201020313 九、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矽鋅礦薄膜 的方法，特別是藉由控制鋅氣化鹽與矽乙醇鹽之水解與解膠 反應’並摻雜不同濃度之錳作為活化劑，以形成清徹之溶 膠，經旋轉塗佈及熱處理後以製備均質單相之矽鋅礦薄膜， 並藉由調整摻雜劑量及改變製程條件控制綠光發射之強度。 【先前技術】 矽酸鋅（ZmSiCh)是屬於ZnO-SiCh二元系統的矽酸鹽材 料，具有α-相、沒-相、及相三種同素異形體，基本上 金屬離子均佔據於四面體配位’其中a-ZmSi〇4亦稱為石夕鋅 礦（willemite)具有斜方六面體結構（rhombohedral)，是唯 一在平衡狀態下可穩定存在的結晶相，而召―相與相是 介穩性結構’尚溫處理後會相變化為a -Z112S i 〇4。已知推雜 φ 錳（Μη)之矽鋅礦（Zn2Si〇4:Mn)因兼具高發光效率、化學安定 性、及熱穩定性’其螢光粉末可應用於照明及陰極射線管（如 美國專利第3,416,019號、第4,925,703號、及第5，188,763 號所揭露），近年來亦被應用於電漿顯示器（PDP)及電場發射 顯示器（FED)之綠光元件（如美國專利第6, 576, 156號、第 5, 688, 438號、第5, 196, 234號等；及中華民國專利第 1267321號、第1290329號等所揭露）。以紫外線（UV)或電能 激發後，Zn2Si〇4: Μη具有發射綠光特性，主要是歸因於自由 5 201020313 電子在活化劑Mn+2離子之基態及激發態I〆％)間的遷 • 移所致。 ' 傳統上製造摻雜猛（Mn)之石夕鋅礦（a -Zn2Si〇4:Mn)薄膜 大多是先以固態反應法製備粉末，再經塗層處理，由於粉末 須經南溫瑕燒（1250〜1350C)方可結晶，易產生氧化辞（zn〇 ) 與/3 - Zn2S i O4偏析相、粒度粗化、及非均質分佈等缺點， 且粉末需經研磨處理’導致不規則粒度型態及降低純度，故 ® 無法獲得可靠之發光強度。a -ZmSiO4:Μη為深具應用潛力之 發光薄膜材料’亦兼具陰極射線致發光、光致發光、及電致 發光等特性，可應用於陰極射線管、平面顯示器、lED照明 元件、及醫療輻射影像用檢測器等，且將石夕鋅礦發光材料薄 ' 膜化可使體積更為節省，亦可應用於薄膜電激發光等元件， 也是目前全彩色顯示器所急需開發的關鍵性零組件。文獻資 料顯示，近年來ZmSi〇4薄膜已分別可利用化學氣相沉積法 ❿（CVD)、濺鍍法（sputtering)、脈衝雷射沉積法（pulsed User deposition)、及溶膠—凝膠法（sol—gel pr〇cess)等方法製 備。 溶膠-凝膠法由於具有精確的化學計量比、高純度、良 好均質性，以及可降低製程溫度等優點，已被應用於製備 ZmSiOcMii粉末，惟以溶膠—凝膠法製備Zn2Si〇4:Mn薄膜之 文獻資料相對較少。已知可將醋酸辞及醋酸錳溶入二甲氧基 6 201020313 乙醇與乙醇胺溶液中配製成溶膠後，以旋轉塗佈方式渡著於 * 氧化石夕（si〇〇上製備ZmSiOcMn薄膜，經熱處理840X後為 ' 氧化辞（Zn0)偏析相結晶，至980。(：以上才開始產生 a-Zn2Si〇4結晶’光激榮光（ph〇t〇iuminescence，PL)光譜之 衰減時間為 21. 3ms(如 Z. Ji, K. Liu, Y. Song，Z. Ye 於 J. Crystal Growth 255 (2003) 353-356 頁所提出）；另有 以醋酸鋅或硝酸辞、矽醇鹽、及硝酸錳為起始原料配製溶 ® 膠’其膠化時間超過三週以上，以旋轉塗佈法於矽/二氧化 碎（Si/Si〇2)接面上製備之薄膜，單層厚度為05/ζιη，需熱 處理800°c以上才開始生成a-Zn2Si〇4結晶，光激螢光光譜 之衰減時間為8. 23ms，且硝酸辞為前驅物的結晶性及發光強 度均優於醋酸鋅系（如r Selomulya，S. Ski, C. H. Kam， Q. Y. Zhang，S. Buddudu 於 Materials Science Engineering B100 (2003) 136-141頁所提出）；亦有將氧化鋅與醋酸猛溶 入淚硝酸中，形成硝酸鹽水溶液後再與矽醇鹽混合水解，經 浸潰塗佈法製備ZmSiO^Mn薄膜，熱處理80(TC以上生成 石-ZmSi〇4結晶’且殘留氧化鋅（Zn0)偏析相，至1〇〇(rc為 a-Zn2Si〇4 結晶（如 J· Lin, D. U. Sanger, M. Mennig，K. Barner 於 Thin Solid Films 360 (2000) 39-45 頁所提出）。 有關ZmSiO^Mn薄膜之溶膠-凝膠技術的文獻資料，主 要是以醋酸鋅、硝酸鋅、或氧化鋅作為鋅源，以氧化矽或矽 7 201020313 醇鹽作為梦源，以硝酸錳及醋酸錳作為錳源，其膠化時間過 於迥長，且通常大量使用二甲氧基乙醇及乙醇胺等多元醇膠 化劑，或以濃酸作催化，此易使膠體薄膜殘留過量之〇 — H* 而降低其發光效率，且甲氧乙醇及乙醇胺具有腐蝕性與毒 性，有害於人體及環保；此外，析晶過程易有偏析氧化鋅 或；5-ZmSi〇4第二相等問題，故選用適當之起始原料與溶劑 方有助於膠體薄膜在應用上的普及化。201020313 IX. Description of the invention: • Technical field to which the invention pertains. The present invention relates to a method for preparing a manganese activated strontium zinc ore film by a sol gel technique, in particular by controlling hydrolysis of a zinc gasification salt and a cesium ethoxide salt. And degumming reaction 'and doping different concentrations of manganese as an activator to form a clear sol, spin coating and heat treatment to prepare a homogeneous single-phase zinc antimony film, and by adjusting the doping amount and changing the process Conditions control the intensity of green light emission. [Prior Art] Zinc silicate (ZmSiCh) is a phthalate material belonging to the ZnO-SiCh binary system. It has α-phase, no-phase, and phase allotropes. Basically, metal ions occupy tetrahedron. Coordination 'where a-ZmSi〇4, also known as the Shimite zinc ore (willemite) has a rhombohedral structure, is the only crystal phase that can exist stably under equilibrium conditions, and the phase and phase are The metastable structure will change to a -Z112S i 〇4 after treatment. It is known that yttrium-zinc ore (Zn2Si〇4:Mn), which is a kind of Φ-manganese (Μη), has high luminous efficiency, chemical stability, and thermal stability. Its fluorescent powder can be applied to illumination and cathode ray tubes (such as In recent years, it has also been applied to green light components of plasma display (PDP) and electric field emission display (FED) (such as U.S. Patent No. 6, in U.S. Patent Nos. 3,416,019, 4, 925, 703, and 5,188, 763). 