201226526 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種以溶凝膠技術製備錳活化鋅鋁尖晶 石（ΖηΑ12〇4:Μη2 + )綠光螢光奈米粉體的方法，尤其是藉由控 制鋅亂化鹽與鋁異丙醇鹽之水解與解膠反應，並摻雜不同 濃度之錳作為活化劑，以形成清徹之溶膠，經縮聚合、膠 化、乾燥及熱處理以製備均質單相之鋅鋁尖晶石螢光奈米 粕體，並藉由調整摻雜濃度及改變熱處理溫度與氣氛，可 • 製得具有高效率發射綠光螢光性質的錳活化鋅鋁尖晶石 (ΖηΑ12〇4:Μη2 + )奈米粉體。 【先前技術】 近年來，能源與環保的問題普遍受到高度重視，國際 間均積極於研發新能源供應技術與綠色材料，其中低污染 與高效率螢光材料的發展成為現今最迫切的課題之一。螢 光材料因具有耗電量低、壽命長、無熱輻射和反應速度佳 等優點，其應用範圍包括日光燈、霓虹燈、發光二極體等 照明設備，及目前備受矚目的顯示器關鍵元件等。9〇年代 日本首先開發出氮化鎵等具有商業應用價值的藍光LEd , 並配合黃光螢光體釔鋁石榴石（YAG，ymium aluminum g net)作為同效率白光光源，開發新式螢光材料應用於照明 設備，為目前產業界及學術界積極研究的一大方向。 鋅銘尖日日石（ΖηΑ12〇4)具有高熔點（約1 98〇°C )、低介電 书數（約1 0)、耐酸鹼性、疏水性及高機械強度等特性是 典型尖晶石（spinel)結構的氧化物陶瓷，工業上主要是應用 於觸媒的催化反應或觸媒載體方面，由於ZnAl2〇4具有直接 3 201226526 寬旎隙[Eg =3·8電子伏特（eV)]，對波長小於wo奈米（nm) 之光波具有良好阻隔作用，可應用於太空梭之抗紫外線光 學塗料（如Olbrich及Cordaro等人於美國專利公報第 5 143888號及5807909號等所揭露）。近年來之文獻研究顯 示經摻雜稀土族元素之Zn A丨2〇4粉體，具有良好的發光特 性，可應用於固體雷射材料、螢光材料、及全彩色顯示器（如 等尺於 J0urnal of AUoys and c〇mp〇und 323 324 P⑽/人279-M2所揭示）。 Φ 傳統上製造ZnAl2〇4螢光粉體大多以固態反應法為 主，已知以固態反應法製備ΖηΑ12〇4螢光粉末，具有機械致 發光（mechano-luminescence)與熱致發光（therm〇luminescence) 特性，可應用於光感測器與應力影像元件（如Matsui等人於201226526 VI. Description of the Invention: [Technical Field] The present invention relates to a method for preparing a manganese-activated zinc-aluminum spinel (ΖηΑ12〇4:Μη2 + ) green fluorescent nano-nano powder by a lyotropic gel technique, in particular It is prepared by controlling the hydrolysis and degumming reaction of zinc chaotic salt and aluminum isopropoxide, and doping different concentrations of manganese as an activator to form a clear sol, which is prepared by condensation polymerization, gelation, drying and heat treatment. Homogeneous single-phase zinc-aluminum spinel fluorescein nano-carbene, and by adjusting the doping concentration and changing the heat treatment temperature and atmosphere, can produce manganese-activated zinc-aluminum spinel with high efficiency of emitting green fluorescent properties ( ΖηΑ12〇4: Μη2 + ) Nano powder. [Prior Art] In recent years, the issues of energy and environmental protection have been highly valued. The international community is actively developing new energy supply technologies and green materials. The development of low-pollution and high-efficiency fluorescent materials has become one of the most urgent issues today. . Fluorescent materials have the advantages of low power consumption, long life, no heat radiation and good reaction speed. Their applications include fluorescent lamps, neon lights, and light-emitting diodes, as well as key components of today's high-profile displays. In the 1990s, Japan first developed a blue-light LEd with commercial application value such as gallium nitride, and used yellow fluorescent yttrium aluminum garnet (YAG, ymium aluminum g net) as the same efficiency white light source to develop new fluorescent materials for lighting. Equipment is a major direction for active research in the industry and academia. Zinc Mingjian Rishengshi (ΖηΑ12〇4) has a high melting point (about 1 98〇 °C), low dielectric number (about 10), acid and alkali resistance, hydrophobicity and high mechanical strength. The oxide ceramic of the spinel structure is mainly used in the catalytic reaction or catalyst carrier of the catalyst, since ZnAl2〇4 has a direct 3 201226526 wide gap [Eg = 3. 8 electron volts (eV) ], which has a good barrier effect on light waves having a wavelength less than the wo nanometer (nm), and can be applied to the anti-ultraviolet optical coating of the space shuttle (as disclosed in U.S. Patent Nos. 5, 143, 888 and 5,807, 909 to Ordrich et al.). . In recent years, literature studies have shown that Zn A丨2〇4 powder doped with rare earth elements has good luminescent properties and can be applied to solid laser materials, fluorescent materials, and full-color displays (such as J2urnal). Of AUoys and c〇mp〇und 323 324 P (10) / person 279-M2 revealed). Φ Traditionally, ZnAl2〇4 phosphor powder is mainly prepared by solid state reaction method. It is known to prepare ΖηΑ12〇4 fluorescent powder by solid state reaction method, which has mechano-luminescence and thermoluminescence (therm〇luminescence). ) Features that can be applied to light sensors and stress imaging components (such as Matsui et al.
