TWI261613B

TWI261613B - Phosphor formulations for low voltage and manufacturing methods thereof

Info

Publication number: TWI261613B
Application number: TW93108217A
Authority: TW
Inventors: Ru-Shi Liu; Chia-Cheng Kang; Whe-Yi Chiang
Original assignee: Pong & Huang Internat Co Ltd
Priority date: 2004-03-26
Filing date: 2004-03-26
Publication date: 2006-09-11
Also published as: TW200532004A

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 五、發明說明α) 【發明所屬之技術領域】本發明係關於一種適合低操作電壓電子束激發之螢光粉體配方及其製備方法，尤其是一種適用於場發射顯示器（field emission display; FED)、各種藉由電子、電漿激發之光電管以及光源之螢光粉體配方及其製備方法。【先前技術】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]

顯示器於現今生活之重要性日益增加，除電腦或網際網路外，電視機，手機，個人數位助理（P D A )與車用資訊系統等，均須透過顯示器控制或傳遞訊息。基於重量、體積及健康方面之理由，各產品採用平面顯示器之比率越來越高。1 9 9 9年全球平面顯示器市場約為1 8 5億美元，此巨幅成長應歸功於液晶顯示器（L C D)之功能提昇與價格下滑。而其他平面顯示器（flat panel display;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)均處於積極發展之階段，其用途包括電漿與投影等大尺寸的家庭影音設備以及市場廣大的行動電話與數位相機等。可望在價格與性能上超越並取代液晶顯示器的技術，正吸引大量資金投入研發。未來顯示器的特性需求在於體積小、省電、高解析度、反應迅速；而製成方面則要求高良率、易大量生產。在眾多的顯示技術中，場發射顯示器（f i e 1 d emission display; FED)號稱是最有機會取代LCD之新技術。F E D之技術原理極類似傳統陰極射線管（c a t h o d e - r a yF 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

第6頁 1261613 ——— ———------ 五、發明說明（2) tube; CRT)，其實FED即為薄型之陰極射線管（cath〇de 一 ray tube; CRT)。考慮結構方面，CRT為由單一電子槍發射電子束撞擊磷光面板，並利用偏向板控制電子束方向，但是F E D並無偏向板，每一像素均由電子發射子 (emitting tip)完成，整個FED由數十萬個主動冷發射子組成。雖然外觀上，F E D像是薄型的C R T，但是F E D之工作電壓（SlkV)則遠小於CRT所需之工作電壓（15〜30kV)。最先提出之場發射原理稱做S p i n d t t y p e微尺寸陣列，陣列中每一單元包括一微小圓孔及其中之金屬圓錐。然於基材上製作圓孔所需之微影技術與製作金屬錐之蒸鍍技術的尺寸限制，均限制顯示器成品大小（每邊 4 0 0 mm)，而且製作成本高。此外，Spindt以…場發射子的尖端也易因損耗而降低壽命。除Spindt type場發射子 (field emitter)之外，產業界正尋求其他場發射具有特性優良、易量產製造、以及價格低廉之替代技術。早期文獻顯示以鑽石結構之碳作為場發射電子，所需之啟動電壓極小，隨後研究發現奈米結構的石墨或奈米碳管亦為良好之場發射材料，其中奈米碳管（carb〇rl nano tube; C N T)之特性尤為顯著’亦最有機會實現商業化。於奈米碳管場發射器（C N T - F E D )中另一重要部分為螢光材料層’此螢光材料層之特性將決定場發射器之光色與放光效率，具相當之研發價值，且目前全世界在於此方面之螢光粉研究仍屬萌芽階段。於相關專利方面，韓國三星公司（Samsung)自1998年起陸續申請十數篇關於低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.

第7頁 1261613 五、發明說明（3) 操作電壓螢光體之專利，並於專利中揭示多種螢光體配方且均稱此些螢光體應用於F E D具有高效率之優點，包括 ZnS、（Zn，Cd)S、ZnS·· Zn、ZnS: Ag、（Zn，Cd)S: Ag，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 為稀土元素）與 Y2Si05等螢光體（如美國專利案號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 與 2 0 0 3 1 9 7 4 6 0，歐洲專利案號0 8 8 2 7 7 6與1 0 5 2 2 7 6，以及法國專利案號 2800509)。另外日本雙葉公司（Futaba Denshi Koggo) 亦申請數篇關於低操作電壓螢光體之專利，其螢光體分別為 SrTi03: pr、ZnGa2 04: Li， p、（Zn，Cd)S: Ag， C1 與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為稀土元素）螢光體（如美國專利案號 5 6 1^ 0 9 8、2 0 0 2 0 5 7 2 2 9與中華民國專利第4 6 4 9 〇2號）。目前商品化之FED所使用之螢光體大致為P22系列螢光體，其中藍光螢光體為ZnS: Ag， C1 ，綠光螢光體為…·· u， u’ Al ，以及紅光螢光體為ns: Eu。該等這些整 ί : 3 ί陰極射線管(C!T)所，之螢光體，為使FED具低日士勺零i思應用於FED時該等這些螢光體並未如在crt 以=:導致勞光體劣化、污染場發射源、降低 :使二氣候之定性較氧化物差，亦容易使… Π =命期縮短。此外’該等這些CRT用發光月匕里^電子撞擊時，其發光效率不佳。 - $ # ΐ於上述之缺點，目前各方均朝向能為低摔作電壓所激發之氧化物勞光材料研究，致力於改善氧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