576, 156, 5, 688, 438, 5, 196, 234, etc.; and the Republic of China Patent No. 1267321, No. 1290329, etc.). After excitation by ultraviolet light (UV) or electric energy, Zn2Si〇4: Μη has a green-emitting property, mainly due to the migration between the ground state and the excited state of the activator Mn+2 ions. Due to the move. Traditionally, the a-Zn2Si〇4:Mn film of the doped Mn (Mn) is prepared by solid-state reaction method and then treated by coating. 1250~1350C) can crystallize, easily produce oxidation (zn〇) and /3 - Zn2S i O4 segregation phase, particle size coarsening, and heterogeneous distribution, etc., and the powder needs to be ground to 'cause irregular particle size pattern And to reduce the purity, so the reliable luminous intensity cannot be obtained. a -ZmSiO4: Μη is a luminescent film material with deep application potential. It also has the characteristics of cathode ray luminescence, photoluminescence, and electroluminescence. It can be applied to cathode ray tubes, flat panel displays, lED lighting components, and medical Radiation imaging detectors, etc., and thinning the shixi zinc ore luminescent material can make the volume more economical, and can also be applied to components such as thin film electro-excitation light, and is also a key component that is urgently needed for development of full-color displays. . According to the literature, in recent years, ZmSi〇4 films have been able to be separated by chemical vapor deposition (CVD), sputtering, pulsed user deposition, and sol-gel method (sol). -gel pr〇cess) and other methods of preparation. The sol-gel method has been applied to the preparation of ZmSiOcMii powder due to its precise stoichiometric ratio, high purity, good homogeneity, and reduced process temperature. However, Zn2Si〇4:Mn film is prepared by sol-gel method. The literature is relatively small. It is known that acetic acid and manganese acetate can be dissolved in dimethoxy 6 201020313 ethanol and ethanolamine solution to prepare a sol, and then a ZmSiOcMn thin film is prepared by spin coating on the oxidized stone. After heat treatment of 840X, it is the crystal of the oxidized (Zn0) segregation phase, to 980. (: The above starts to produce a-Zn2Si〇4 crystal. The decay time of the ph〇t〇iuminescence (PL) spectrum is 21. 3ms. (eg Z. Ji, K. Liu, Y. Song, Z. Ye, J. Crystal Growth 255 (2003) pp. 353-356); otherwise zinc or nitrate, sterol, and manganese nitrate A film prepared by spin coating on a crucible/dioxide crumb (Si/Si〇2) joint with a single layer thickness of 05/ζιη, prepared as a starting material for the starting material. The heat treatment of 800 ° C or more is required to start the formation of a-Zn2Si〇4 crystal. The decay time of the photo-activated fluorescence spectrum is 8.23 ms, and the crystallinity and luminescence intensity of the precursor of the nitric acid are superior to those of the zinc acetate system. r Selomulya,S. Ski, CH Kam, QY Zhang,S. Buddudu at Materials Science Engineering B100 (200 3) pp. 136-141); zinc oxide and acetic acid are also dissolved into tear nitric acid to form a nitrate aqueous solution, which is then hydrolyzed with cerium alkoxide, and ZmSiO^Mn film is prepared by dipping coating method. 