Applied Physics Letters 78 (2001), 1068-1070 A Physical β所揭示），惟固態反應是依賴擴 散過程，需藉助高溫（約1200°C )長時間處理，基本上是耗 能咼成本製程，易造成粉體粗化（粒徑大於微米尺度）、偏析 • 氧化鋅（Zn0)與α -Al2〇3結晶相、活化劑非均質分布，以及 純度低等缺點’故無法獲得可靠之發光強度。 另外，目前研發技術已發展出以溶膠_凝膠法製備摻鈷 鋅鋁尖晶石（ZnAl2〇4:l%C〇2 + )螢光粉體（如Duan等人於义Applied Physics Letters 78 (2001), 1068-1070 A Physical β revealed), but the solid state reaction is dependent on the diffusion process, and needs to be treated with high temperature (about 1200 ° C) for a long time, which is basically a power consumption and cost process, which is easy to cause Powder coarsening (particle size larger than micrometer scale), segregation, zinc oxide (Zn0) and α-Al2〇3 crystal phase, actinator heterogeneous distribution, and low purity, so that reliable luminous intensity cannot be obtained. In addition, the current research and development technology has developed a sol-gel method to prepare cobalt-doped zinc-aluminum spinel (ZnAl2〇4:l%C〇2 + ) fluorescent powder (such as Duan et al.
Alloys and Compounds, 386(2003),3U-3】4 所揭示），以碓酸 鋅及硝酸鋁為前驅物所備製出的螢光粉體，該螢光粉體具 有紅綠光[650至530奈米（nm)]的放射特性，但前述之以溶 膠-凝膠法製備螢光粉體仍具有下述缺點：由於硝酸鹽含大 量結晶水，製程不易控制，需借助添加大量高濃度檸檬酸 4 201226526 溶液或明膠作為膠化劑，此易導致該粉體因殘留過量之 0-H等官能基而降低放射強度。 習知以溶膠—凝膠技術製備陶瓷粉末具有高均質性 '奈 米晶型、低溫製程、及設備成本低等優點，且已知前^ 及溶液濃度等製程條件會強烈影響溶凝膠狀態，進而顯著 影響往後膠體產物之均質性及特性（如發明人於中華民國專 利第274048號所揭露）。尤其對多成份係材料而言，不同的 前趨物其水解與縮聚合速率有顯著差異，&易導致膠體在 析晶過程中產生偏析的第二相；換言之，前述之以溶膠—凝 膠技術備製鋅鋁尖晶石（ZnA12〇4)登光粉體，目前仍具有許 夕限制及缺點’ 能選取適當的前驅物，冑由水解及解^ 反應配製清澈透明之溶膠，使膠粒分子呈均勻懸浮分散， 不需添加任何膠化劑，直接經縮聚合反應製備（ΖηΑ12〇4)螢 光粉體，可使粉體具有單相均質的結構，#可使生成粉體 具有奈米晶型及奈米粒徑之特性，研發出此溶膠一凝膠法製 備ΖηΑ1204:Μη2 +螢光粉體的方法於應用上實深具意義此於 應用上實深具意義。相較於習用之固態反應技術，以溶膠― 凝膠法製備ΖηΑ12〇4:Μη2+螢光粉體另—項優點，亦可具有 低溫量產奈米粉體之潛力，且設備較簡單，可大幅降低製 造成本。 迄今國内外尚未有關於以混合金屬醇鹽與金屬氣化 鹽’直接經水解、解膠、與縮聚合反應，@不需添加任何 膠化劑’並經不同熱處理程條件，製備具有均質單相且高 發光強度之猛活化鋅銘尖晶石（ZnAl2〇4:Mn2 + ) f光奈米粉 體之溶膠-凝膠技術提出。 201226526 綜合上述’本發明係提供一種以溶凝膠技術製備錳活化 辞紹尖晶石（ΖηΑ12〇4:Μη2 + )綠光螢光奈米粉體的方法用以 解決上述等問題。 【發明内容】 本發明之目的係在於提供一種以溶凝膠技術製備錳活 化鋅銘尖晶石綠光螢光奈米粉體的方法，為使用一種溶膠— 凝膠技術，藉由控制金屬氯化鹽與金屬醇鹽之水解與解膠 反應，而不需添加任何膠化劑，以掺雜錳為活化劑，經縮 聚合、膠化、乾燥及熱處理製備鋅鋁尖晶石螢光奈米粉體， 並由調整摻雜劑量及改變熱處理條件控制綠光發射強度。 本發明之次一目的，即在於提供一種可製得均質性、 奈米晶型、奈米粒徑、窄粒徑分佈之溶凝膠技術以製備均 貝單相之錳活化鋅鋁尖晶石（ZnA12〇4:Mn2 + )高效率綠光螢 光奈米粉體。 本發明之另-目的係在於提供一種具有高純度、奈米Alloys and Compounds, 386 (2003), 3U-3] 4), a phosphor powder prepared by using zinc citrate and aluminum nitrate as a precursor, the phosphor powder having red-green light [650 to Radiation characteristics of 530 nm (nm), but the preparation of the phosphor powder by the sol-gel method described above still has the following disadvantages: since the nitrate contains a large amount of crystal water, the process is difficult to control, and it is necessary to add a large amount of high-concentration lemon. Acid 4 201226526 Solution or gelatin acts as a gelling agent, which tends to cause the powder to reduce the radiation intensity by leaving an excess of functional groups such as 0-H. It is known that the preparation of ceramic powder by sol-gel technology has the advantages of high homogeneity 'nano crystal form, low temperature process, low equipment cost, etc., and process conditions such as pre-solution and solution concentration are strongly affected to affect the sol-gel state. Further, it affects the homogeneity and characteristics of the colloidal product in the future (as disclosed by the inventor