第8頁 1261613 五、發明說明（4) 材料其發光強度，期能應用於FED產業。【發明内容】本發明之目的在於提供一種螢光材料，其主體晶格為BaMgA 11()017氧化物，摻雜銪離子或同時摻雜銪與錳離子，受電子束激發後可得藍色或藍綠色之螢光。其光色純且發光強度高，與硫化物相比結構穩定性高，除可適合用於FED之螢光材料，由於其光色純且發光強度高，更可應用於各種藉由電子、電漿激發之光電管以及光源之螢光材料。亦即，本發明係藉由下列之技術手段實現上述之目的；其包括有：係由以下各項發明所構成·· 一種以BaMgA 11Q017為主體晶格的螢光粉體配方，受低電壓激發源激發可產生藍色或藍綠色之螢光，其主體晶格材料配方係為（B a^E ux) Mg A 11Q017 或（Bai—χΕ ux ) ( Mg卜 yMny) Al10O17 (0.0001 S0.5 與 0.0001 Sy S0.5 或 0.05 $ 0 . 2與0 . 0 5 $ y $ 0 . 2 )，該主體晶格材料配方係藉由固態反應法合成，其螢光粉體配方的製備方法包括下列之步驟： a. 原料混合：其原料包括鋇、銪、鎂、錳與鋁元素，係還原自其金屬氧化物或其鹽類，再由一種或多種化合物組成鋇化合物、銪化合物、鎮化合物、猛化合物及紹化合物，進行燒結； b. 燒結：需在還原氣環境（混合氫氣等之混合氣體環境）中以溫度1 4 0 0〜1 8 0 0 °C下進行預燒結6〜2 4小時。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 五、發明說明（5) 此主體晶格材料配方也可藉由共沉澱法、凝膠法或微乳膠法所成群之方法所形成。該低電壓激發源係選自奈来碳管（c a r b ο η n a η 〇 t u b e emitter ;CNT)、表面傳導電子源（surface conduction electron emitter ;SED)、衝擊式表面電子源 (ballistic electron surface emitter ; BSD)及金屬絕緣體發射源（metal insulator metal emitter ;MIM)等所成群之電子激發源；其激發源之電壓$ 1 k V，激發源係為電漿激發源。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.

【實施方式】實施例一：將0.6274克之氧化鋇（BaO)、0·800克氧化銪 (Eu2 03 )、〇· 1 8 3 3 克氧化鎂（MgO)與2. 3173 克氧化鋁（α12〇3) (即依（B a 〇 9 E u。M ) M g A 1 i 〇 0丨7之比例）充分混合，以研蛛加以研磨充分混合，將均勻之混合物置於氧化I呂掛竭中，後將氧化鋁坩堝置入高溫爐於還原氣氛環境下以丨6 5 〇預燒結1 2小時，燒結過程之昇溫及降溫速率均為5艽/m丨n。燒結完畢，以研蛛加以研磨，使其成為顆粒均勻之粉末’即付成品。實施例二：[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:

將1.8947克之氧化鋇（BaO)、0.2416克氧化銪 (Eu2〇3)、〇·5 0 9 1 克氧化鎂（MgO)、7.〇〇〇〇克氧化鋁（Al2〇3) 與〇· 1 2 6 3 克碳酸猛（MnC03)(即依（BauEw.JUg。92Mn/〇8)3 A 11Q01?之比例）充分混合，以研缽加以研磨充分混合，將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