80 (formed above TC to form stone-ZmSi〇4 crystal' and residual zinc oxide (Zn0) segregation phase to 1 〇〇 (rc is a-Zn2Si〇4 crystal (eg J. Lin, DU Sanger, M. Mennig, K. Barner, Thin Solid Films 360 (2000), pp. 39-45.) The literature on sol-gel technology for ZmSiO^Mn films is based on zinc acetate, zinc nitrate, or zinc oxide as a source of zinc for oxidation.矽 or 矽7 201020313 Alkoxide as a source of dreams, with manganese nitrate and manganese acetate as the source of manganese, the gelation time is too long, and usually a large amount of polyol gelling agent such as dimethoxyethanol and ethanolamine is used, or Acidic catalysis, which tends to make the colloidal film residual excessive 〇-H* and reduce its luminous efficiency, and methoxyethanol and ethanolamine are corrosive and toxic, harmful to the human body and environmental protection; in addition, the crystallization process is prone to segregation of zinc oxide Or; 5-ZmSi〇4 second equal problem, so choose When the starting material with a solvent party assisting the colloidal film popularity in the application.
對ZmSi〇4:Mn矽辞礦薄膜而言，主體晶格的結構及活化 劑的電子組態均會影響其發光特性，由於Zn2Si()4：t同素異 形鱧’不同的結晶結構其結晶場相異，會影響放射波長；且 對應用於顯示器元件而言，為避免影像暫留，其衰減時間（餘 彈）需小於i〇ms(如美國專利帛5 518 655號所揭露）。習知 增加摻雜錳⑽濃度可降低衰減時間，但同時也會降低發光 強度’故極需開發新型溶膠一凝膠技術以製備具有均質單 相、及低衰減時間之摻料辞礦薄膜且兼具高發光效率， 以顯著提升其應用性及普及化。 基本上影響溶膠-凝勝 硬膠Csol-gel)轉換的因素，其控制條 件主要是前驅物、系統濃度、唆細 ， 度，奋劑、催化劑、pH值及反應溫 度等。對氧化物陶瓷而言，P m 已知〉谷膠之製程條件會強烈影響 溶膠之狀態’此亦將顯著影缴分 苦京/警住後膠體薄膜之均質性及其分 子結構。尤其對多成份係材料而 何斜而S ’不同的前趨物其水解與 8 201020313 縮聚合速率有顯著差異’此易導致膠趙在析晶過程中產生偏 * 析的第二相。換言之’若能控制不同前趨物之水解、解膠、 • 與縮聚合反應’且不添加任何膠化劑，配製均質之耀[體薄 滕’再藉由不同熱處理條件以製備具有奈米晶型且均質單相 之短活化梦辞破薄膜，可有效提升其發光穩定性及實用化。 相較於習用之沈積或濺鍍技術，以溶膠—凝膠（sol一gel)法製 備ZmSiCh: Μη石夕辞確薄膜另一項優點，是可利用旋轉塗佈方 參式直接塗佈在基板上，具有量產及大面積化之潛力，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直接藉由控制鋅、錳氣化鹽及 發乙醇鹽之水解、解膠、及縮聚合反應，並經不同製程條件， 製備具有均質單相、高發光強度、及低衰減時間之錳活化矽 鋅礦（a - ZmSiOd Μη)高效率發光薄膜之溶膠-凝膠技術提 出。 ⑩【發明内容】 本發明之目的即在於提供一種可製得均質單相、高發光 強度、低衰減時間之溶膠_凝膠技術以製備奈米晶型錳活化矽 辞礦高效率發光薄膜。 本發明之次一目的係在於提供一種以溶凝膠技術製備錳 活化矽鋅礦薄膜的方法，為使用一種溶膠-凝膠技術，藉由控 制水解與膠化反應’以摻雜錳為活化劑’經旋轉塗佈可低溫 口成均質單相之矽鋅礦薄膜，並由調整摻雜劑量及改變熱處 9 201020313 理親*氣控制綠光發射之強度。 本發明之另一目的係在於提供一種具有高純度、奈米晶 型、高均質性、高效率綠光強度、低成本設備簡單，及降 低製程溫度等多項優點的奈米晶型錳活化矽鋅礦薄膜。 本發明之又一目的係在於提供一種以溶凝膠技術製備均 質單相及奈米晶型之錳活化矽鋅礦薄膜’其具有高發光效率 及低哀減時間之特性。 本發明之再一目的係在於提供一種直接藉由控制鋅錳 氣化鹽、及矽乙醇鹽之水解、解膠、及縮聚合反應，並經不 同製程條件’製備具有均質單相、高發光強度及低衰減時 間之錳活化矽鋅礦高效率發光薄膜之溶膠凝膠技術。 可達成上述發明目的之以溶凝膠技術製備錳活化矽鋅礦 薄膜的方法，包括有： 藉由控制辞氣化鹽與矽乙醇鹽（矽化合物）之水解與解膠 反應’並#雜不同濃度之錳作為活4匕齊丨，以形成清徹之溶 膠，經旋轉塗佈於矽基板或石英基板及熱處For the ZmSi〇4:Mn矽 remnant film, the structure of the host lattice and the electronic configuration of the activator will affect its luminescence properties, due to the different crystal structure of Zn2Si()4:t allomorphic 其' The field is different and affects the wavelength of the radiation; and for the display component, the attenuation time (remaining bomb) is less than i〇ms (for example, as disclosed in US Pat. No. 5,518,655). It is conventionally known that increasing the concentration of doped manganese (10) can reduce the decay time, but at the same time it also reduces the luminescence intensity. Therefore, it is extremely necessary to develop a new sol-gel technique to prepare a mixed reed film with homogeneous single phase and low decay time. It has high luminous efficiency to significantly enhance its applicability and popularization. The factors that basically affect the conversion of sol-gel hard rubber Csol-gel are mainly precursors, system concentration, enthalpy, degree, agent, catalyst, pH and reaction temperature. For oxide ceramics, the P m is known to be > the process conditions of the gluten will strongly affect the state of the sol. This will also significantly affect the homogeneity of the colloidal film and its molecular structure. Especially for multi-component materials, the precursors