of the Republic of China Patent No. 274048). Especially for multi-component materials, different precursors have significant differences in hydrolysis and polycondensation rates, & a second phase which tends to cause segregation of the colloid during crystallization; in other words, the aforementioned sol-gel The technology prepares zinc-aluminum spinel (ZnA12〇4) as a light-weight powder, which still has the limitations and disadvantages of the present. It can select the appropriate precursor, and prepare a clear and transparent sol from hydrolysis and hydrolysis to make the rubber particles. The molecules are uniformly suspended and dispersed, and no phosphorous agent is added, and the phosphor powder is directly prepared by polycondensation polymerization, so that the powder has a single-phase homogeneous structure, and the resulting powder has a nanometer-like structure. The characteristics of crystal form and nanometer particle size have been developed. The method of preparing ΖηΑ1204:Μη2 + fluorescent powder by the sol-gel method has a profound significance in application. Compared with the conventional solid-state reaction technology, the sol-gel method for preparing ΖηΑ12〇4: Μη2+ fluorescent powder has the other advantages, and can also have the potential of low-temperature mass production of nano-powder, and the device is relatively simple and can be greatly reduced. manufacturing cost. So far, there has not been any domestic and international research on the simultaneous hydrolysis, degumming, and polycondensation of mixed metal alkoxides and metal gasification salts, @no need to add any gelling agent' and different homogeneous heat treatment conditions to prepare a homogeneous single phase. And the high luminescence intensity of the activated zinc-based spinel (ZnAl2〇4: Mn2 + ) f light nano-powder sol-gel technology proposed. 201226526 In summary, the present invention provides a method for preparing a manganese-activated spinel (ΖηΑ12〇4:Μη2 + ) green light fluorescent nano-powder by a lyotropic gel technique to solve the above problems. SUMMARY OF THE INVENTION The object of the present invention is to provide a method for preparing manganese activated zinc spinel green light fluorescent nanometer powder by sol gel technique, by using a sol-gel technique, by controlling metal chloride salt and Hydrolysis and degumming reaction of metal alkoxide without adding any gelling agent, doping manganese as activator, preparing zinc-alumina spinel fluorescent nano-powder by condensation polymerization, gelation, drying and heat treatment, and adjusting The doping dose and changing the heat treatment conditions control the green light emission intensity. A second object of the present invention is to provide a sol-gel technique capable of producing homogenization, nanocrystal form, nanometer particle size, and narrow particle size distribution to prepare a manganese-activated zinc-aluminum spinel of a single-phase single phase. (ZnA12〇4: Mn2 + ) High-efficiency green fluorescent nano-nano powder. Another object of the present invention is to provide a high purity, nano
。構㈤均質f生、咼效率綠光強度、低成本、設備簡單， 及降低製私,皿度等多項優點的錳活化鋅鋁尖晶石 (ΖηΑ12〇4:Μη2 + )螢光奈米粉體。 可達成上述發明、 目的之从溶凝膠技術製備錳活化矽鋅 紹尖晶石綠光螢光奈米粉 甘总—1 止 歷之方法’其係包括以下步驟： 製備一透明溶脒夕半_ 少V驟·依化學計量比’分別量取氣 化鋅[ZnCl2]質量介於1 乳 科曰Λ K5g及鋁異丙醇鹽[AKOCsHA,·! 質量介於3.8至4.5e，而本m ；3j 有同時溶於醇溶劑中混合並攪拌反 應’同時加入一含有錳離六 .