 (x20.1) sample prepared according to an embodiment of the present invention. Fig. 1(b) is an X-ray powder diffraction pattern of a sample (Bai_xEux) (Mg!_yMny) A 110〇17 (x = 0.1, y = 0.08) prepared according to an embodiment of the present invention. Figure 1 (c) is a standard X-ray powder diffraction pattern of BaMgAl1Q017.

Figure 2 is a diagram of U) prepared according to an embodiment of the present invention as (Bai_xEux) MgAl10O17 (X = 0·1) and (a) is (Ba BuxEUxKMgbyMndAluOn (X =0 · 1 , y = 0 · 0 8 The light emission spectrum of the sample. Fig. 3 shows the light emission spectrum of (Fig. 2) on the CIE chromaticity coordinate map.

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Claims (1)

1261613 1 · A fluorescent powder formulation suitable for low-operating voltage electron beam excitation, which is based on BaMg A 1′′” as a main crystal lattice, which is excited by a low-voltage excitation source to produce aged or blue-green fluorescent light, wherein the B a M g A 1! 〇0 i7 is the main crystal material 酉 方 is (BahEuJMgAluOn, where 0 · 0 5 $ X $ 0 . 2 and 0 . 〇〇5 $ y S 0 · 2, which is coprecipitated The method is formed by a gel method or a micro-emulsion method. 2. The phosphor powder powder composition suitable for low-operating voltage electron beam excitation according to the first aspect of the patent application, wherein the low-voltage excitation source is selected from the group consisting of nano carbon Carbon nanotube emitter (CNT), surface conduction electron emitter (SED), ballistic electron surface emitter (BSD) and metal insulator metal source (metal insulator metal emi 11 er ; Μ IM A group of electronic excitation sources, etc. 3 · A fluorescent powder formulation suitable for low operating voltage electron beam excitation as described in claim 1 of the patent application, wherein the excitation source voltage is ^ 1 kV. Manufacturing as applied The preparation method of the phosphor powder powder suitable for low operating voltage electron beam excitation according to the first item of the first aspect, wherein the BaMgAUn is a host crystal material material is synthesized by a solid state reaction method, which comprises the following steps: a. b · Sintering: Pre-sintering is carried out for 6 to 2 hours in a reducing gas atmosphere (mixed gas atmosphere such as mixed hydrogen) at a temperature of 1 400 to 1 800 °: 5 The preparation method of item 4, wherein the raw material mixing system forms (Bai_xEnx) MgAllG〇i7 or (Babu xEUx) (Mgbu yMny) Al1() 017 1261613 VI. The scope of application for patents, including the source of lanthanum, cerium, town, and smelting elements, is selected from the group consisting of metal oxides or their salts, and then sintered in a reducing environment. 6. The preparation method of claim 5, wherein the bismuth compound, hydrazine compound, cation compound, stimulating compound, and indole compound are composed of one or more compounds. 7. The preparation method of claim 4, wherein the optimum sintering is carried out in a reducing gas atmosphere at a temperature of 14,000 to 1880 ° C for pre-sintering for 10 to 15 hours. 8. The preparation method of claim 4, wherein the other optimum sintering is performed in a reducing gas atmosphere at a temperature of 1 500 to 1700 ° C for pre-sintering for 10 to 15 hours. 9. The preparation method of claim 4, wherein the reducing environment during sintering is mixed with a mixed gas atmosphere such as hydrogen nitrogen. The preparation method of claim 4, wherein the BaMgA 110〇17 is one of a group selected from the group consisting of a coprecipitation method, a gel method, and a microemulsion method. The formation of the law. Page 15