with different S''s are hydrolyzed to have a significant difference from the rate of polycondensation of 8 201020313', which easily leads to the formation of a second phase of the precipitation during the crystallization process. In other words, if you can control the hydrolysis, degumming, and polycondensation of different precursors, and do not add any gelling agent, prepare a homogenous ray [body thin Teng' and then prepare the nanocrystals by different heat treatment conditions. The short-acting and simple single-phase short-acting dream breaks through the film, which can effectively improve its luminous stability and practical use. Compared with conventional deposition or sputtering techniques, ZmSiCh is prepared by sol-gel method: Another advantage of Μη石夕辞膜 is that it can be directly coated on the substrate by spin-coated ginseng. In addition, it has the potential of mass production and large area, and the equipment is relatively simple, which can greatly reduce the manufacturing cost. So far, there has not been any domestic and international research on the hydrolysis, degumming, and polycondensation of zinc, manganese gasification salts and ethoxide salts, and the preparation of homogeneous single phase, high luminous intensity, and low attenuation through different process conditions. The time-dependent Mn-activated yttrium-zinc ore (a-ZmSiOd Μη) high-efficiency luminescent film was proposed by sol-gel technique. [Explanation] The object of the present invention is to provide a sol-gel technique capable of producing homogeneous single phase, high luminescence intensity and low decay time to prepare a nanocrystalline manganese-activated yttrium high-efficiency luminescent film. A second object of the present invention is to provide a method for preparing a manganese activated strontium zinc ore film by a sol-gel technique, which uses a sol-gel technique to control the hydrolysis and gelation reaction by using manganese as an activator. 'Rotating coating can form a homogeneous single-phase yttrium zinc ore film at a low temperature, and adjust the doping amount and change the intensity of the green light emission by adjusting the heat. Another object of the present invention is to provide a nanocrystalline manganese-activated bismuth zinc having high purity, nano crystal form, high homogeneity, high efficiency green light intensity, low cost, simple equipment, and reduced process temperature. Mineral film. Still another object of the present invention is to provide a manganese-activated bismuth zinc ore film which is prepared by a sol-gel technique and which has a high luminous efficiency and a low mitigation time. A further object of the present invention is to provide a homogeneous single phase, high luminous intensity by directly controlling the hydrolysis, degumming, and polycondensation of zinc-manganese gasification salts and hydrazine ethoxide salts, and preparing under different process conditions. And sol-gel technology of high-efficiency luminescent film of manganese-activated yttrium ore with low decay time. A method for preparing a manganese-activated bismuth zinc ore film by a sol-gel technique, which comprises the following objects, comprising: controlling the hydrolysis and degumming reaction of a gasified salt and a hydrazine ethoxide (a hydrazine compound) The concentration of manganese is used as a living enthalpy to form a clear sol, which is spin coated on a ruthenium substrate or a quartz substrate and a hot spot.