曲成八 子/合液進行反應’前述之錳離子 濃度介於0.2幻〇·〇莫耳 雊千 之間’於一反應溫度下反應，形〖s) 6 201226526 成一混合溶液；繼之，將該混合溶液加入水與鹽酸溶液， 於一反應條件下進行水解與解膠反應，形成一均勻分散膠 粒分子懸浮液，將水解反應後之前述懸浮液於2〇{)(：至3〇<t 下靜置一段時間以製得該透明溶膠； 製備一鋅鋁尖晶石螢光奈米粉體之步驟：將依上述步 驟之透明溶膠於一縮聚合反應條件下進行縮聚合反應，以 獲得一透明凝膠，將該凝膠經乾燥溫度介於8〇至2〇〇<t之. Structure (5) Mn-activated zinc-aluminum spinel (ΖηΑ12〇4:Μη2 + ) fluorescent nano-powder with homogeneous green, light-efficiency green light intensity, low cost, simple equipment, and reduced manufacturing, dish and other advantages. The invention can achieve the above-mentioned invention and the purpose of preparing a manganese-activated bismuth-zinc-spinel green light-fluorescent nano-powder from the sol-gel technique. The method includes the following steps: preparing a transparent solution 脒 半 _ less V Depending on the stoichiometric ratio, the amount of zinc hydride [ZnCl2] is determined to be between 1 breast 曰Λ K5g and aluminum isopropyl alkoxide [AKOCsHA,·! The mass is between 3.8 and 4.5e, and this m; 3j has At the same time, it is dissolved in an alcohol solvent and stirred and reacted. 'At the same time, a manganese-containing hexa- hexa-octane/liquid mixture is added to carry out the reaction. The aforementioned manganese ion concentration is between 0.2 〇 〇 〇 〇 雊 ' ' ' Reaction at temperature, shape 〖s) 6 201226526 into a mixed solution; then, the mixed solution is added to water and hydrochloric acid solution, under a reaction condition for hydrolysis and degumming reaction to form a uniform dispersion of colloidal molecular suspension, The suspension after the hydrolysis reaction is allowed to stand at 2 〇{) (: to 3 Torr) for a period of time to prepare the transparent sol; the step of preparing a zinc aluminum spinel fluorescein nano powder: according to the above steps The transparent sol is subjected to a polycondensation reaction condition The polymerization reaction is carried out to obtain a transparent gel which is dried at a temperature of from 8 Torr to 2 Torr.
間，乾燥並細化成-膠體粉末；繼之，將該膠體粉末進行 煆燒，煆燒溫度介於600至1000。〇之間，於煆燒時間為2 至i〇小時之間，可獲得-均f單相之鋅料晶石（ZnAi2〇4) 螢光奈米粉體。 較佳的，所ϋ之方法，冑述之製備透明溶膠之步驟，將質 量約Κ39 g的氯化鋅（ZnCl2)及質量約4 17 g的链異丙醇鹽 [ΑΚΟί：3^)'3]，同時溶於濃度介於〇 3至〇 5莫耳/升之間的 曱醇或乙醇。 較佳的，所述之方 >去，前述之製備透明溶膠之步驟，所述 之水濃度介於G.5至2.0莫耳/升之間與鹽酸溶液濃度介於 (Μ至0.3莫耳/升之間，該反應條件的溫度為说及時間介 於0.5至2小時之間。 所述之製備該奈米粉體的步驟 較佳的，所述之方法， 該縮聚合反應條件為25°C及相對濕度於55至8〇%下進行， 以及所述之乾燥溫度為80。(：至200。(：。 月J述之製備戎奈米粉體的步驟 較佳的，所述之方法， 莫耳％，煆燒溫度為 且於煆燒時間為2至 所述之該錳離子的濃度為〇·2至1〇 〇 1 0 0 0 °C，以加熱速度約為1 〇。〔〕/分鐘， 7 201226526 1 〇小時進行。 較佳的，所述之方法，其中該膠體粉末進行煆燒’於空 氣爐或Ν2-Η2還原氣氛中進行瑕燒。 本發明係提供一種鋅銘尖晶石綠光螢光奈米粉體，其 係由上述之方法所製成。 較佳的，所述之鋅鋁尖晶石綠光螢光奈米粉體，經熱 處理600至1000°C後，該奈米粉體的平均晶粒度介於12 至20奈米（nm)之間。 較佳的，所述之鋅紹尖晶石綠光螢光奈米粉體，經熱 處理1000°C後，該奈米粉體的顆粒度介於20至25奈米（nm) 之間。 季父佳的，所述之鋅鋁尖 米粉體之激發光波長約460奈米（nm)，以及發射波長約5 1 奈米（nm) ’其中錳離子摻雜濃度為3〇莫耳％，且經還原翁 氛煆燒lOOOt，煆燒時間1〇小時，具有最佳發光強度。 以上述方法製得之螢光粉體經煆燒熱處理000至1〇〇< 乞後，平均晶粒度為12至20奈米（nm)，其中，經煆燒熱處 里800 c後，無明顯的重量損失，經煆燒熱處理1 〇⑼。c後， ，體顆粒度為2G至25奈米（nm) ’粉末呈近球形外觀，且粒 仫刀。佈窄。由螢光光譜顯示當錳離子摻雜濃度為㈢至I。·。 f耳之間’以波長為46〇奈米㈣藍光激發後具有發射 2率綠光的特性’放射峰波長為512奈米（叶其中猛離 r燒^農度為3〇莫耳％具有最佳發光強度，且經還原氣氛 版燒;Γ，烺燒時間1G小時，具有最佳發光強度。 所提供之以溶凝膠技術製備猛活化辞銘尖晶石! 201226526 螢光奈米粉體及其方法，經由以上之說明，更具有下列之 優點： 1.本發明操作步驟容易且不需添加任何膠化劑，僅需 藉由低水量與鹽酸電解質控制水解與解膠反應，即可使膠 粒分子呈均勻懸浮分散，可以直接經縮聚合反應製備出錳 活化鋅鋁尖晶石（ΖηΑ12〇4:Μη2+)螢光粉體，顯著提高純度， 亦可低溫合成均質單相鋅鋁尖晶石結構，對於節省能源具 有顯著功效。 # 2.所述之猛活化鋅鋁尖晶石（ΖηΑ12〇4:Μη2 + )奈米營光 粉體，具有高均質性、奈米晶型及奈米粒徑特性，且備製 該粉體所需設備簡單，可有效降低成本。 3.所述之錳活化辞鋁尖晶石（ZnAi2〇4:Mn2 + )奈米螢光 粉體，具有高效率發射綠光特性，且可藉由調整活化劑（錳 離子）濃度及熱處理條件而控制發光強度，可廣泛應用於各 式照明設備、顯示器元件、光感測器、汽機車的儀表面板、 警示燈及交通號總等各種不同領域。 鲁 4·所述之錳活化鋅鋁尖晶石（ΖηΑ12〇4:Μη2 + )奈米螢光 粉體，具有奈米化及窄粒徑分布，在光學塗膜應用上具有 薄化膜厚、增加緻密特性、及顯著提升發光效率，適用於 陰極射線管（CRT )、電漿顯示器（PDP )、場發射顯示器 (FED )及電致發光等各種不同領域之顯示器元件。 5. 本發明所使用之溶膠—凝膠法亦可應用於製備鋅銘 尖晶石薄膜’有助於開發此材料應用於未來大面積化全彩 色顯示器、場發射顯示器、白光LED及照明設備。 6. 本發明之錳活化鋅鋁尖晶石（ZnA丨2〇4:Mn2 + )奈米綠 9 201226526 光螢光粉體，可應用於白光LED並有效改善目前白光led 發光不自然的問題，且具有耗電量低、壽命長和反應速度 佳等優點。 7.本發明所使用的溶膠-凝膠技術，藉由控制水解與膠 化反應，以掺雜錳離子為活化劑，可低溫合成均質單相辞 鋁尖晶石奈米粉體，並由調整摻雜濃度及改變熱處理條件 控制綠光發射之強度。與其他習用的製程相較，具有高純 度、奈米晶型與粒徑、高均質性、高效率綠光強度、低成 本' 設備簡I，及降低製程溫度等多項優點。可廣泛應用 於照明設備、發光二極體、顯示器發光元件、光致發光元 件、電致發光it件、陰極射線管（CRT)、電襞顯示器（pDp)、 場發射顯示器（FED)、生醫感測器、雷射半導體、透明導 電材料、雷射半導體及醫療產業等各種不同領域，以及醫 療產業等各種不同領域。 