第10頁 1261613 五、發明說明（6) 均勻之混合物置於氧化鋁坩堝中，後將氧化鋁坩堝置入高溫爐於還原氣氛環境下以1 6 5 0 °C預燒結1 2小時，燒結過程之昇溫及降溫速率均為5 °C / m i η。燒結完成後，以研缽加以研磨，使其成為顆粒均勻之粉末，即得成品。根據本發明實施例所製備之（Ba^EuJMgAU? (X = 0.1)與（Ba!—χΕιιχ)(Μ§1ιΜη7)Α11()017 (X = 0.1，y = 0.08)樣品，以X光粉末繞射儀鑑定其晶相純度，結果如「第1圖 (a)與（b)」所示。經與「第1圖（c)」之標準BaMgAlnC^Jb 合物（J C P D S η 〇 : 2 6 - 0 1 6 3 ) X光粉末繞射圖譜比較，可知本發明所揭示之螢光體為單一相，具六方晶系 (hexagonal)之結構，其晶格常數為8=1)=5.62 A， c = 8.781 A ; a = β = 90° ，γ = 120° ° 「第2圖」為本發明之實施例所製備之（Ba^xEuJ MgAl10O17 (X = 0.1)與（BapxEUxKMg 卜 yMny)Al10O17 (X = 0 . 1 ，y = 0 . 0 8 )樣品之光發射光譜圖。由結果可知，經由低電壓之電子束激發，此二種螢光體發射藍色及藍綠色之螢光。將發射光譜之數據以1 9 3 1年由國際照明委員會（Commission Internationale de l’Eclairage，CIE) 所制定之色度座標圖（chromaticity diagram)之公式換算成此螢光體所代表之色度座標，標示於「第3圖」。其相當於X = 0.1481 與y = 0.0659之藍光以及X = 0.1470 與y = 0.2777之藍綠光，由色度座標圖得知固定銪元素含量而增加錳元素之含量將使螢光體光色自藍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

第11頁 1261613 五、發明說明（7) 色向綠色範圍移動，可藉改變摻雜離子之濃度而改變螢光體之發光光色。第12頁 1261613 圖式簡單說明第1圖（a)，係根據本發明之實施例所製備之（Ba^EUx) MgAl10O17 (x二0. 1 ) 樣品之X光粉末繞射圖譜。第1圖（b)，為根據本發明之實施例所製備之（Bai_xEux) (Mg!_yMny) A 110〇17 (x = 0.1 ，y = 0.08)樣品之X 光粉末繞射圖譜。第1圖（c)，為BaMgAl1Q017之標準X光粉末繞射圖譜。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.

第2圖，係根據本發明之實施例所製備之U)為（Bai_xEux) MgAl10O17 (X = 0· 1)與（a)為（Ba卜xEUxKMgbyMndAluOn (X =0 · 1 ，y = 0 · 0 8 )樣品之光發射光譜圖。第3圖，係將（第2圖）之光發射光譜標定於C I E色度座標圖。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.

第13頁Page 13

Claims

12616131261613

1 · 一種適合低操作電壓電子束激發之螢光粉體配方，係、以BaMg A 1』”為主體晶格，受低電壓激發源激發可產生龄色或藍綠色之螢光，其中該B a M g A 1! 〇 0 i7為主體晶袼材料酉己方係為（BahEuJMgAluOn ，其中0 · 0 5 $ X $ 0 . 2與0 . 〇〇 5 $ y S 0 · 2，其係由共沉澱法、凑是膠法或微乳膠法所形成。 2 . 如申請專利範圍第1項所述適合低操作電壓電子束激發之螢光粉體配方，其中該低電壓激發源係選自奈米碳管（carbon nanotube emitter ;CNT)、表面傳導電子源 (surface conduction electron emitter ； S E D)、衝擊式表面電子源（ballistic electron surface emitter ; BSD)及金屬絕緣體發射源（metal insulator metal e m i 11 e r ; Μ I M )等所成群之電子激發源。 3 ·如申請專利範圍第1項所述適合低操作電壓電子束激發之螢光粉體配方，其中該激發源之電壓^ 1 kV。 4 · 一種用以製造如申請專利範圍第1項所述適合低操作電壓電子束激發之螢光粉體配方的製備方法，該 BaMgAUn為主體晶袼材料配方係藉由固態反應法合成，其包括下列之步驟： a. 原料混合； b ·燒結：需在還原氣環境（混合氫氣等之混合氣體環境）中以溫度1 4 0 0〜1 8 0 0 t：下進行預燒結6〜2 4小時。 5 ·如申請專利範圍第4項之製備方法，其中該原料混合係形成（Bai_xEnx)MgAllG〇i7 或（Ba卜xEUx)(Mg卜yMny)Al1()017 之配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 六、申請專利範圍方，其中包括鋇、銪、鎮、猛與紹元素來源係選自其金屬氧化物或其鹽類，再於還原環境中進行燒結。 6. 如申請專利範圍第5項之製備方法，其中，該鋇化合物、銪化合物、鎮化合物、猛化合物及铭化合物係由一種或多種化合物所組成。 7. 如申請專利範圍第4項之製備方法，其中，最佳的燒結係於還原氣環境、溫度1 4 0 0〜1 8 0 0 °C下進行預燒結1 0 〜1 5小時。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. 如申請專利範圍第4項之製備方法，其中，另一最佳燒結係於還原氣環境、溫度1 5 0 0〜1 7 0 0 °C下進行預燒結 1 0〜1 5小時。 9. 如申請專利範圍第4項之製備方法，其中，燒結時之還原環境係混合氫氮等之混合氣體環境。 1 0 .如申請專利範圍第4項之製備方法，其中，該 BaMgA 110〇17為主體晶格材料酉己方係藉由選自共沉澱法、凝膠法和微乳膠法的群組之一的製法形成。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.

第15頁Page 15