理 600 〜1200〇C 後，以製備均質單相之矽鋅礦薄膜。以此方法製得之矽鋅礦 薄膜分別經熱處理800〜120(rc後，平均晶粒度分別為 Μ·5 45nn^螢光光譜顯示當錳活化劑摻雜濃度為〇2〜2〇〇 莫耳（％)具有發射綠光的特性，放射峰波長為528(±4)nm，衰 減時間（餘輝；T：1/e)為2G.2〜G.6ms，其中猛活化劑摻雜濃度為 201020313 8.0莫耳（％) ’鍍膜層數為五層，且經熱處理12〇〇c，具有最 ' 佳發光強度。 ' 【實施方式】 請參閱圖一，本發明所提供之以溶凝膠技術製備錳活化 梦鋅礦薄膜，其包括提供一基板，並於該基板上形成多層結 構’該多層結構主要以鋅氣化鹽與矽乙醇鹽再摻雜錳活化劑 製得的溶膠，經旋轉塗佈於基板，待多層結構乾燥後，再經 〇 還原氣體熱處理以獲得梦辞礦薄膜。 其中該基板主要為梦基板或石英基板’該鋅氣化鹽與石夕 乙醇鹽的組成為含矽乙醇鹽的乙醇溶液（矽乙醇鹽以115ml 、 溶於乙醇溶劑中，而乙醇濃度為2莫耳/升）並加入去離子水 與鹽酸溶液（鹽酸濃度為莫耳/升）後，再與含氣化鋅的乙 醇溶液（氣化鋅14.05g加入乙醇溶劑中，而乙醇濃度為2莫 耳/升）混合製得，其中該氣化鋅加入乙醇溶劑中於恆溫水槽 ®中均勻攪拌〇.5〜i.0小時，攪拌溫度為60。(：，次之，該鋅氣 化鹽溶液冷卻至室溫後與矽乙醇鹽溶液混合，並加入錳活化 劑實施摻雜處理，繼之將混合溶液置於恆溫水槽中進行回流 冷凝，亦再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，水解反應後於室溫下靜置以製得溶膠 而本發明該錳活化矽鋅礦薄膜的方法，其包含下列步 驟： ’ ⑷提供含矽乙醇Μ乙醇並加入去料水與鹽酸溶 11 201020313 液；主要將11.5ml的矽乙醇鹽溶於乙醇溶劑中，並加入2ml 的去離子水與鹽酸溶液於室溫均勻混合攪拌〇 5小時，乙醇 • 濃度為2莫耳/升，鹽酸濃度為〇丨莫耳/升； (b)提供含氣化鋅的乙醇與步驟中的組成混合，並加 入氣化錳實施摻雜處理；主要將14.05g的氣化鋅加入乙醇溶 劑中於怪溫水槽中均勻攪拌0.54.0小時，攪拌溫度為 60°C，而乙醇濃度為2莫耳/升； 〇 (c)冷凝步驟（b)中的組成並再加入水與鹽酸，形成一溶 膠；其中步驟（c)係採溶膠-凝膠法膠體化步驟（b)中之組成， 混合溶液置於恆溫水槽中進行回流冷凝，進行水解與解膠反 應使膠粒分子呈均勻懸浮分散，反應時間為〗〜2小時，反 -應溫度為25°C，再將水解反應後之產物於室溫下靜置以製得 溶膠，水濃度為0.5〜2.0莫耳/升，鹽酸濃度為〇丨〜❹」莫 耳/升； ❹ （d)鍍膜步驟（c)中的溶膠在基板上，使基板形成一膠體 薄膜； (e) 重複實施步驟（d)使基板上形成多層結構； (f) 乾燥的單層或多層結構經氮氫混合氣的還原氣體熱 處理以獲得矽鋅礦薄臈。 為更詳盡說明本發明，將本發明區分成兩部分説明； (一）製備透明之溶膠程序·· 12 201020313 首先，將秒乙醇鹽〔Si(OC2H5)4〕u 5ml溶於乙醇溶刺 中並加入2ml的去離子水與鹽酸溶液於室溫均勻混合攪拌 • 〇,5小時，乙醇濃度為2莫耳/升，鹽酸濃度為〇」莫耳/升； 另取14.05g的氣化辞加入乙醇溶劑中於恆溫水槽中均 勻搜拌0.5〜1.0小時，授拌溫度為航，而乙醇濃度為2莫 耳/升； 、 待辞氣化鹽（氣化辞）溶液冷卻至室溫後與矽乙醇鹽溶液 ® 混合，並加入錳活化劑（氣化錳）實施摻雜處理，錳離子濃度 為 0.2-20.0 莫耳（。/0); 繼之，將混合溶液置於恆溫水槽中進行回流冷凝，再加 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’反應時間為1〜2小時，反應溫度為25。(：，水與鹽 酸濃度分別為0.5〜2.0莫耳/升及〇.1〜〇.3莫耳/升。將水解 反應後之產物於室溫下靜置以製得清澈透明之溶膠。 ® (二）製備奈米晶型石夕鋅礦薄膜： 將依上述方法製得之透明溶膠於25°C及相對濕度55% 下能進行縮聚合反應，於溶膠黏度為20〜lOOmPa.s時，將 基板置於旋轉塗佈機上作鍍膜處理亦均化薄膜表面的厚 度，基板分別為矽基板或石英基板，轉速為3000〜4000Γριη， 旋轉時間為20sec，單層膠體薄膜經乾燥後，可依前述方式 實施第二層〜第五層鍍膜，以製備不同鍍膜層數之膠體薄 13 201020313 膜，繼之，將薄膜分別置於氮氫混合氣（Nz/H2)還原氣體中熱 處理（燒結），燒結溫度為500〜1200°C，燒結時間為2〜6小 * 時，加熱速度為3°C /min，經燒結600°C後開始產生梦辞礦 (a-ZnsSiO4)結晶，燒結600〜1200°C後均可獲得均質單相且具 有斜方六面體結構之矽鋅礦（a-ZnsSiO4)薄膜（請參閱第2 圖），不同的溶液濃度、錳活化劑摻雜濃度、及基板材料對結 晶行為無明顯影響，結晶性均隨燒結溫度與時間增加而辦 β加。 以此方法製得之矽辞礦薄膜分別經熱處理 800〜1200°C，2〜6小時後，平均晶粒度分別為16 5〜35 〇nm 及18.0〜45.0nm(依Scherrer方程式）。經熱處理9〇〇〜12〇〇〇c 後該矽鋅礦薄膜的螢光激發光譜顯示於波峰為27〇nm處具 有最高激發強度（請參閲第3圖），以波長為27〇11111之紫外線 激發後，螢光發射光譜顯示當氣化錳活化劑摻雜濃度為 0.2〜20.0莫耳（％)均具有發射綠光的特性，放射峰波長為 528(±4)nm，發光強度隨熱處理溫度與時間增加而增加（請參 閱第4圖），經熱處理120(rc後，薄膜厚度依鍍膜層數分別 為 11 〇±1 Onm(單層）、320±20nm(三層）、及 58〇±2〇nm(五層）， 發光強度隨錳活化劑摻雜濃度及鍍膜層數而異，衰減時間（餘 輝；t1/e)為20.2〜0.6ms(請參閱第5圖與第6圖），其中錳活化 劑摻雜濃度為莫耳（％)時，衰減時間可為 201020313 4·8〜0.8ms，當猛活化劑換雜濃度為8_0莫耳（％)，鑛嫉層數 為五層’且經熱處理120(TC，時間為6小時，具有最佳發光 - 強度。 本發明所提供之以溶凝膠技術製備錳活化矽鋅礦薄膜 的方法’經由以上之說明，更具有下列之優點： (1) 本發明之錳活化矽鋅礦薄膜可利用旋轉塗佈方式直 接塗佈在基板上’具有量產及大面積化之潛力，且設備較簡 ® 單，可大幅降低製造成本。 (2) 操作容易且顯著縮短製程時間，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，除可顯著縮短膠化時程亦可低溫合成奈米晶型且均質 單相矽辞礦，對於改善可靠發光效率、穩定性發光、及節省 能源具有顯著功效。 (3) 本發明之錳活化矽鋅礦薄膜，具有高發光效率及低衰 ❹減時間之特性’其中錳活化劑摻雜濃度為4 〇~12 〇莫耳㈤ 時，衰減時間可為4.8〜0.8ms，適用於顯示器元件，且不添 加任何多元醇或膠化劑，具有高亮度、高純度、及環保特色， 可顯著提升其應用性及普及化。 (4) 本發明之矽鋅礦薄膜具有高效率發射綠光特性，且可 藉由調整活化舰度、渡層數目、及熱處理條件，控制石夕辞 礦的發光強度，可廣泛應用於各式照明設備、顯示器元件、 15 201020313 及交通號誌等各種 光感測器、汽機車的儀表面板、警示燈 不同領域。 ⑺本發明之綠歧活切_相，可應用於白光咖 善目前白光LED發光不自然㈣題1具有耗電量 低、壽命長和反應速度佳等優點。 參 (6)本發明之短活切辞韻膜，具㈣化膜厚特性，經 處理12〇〇C後，單層薄膜厚度可為u〇(±i〇)nm，且僅需藉 由渡層數目即可控制膜厚，適用於陰極射線管、電漿顯示 器、場發射顯示器、電致發光等各種不同領域之顯示器元 件’亦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、及照明設備。 綜上所述，本案不但在低溫合成單相矽辞礦薄膜及其空 間型態上確屬創新，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，爰依法提 • 出申請，懇請貴局核准本件發明專利申請案，以勵發明， 至感德便。 【圖式簡單說明】 圖一為本發明具體實施例之製備流程圖。 圖二為本發明具體實施例之X-光繞射圖。 圖三為本發明具體實施例之螢光激發光譜。 圖四為本發明具體實施例之發光強度隨熱處理溫度及 時間變化圖。 201020313 圖五為本發明具體實施例之摻雜濃度與發光強度及衰 減時間（餘輝）之關係圖。 圖六為本發明具體實施例之發光強度隨薄膜渡層數目 變化圖。 