綜上所述，本案不但在低溫合成單相辞紹尖晶石營光 粉體及其奈米型態上確屬創新，並能較習用物品增進上述 多項功效’應已充分符合新穎性及進步性之法定發明專利 要件’妥依法提出申請’㈣#局核准本件發明專利申 請案，以勵發明，至感德便。 【實施方式】 為能詳細瞭解本發明的技術特徵和實用功效，並可依 照說明書的内容來實施，兹進-步以如圖丨至圖7之較佳 實施例，詳細說明如后： 實施例 請參閱圖1，本發明所接扯4、 奉發月所k供之以溶凝膠技術製備猛活化「 10 201226526 鋅銘尖晶石螢光奈米㈣之方法，製造流程料如下： 首先製備-透明溶膠之步驟：分別取質量約139 §的 氣化辞（㈤箱f量約4.1 7 g的紹異丙醇鹽〔A丨(〇C3H7)i3〕 溶於曱醇或乙醇溶劑中並㈣1小時，醇溶劑濃度為0.4莫 耳/升/皿度為25 C下反應，並加入氣化猛（MnCl2)實施播雜 處理形成❿合谷液，該混合溶液中的猛離子（心2巧濃度 介於0.2至1〇·〇莫耳％之間；The mixture is dried and refined into a colloidal powder; the colloidal powder is then calcined at a temperature between 600 and 1000. Between the crucibles, during the calcination time between 2 and i〇 hours, a single-phase zinc-site spar (ZnAi2〇4) fluorescent nano-nano powder can be obtained. Preferably, the method described is a step of preparing a transparent sol, a zinc chloride (ZnCl2) having a mass of about 39 g and a chain isopropoxide [ΑΚΟί: 3^) of a mass of about 4 17 g. ], while being dissolved in sterol or ethanol at a concentration between 〇3 and 〇5 mol/l. Preferably, the method described above, the step of preparing the transparent sol, wherein the water concentration is between G.5 and 2.0 m/liter and the concentration of the hydrochloric acid solution is between (Μ to 0.3 m). Between / liter, the temperature of the reaction condition is between 0.5 and 2 hours. The step of preparing the nano-powder is preferably, the method, the polycondensation reaction condition is 25 ° C and the relative humidity are carried out at 55 to 8〇%, and the drying temperature is 80. (: to 200. (:.) The step of preparing the nano-powder powder is preferred, the method, Mohr%, the calcination temperature is 2 and the calcination time is 2 to the concentration of the manganese ion is 〇·2 to 1〇〇100 °C, and the heating rate is about 1 〇. In a minute, 7 201226526 1 〇 hour. Preferably, the method wherein the colloidal powder is subjected to simmering in an air furnace or a Ν2-Η2 reducing atmosphere for simmering. The present invention provides a zinc-like spinel green light. Fluorescent nano-powder, which is prepared by the above method. Preferably, the zinc-aluminum spinel green fluorescent nano-nano powder The average grain size of the nano-powder is between 12 and 20 nanometers (nm) after heat treatment at 600 to 1000 ° C. Preferably, the zinc-spun spinel green fluorescent nano-nano powder After heat treatment at 1000 ° C, the nano-powder has a particle size of between 20 and 25 nanometers (nm). Ji Jijia, the zinc-aluminum tip rice powder has an excitation light wavelength of about 460 nm ( Nm), and the emission wavelength is about 5 1 nanometer (nm) 'where the manganese ion doping concentration is 3 〇 mol%, and the reduced smoldering smoldering lOOOOt, the smoldering time is 1 〇 hour, and has the best luminescence intensity. The phosphor powder obtained by the above method is subjected to a heat treatment of 000 to 〇〇 〇〇 ,, and the average grain size is 12 to 20 nanometers (nm), wherein after the heat is 800 c, No obvious weight loss, after heat treatment 1 〇(9).c, the body particle size is 2G to 25nm (nm) 'The powder has a nearly spherical appearance, and the granule is narrow. It is shown by fluorescence spectrum. When the doping concentration of manganese ions is (3) to I.· f between the ears is excited by a blue light at a wavelength of 46 〇 nanometer (4) blue light. 512 nm (the leaf is fiercely r roasting ^ farming degree is 3 〇 mol % has the best luminescence intensity, and is burned by reducing atmosphere; Γ, 烺 burning time 1G hour, has the best luminescence intensity. The lyophilized gel technology prepares the swelled reed spinel! 