【主要元件符號說明】 無After 600 to 1200 〇C, a homogeneous single-phase yttrium zinc ore film is prepared. The zinc antimony ore film prepared by this method is respectively heat treated at 800~120 (after rc, the average grain size is Μ·5 45nn^ fluorescence spectrum shows when the manganese activator doping concentration is 〇2~2〇〇莫The ear (%) has the characteristic of emitting green light, the emission peak wavelength is 528 (±4) nm, and the decay time (afterglow; T:1/e) is 2G.2~G.6ms, wherein the activator doping concentration It is 201020313 8.0 Mo Er (%) 'The number of coating layers is five layers, and after heat treatment 12〇〇c, it has the best 'luminescence intensity.' [Embodiment] Please refer to Figure 1, the sol gel provided by the present invention The invention comprises the steps of: preparing a manganese activated dream zinc ore film, comprising: providing a substrate, and forming a multi-layer structure on the substrate; the multi-layer structure is mainly prepared by using a zinc gasification salt and a barium glycolate and then doping a manganese activator, and rotating After being coated on the substrate, after the multi-layer structure is dried, it is further heat-treated by a ruthenium reducing gas to obtain a dream mineral film. The substrate is mainly a dream substrate or a quartz substrate, and the composition of the zinc gasification salt and the stone ethoxide salt is ruthenium-containing. Ethanol salt in ethanol solution (矽 ethanol salt in 115ml, soluble in ethanol solvent Medium, while the ethanol concentration is 2 mol / liter) and adding deionized water and hydrochloric acid solution (hydrochloric acid concentration of mol / liter), and then with the zinc solution containing zinc oxide (1. 05g of zinc oxide added to the ethanol solvent And the ethanol concentration is 2 m / liter), wherein the vaporized zinc is added to the ethanol solvent and uniformly stirred in a constant temperature water bath® for 5 to 1.0 hours, and the stirring temperature is 60. (:, second After the zinc vaporized salt solution is cooled to room temperature, it is mixed with the cesium ethoxide solution, and a manganese activator is added for doping treatment, and then the mixed solution is placed in a constant temperature water tank for reflux condensation, and water and hydrochloric acid solution are further added. The method for performing the hydrolysis and the degumming reaction to uniformly disperse and disperse the colloidal molecules, and then allowing to dissolve at room temperature to obtain a sol, and the manganese-activated bismuth ore thin film of the present invention comprises the following steps: ' (4) providing矽 Ethanol Μ ethanol and add decontamination water and hydrochloric acid solution 11 201020313 solution; mainly dissolve 11.5ml of hydrazine ethoxide in ethanol solvent, and add 2ml of deionized water and hydrochloric acid solution to mix and mix at room temperature for 5 hours. Ethanol • Rich 2 mol / liter, the concentration of hydrochloric acid is 〇丨 mol / liter; (b) providing zinc containing zinc oxide mixed with the composition in the step, and adding manganeseated manganese to carry out doping treatment; mainly 14.05 g of gas Zinc is added to the ethanol solvent and uniformly stirred in a strange temperature water bath for 0.54.0 hours, the stirring temperature is 60 ° C, and the ethanol concentration is 2 mol / liter; 〇 (c) the composition in the condensation step (b) and then added Water and hydrochloric acid form a sol; wherein step (c) is a composition of the sol-gel colloidal step (b), and the mixed solution is placed in a constant temperature water bath for reflux condensation to carry out hydrolysis and