201226526 The fluorescent nano-powder and its method, through the above description, have the following advantages: 1. The operation steps of the invention are easy and no need to add any gelling agent, Only by controlling the hydrolysis and degumming reaction with low water and hydrochloric acid electrolyte, the micelle molecules can be uniformly suspended and dispersed, and the manganese activated zinc-aluminum spinel (ΖηΑ12〇4:Μη2+) can be directly prepared by condensation polymerization. The light powder can significantly improve the purity, and can also synthesize a homogeneous single-phase zinc-aluminum spinel structure at a low temperature, which has a remarkable effect on energy conservation. # 2. The stimuli-activated zinc-aluminum spinel (ΖηΑ12〇4:Μη2 + ) nano-light powder, which has high homogeneity, nano crystal form and nanometer particle size, and prepares the powder The required equipment is simple and can effectively reduce costs. 3. The manganese-activated aluminum spinel (ZnAi2〇4:Mn2+) nano-fluorescent powder has high-efficiency emission green light characteristics, and can adjust the activator (manganese ion) concentration and heat treatment conditions. The control luminous intensity can be widely applied to various types of lighting equipment, display components, light sensors, instrument panels of steam locomotives, warning lights and traffic numbers. The manganese-activated zinc-aluminum spinel (ΖηΑ12〇4:Μη2 + ) nano-fluorescent powder described in Lu 4· has a nanometer and narrow particle size distribution, and has a thin film thickness in optical coating application. It increases the density and significantly improves the luminous efficiency. It is suitable for display components in various fields such as cathode ray tube (CRT), plasma display (PDP), field emission display (FED) and electroluminescence. 5. The sol-gel method used in the present invention can also be applied to the preparation of a zinc-like spinel film, which contributes to the development of this material for future large-area full color display, field emission display, white LED and lighting equipment. 6. The manganese-activated zinc-aluminum spinel (ZnA丨2〇4:Mn2+) nano green 9 201226526 light phosphor powder can be applied to white LEDs and effectively improve the current unnatural problem of white light LED illumination. It has the advantages of low power consumption, long life and good reaction speed. 7. The sol-gel technique used in the present invention can synthesize a homogeneous single-phase aluminum spinel nano-powder by low-temperature synthesis by controlling the hydrolysis and gelation reaction with doping manganese ions as an activator. The heterogeneous concentration and changing the heat treatment conditions control the intensity of the green light emission. Compared with other conventional processes, it has many advantages such as high purity, nano crystal form and particle size, high homogeneity, high efficiency green light intensity, low cost, simple device I, and reduced process temperature. Can be widely used in lighting equipment, light-emitting diodes, display light-emitting elements, photoluminescent elements, electroluminescent elements, cathode ray tubes (CRT), electro-optical displays (pDp), field emission displays (FED), biomedical Various fields such as sensors, laser semiconductors, transparent conductive materials, laser semiconductors, and the medical industry, as well as various fields such as the medical industry. In summary, this case is not only innovative in the low-temperature synthesis of single-phase rhetoric scutellite powder and its nano-type, but also can enhance the above-mentioned multiple functions compared with conventional articles' should have fully met the novelty and progress. The legal statutory invention patent element 'to apply properly according to law' (four) # Bureau approved this invention patent application, in order to invent invention, to the sense of virtue. [Embodiment] In order to understand the technical features and practical effects of the present invention in detail, and in accordance with the contents of the specification, the following is a detailed description of the preferred embodiment of the present invention as follows: Referring to Fig. 1, the method of the present invention is to prepare a method for preparing a vigorously activated "10 201226526 zinc indica spinel fluorescent nanometer (4) by a lyophilic technique, and the manufacturing process is as follows: First, preparation - transparent The sol step: respectively take a gasification of about 139 § ((5) box f amount of about 4.1 7 g of isopropyl isopropoxide [A 丨 (〇 C3H7) i3] dissolved in decyl alcohol or ethanol solvent and (iv) 1 hour, The alcohol solvent concentration is 0.4 m / liter / the dish is 25 C, and the gasification is pulverized (MnCl2) to carry out the miscellaneous treatment to form the glutinous solution, and the violent ion in the mixed solution (heart 2 concentration is between 0.2) Between 1〇·〇莫耳%;
繼之，將該混合溶液置於饥值溫水槽中進行回流冷 凝’加入水與鹽酸溶液進行水解與解膠反應，使膠粒分子 呈均勻懸浮分散’反應時間介於〇·5至2小時之間、反應溫 度為25。(： ’水的濃度介於G.5至2.Q莫耳/升之間及鹽酸的 濃度介於0.1至0.3莫耳/升之間；將水解反應後之前述懸浮 液於室溫下靜置一段時間以製得一清澈透明溶膠。 製備一鋅銘尖晶石螢光奈米粉體之步驟：將依上述方 法製得之透明溶膠於25°C及相對濕度55%下進行縮聚合反 應’以獲得一透明凝膠； 將該凝膠經80°C乾燥並細化成膠體粉末，繼之，將粉 末置於甜鋼中在空氣爐或N2_H2還原氣氛中進行煆燒程 序，設定煆燒熱處理溫度介於6〇〇至1 〇〇〇°C之間，加熱速 度為10t/分鐘’煆燒時間為2至1〇小時之間，煆燒完畢， 爐冷至室溫，可獲得一均質單相之錳活化鋅鋁尖晶石 (ΖηΑ12〇4:Μη2 + )粉體；藉由控制該煆燒程序的煆燒溫度及時 間’可以獲得該均質單相之鋅鋁尖晶石結構，適當的煆燒 溫度及時間可以增加粉體之結晶性。 如圖2所示，由上述步驟所製得之錳活化鋅鋁尖晶石[ 11 201226526 (ΖηΑ1204.Μη )螢光奈米粉體經過假燒熱處理後該煆燒溫 度介於600至100(rc之間，獲得該螢光奈米粉體的平均晶 粒度介於12至20奈米（nm)之間。 如圖3所不，該螢光奈米粉體（ΖηΑ1204)經熱處理後， 分別於溫度為30至12(rc及2〇〇至7〇〇<t之間有主要重量 損失，經熱處理80(rc後，無明顯的重量損失；經熱處理 i〇〇〇°c後，該螢光奈米粉體的顆粒度介於2〇至25奈米（nm) 之間，如圖4所示，不同錳離子濃度摻雜於鋅鋁尖晶石粉 • 體中，其中圖4(a)Mn2+=3.〇莫耳％及圖MWMn2、6·。莫 耳/〇，圖示所呈現的粉末呈近球形外觀，且粒徑分佈窄，錳 摻雜濃度及熱處理氣氛對其結晶性、熱重損失、晶粒度、 與顆粒度無顯著影響，惟錳離子摻雜濃度高於5 〇莫耳％ 時，會略為增加粉體之結團狀態，且錳離子摻雜濃度會顯 著影響發光強度。 如圖5所示，該猛活化鋅铭尖晶石粉體經嵌燒1 〇 〇 〇 t 後之螢光放射光譜，顯示當錳離子摻雜濃度介於〇 2至1〇 〇 * 莫耳％之間，經熱處理溫度800至100(TC後，以波長約 460nm藍光（λ ex = 460nm)激發後，具有發射綠光特性，放射 峰波長約512nm( λ em = 512nm) ’此歸因於自由電子在活化劑 Μη離子之Τ1 — A!能階間的遷移所致，其中猛離子換雜 濃度為3.0莫耳％具有最佳發光強度，如圖$及圖6所示， 且經還原氣氛煆燒100(TC，煆燒時間1〇小時，具有最佳發 光強度，如圖7所示。Then, the mixed solution is placed in a hunger-type warm water tank for reflux condensation. 'Water and hydrochloric acid solution are added for hydrolysis and degumming reaction, so that the micelle molecules are uniformly suspended and dispersed. The reaction time is between 至·5 and 2 hours. The reaction temperature was 25. (: 'The concentration of water is between G.5 and 2.Q mol/L and the concentration of hydrochloric acid is between 0.1 and 0.3 mol/L; the suspension after hydrolysis is allowed to stand at room temperature Set a period of time to prepare a clear transparent sol. Step of preparing a zinc-like spinel fluorescein nano-powder: the transparent sol obtained by the above method is subjected to polycondensation at 25 ° C and a relative humidity of 55% to obtain a transparent gel; the gel is dried at 80 ° C and refined into a colloidal powder, and then the powder is placed in a sweet steel in an air furnace or N 2 -H 2 reducing atmosphere to carry out a calcination procedure, and the heat treatment temperature is set to be between Between 6〇〇 and 1 〇〇〇°C, the heating rate is 10t/min. The simmering time is between 2 and 1 〇h. After the simmering is completed, the furnace is cooled to room temperature to obtain a homogeneous single-phase manganese. Activated zinc-aluminum spinel (ΖηΑ12〇4:Μη2 + ) powder; the homogeneous single-phase zinc-aluminum spinel structure can be obtained by controlling the calcination temperature and time of the calcination program, and the appropriate calcination temperature And time can increase the crystallinity of the powder. As shown in Figure 2, the manganese produced by the above steps Zinc-aluminum spinel [11 201226526 (ΖηΑ1204.