degumming reaction to make the rubber particles The molecule is uniformly suspended and dispersed, the reaction time is 〖~2 hours, the reverse-should temperature is 25 °C, and the product after the hydrolysis reaction is allowed to stand at room temperature to obtain a sol, the water concentration is 0.5~2.0 mol/ l, the concentration of hydrochloric acid is 〇丨~❹"mol / liter; ❹ (d) coating the sol in step (c) on the substrate to form a colloidal film on the substrate; (e) repeating step (d) on the substrate Forming a multilayer structure; (f) a reduced single or multi-layer structure with a reducing gas of a nitrogen-hydrogen mixture Thermal treatment to obtain a thin silicon zinc Ge. In order to explain the present invention in more detail, the present invention is divided into two parts; (1) Preparation of transparent sol procedure·· 12 201020313 First, 5 ml of sec-ethanol salt [Si(OC2H5)4]u is dissolved in ethanol spur and Add 2ml of deionized water and hydrochloric acid solution and mix and mix evenly at room temperature. • 〇, 5 hours, the concentration of ethanol is 2 mol/L, the concentration of hydrochloric acid is 〇"mol / liter; another 14.0 g of gasification is added to ethanol. The solvent is uniformly mixed in a constant temperature water bath for 0.5 to 1.0 hours, the mixing temperature is aeronautical, and the ethanol concentration is 2 mol/l; and the gas to be degassed (gasification) is cooled to room temperature and then ethanol is added. The salt solution is mixed and added with a manganese activator (manganese gasification) for doping treatment. The manganese ion concentration is 0.2-20.0 mol(./0). Then, the mixed solution is placed in a constant temperature water bath for reflux condensation. Further, water and hydrochloric acid solution are added for hydrolysis and degumming reaction to make the colloidal molecules uniformly suspended and floated. The reaction time is 1 to 2 hours, and the reaction temperature is 25. (: The concentration of water and hydrochloric acid is 0.5 to 2.0 m/liter and 〇.1 to 〇.3 mol/liter, respectively. The product after the hydrolysis reaction is allowed to stand at room temperature to obtain a clear transparent sol. (2) preparing a nanocrystalline crystal shixi zinc ore film: the transparent sol obtained by the above method can be subjected to polycondensation polymerization at 25 ° C and a relative humidity of 55%, and when the sol viscosity is 20 to 100 mPa·s, The substrate is placed on a spin coater for coating treatment to homogenize the thickness of the surface of the film. The substrate is a ruthenium substrate or a quartz substrate, and the rotation speed is 3000~4000 Γριη, and the rotation time is 20 sec. After the single-layer colloid film is dried, The second layer to the fifth layer are coated in the foregoing manner to prepare a colloidal thin film 13 201020313 with different coating layers, and then the film is separately heat treated (sintered) in a reducing gas of nitrogen-hydrogen mixed gas (Nz/H2). When the sintering temperature is 500~1200°C, the sintering time is 2~6 small*, the heating rate is 3°C/min, and after sintering 600°C, the crystal of a-ZnsSiO4 is formed, and the sintering is 600~1200. After °C, you can obtain a homogeneous single phase and have a rhombohedral structure. Zinc ore (a-ZnsSiO4) film (see Figure 2), different solution concentrations, manganese activator doping concentration, and substrate materials have no significant effect on crystallization behavior, crystallinity increases with sintering temperature and time. The ruthenium film obtained by this method is