Μη) fluorescent nano-powder after calcination heat treatment, the calcination temperature is between 600 and 100 (rc), and the average grain size of the fluorescent nano-powder is obtained. Between 12 and 20 nanometers (nm). As shown in Fig. 3, the fluorescent nano-powder (ΖηΑ1204) is heat-treated, respectively, at a temperature of 30 to 12 (rc and 2 〇〇 to 7 〇〇 < There is a major weight loss between t, after heat treatment 80 (rc, no significant weight loss; after heat treatment i〇〇〇 °c, the particle size of the fluorescent nano-nano is between 2 〇 and 25 nm (nm Between, as shown in Figure 4, different manganese ion concentrations are doped in the zinc-aluminum spinel powder body, wherein Figure 4 (a) Mn2+ = 3. 〇 mol% and Figure MWMn2, 6 · Moh / 〇, the powder presented has a nearly spherical appearance and a narrow particle size distribution. The manganese doping concentration and heat treatment atmosphere have no significant effect on its crystallinity, thermal weight loss, grain size, and particle size, but manganese ion doping. When the impurity concentration is higher than 5 〇 mol%, the agglomeration state of the powder is slightly increased, and the manganese ion doping concentration significantly affects the luminescence intensity. The fluorescence emission spectrum of the activated zinc spinel powder after 1 〇〇〇t is shown, and the manganese ion doping concentration is between 〇2 and 1〇〇*mol%, and is heat treated. After the temperature of 800 to 100 (after TC, after excitation with a wavelength of about 460 nm blue light (λ ex = 460 nm), it has a green emission characteristic, and the emission peak wavelength is about 512 nm (λ em = 512 nm). This is attributed to the free electrons in the activator Μη. Ion Τ1 — A! The transition between the energy levels of the energy, the violent ion exchange concentration of 3.0 mol% has the best luminescence intensity, as shown in Figure $ and Figure 6, and the reduction atmosphere is 100 (TC, The calcination time is 1 hour and has the best luminous intensity, as shown in Figure 7.
12 201226526 【圖式簡單說明】 圖1為本發明具體實施例之製備流程圖。 圖2為本發明具體實施例粉末經煆燒丨〇〇〇。(3後之χ_光 繞射圖。 圖3為本發明具體實施例粉末經乾燥後之熱重分析曲 線。 圖4為本發明具體實施例（a) Mn2 + = 3.0莫耳％及（b) 鲁 Μη2 + = 6·〇莫耳％之錳活化辞鋁尖晶石粉體經煆燒1000〇C後 之微觀圖片。 圖5為本發明具體實施例錳活化鋅鋁尖晶石粉體經煆 燒1000°C後之螢光放射光譜。 圖ό為本發明具體實施例錳活化辞鋁尖晶石發光強度 與链離子（Μη2 + )摻雜濃度之關係圖。 圖7為本發明具體實施例錳活化鋅鋁尖晶石之發光強 度與熱處理條件之關係圖。 【主要元件符號說明】 (無）12 201226526 [Simplified illustration of the drawings] Fig. 1 is a flow chart showing the preparation of a specific embodiment of the present invention. Figure 2 is a graph of the powder of the embodiment of the present invention. Fig. 3 is a thermogravimetric analysis curve of the powder after drying according to a specific embodiment of the present invention. Fig. 4 is a specific embodiment of the invention (a) Mn2 + = 3.0 mol% and (b)微观 Μ Μ 2 + = 6 · 〇 Mo Er % of manganese activated aluminum spinel powder after simmering 1000 〇 C microscopic picture. Figure 5 is a specific embodiment of the invention manganese activated zinc aluminum spinel powder Fluorescence emission spectrum after calcination at 1000 ° C. Figure ό is a graph showing the relationship between the luminescence intensity of manganese activated spinel spinel and the doping concentration of chain ions (Μη 2 + ) according to a specific embodiment of the present invention. Diagram of the relationship between the luminous intensity of manganese-activated zinc-aluminum spinel and heat treatment conditions. [Main component symbol description] (none)