subjected to heat treatment at 800 to 1200 ° C for 2 to 6 hours, and the average grain size is 16 5 to 35 〇 nm and 18.0 to 45.0 nm, respectively (according to the Scherrer equation). After heat treatment of 9〇〇~12〇〇〇c, the fluorescence excitation spectrum of the bismuth zinc ore film shows the highest excitation intensity at 27〇nm (see Figure 3), with a wavelength of 27〇11111. After ultraviolet excitation, the fluorescence emission spectrum shows that when the doping concentration of the vaporized manganese activator is 0.2~20.0 mol (%), it has the characteristic of emitting green light, the emission peak wavelength is 528 (±4) nm, and the luminous intensity is related to the heat treatment. The temperature and time increase and increase (see Figure 4). After heat treatment 120 (rc, the thickness of the film depends on the number of coating layers: 11 〇 ± 1 Onm (single layer), 320 ± 20 nm (three layers), and 58 〇. ±2〇nm (five layers), luminous intensity with manganese activator doping concentration and coating The number of layers varies, and the decay time (afterglow; t1/e) is 20.2~0.6ms (refer to Figure 5 and Figure 6). When the doping concentration of manganese activator is Mo (%), the decay time can be For 201020313 4·8~0.8ms, when the concentration of the activator is 8_0 mol (%), the number of layers is 5 layers' and the heat treatment is 120 (TC, the time is 6 hours, with the best luminescence - strength The method for preparing a manganese activated strontium zinc ore film by a sol-gel technique provided by the present invention has the following advantages through the above description: (1) The manganese-activated bismuth ore film of the present invention can be spin-coated. Direct coating on the substrate has the potential to be mass-produced and large-area, and the equipment is simple and simple, which can greatly reduce the manufacturing cost. (2) Easy to operate and significantly shorten the process time. Only by controlling the hydrolysis and degumming reaction with low water and hydrochloric acid electrolyte, the micelle molecules can be uniformly suspended and dispersed, in addition to significantly shortening the gelation time course and low temperature synthesis. The nanocrystalline and homogeneous single-phase rhodium minerals have significant effects on improving reliable luminous efficiency, stable luminescence, and energy saving. (3) The manganese-activated bismuth zinc ore film of the present invention has high luminous efficiency and low fading and time-reducing characteristics. When the doping concentration of the manganese activator is 4 〇~12 〇m (5), the decay time can be 4.8~ 0.8ms, suitable for display components, without adding any polyol or gelling agent, with high brightness, high purity, and environmental protection features, can significantly enhance its applicability and popularization. (4) The bismuth zinc ore film of the present invention has high-efficiency emission green light characteristics, and can control the luminescence intensity of Shixia dynasty by adjusting the activation degree, the number of layers, and heat treatment conditions, and can be widely applied to various types. Lighting equipment, display components, 15 201020313 and traffic signs, various light sensors, instrument panels for motorcycles, warning lights in different fields. (7) The green hybrid _ phase of the present invention can be applied to white light coffee. At present, white light LED illumination is unnatural (4). Title 1 has the advantages of low power consumption, long life and good reaction speed. Reference (6) The short live-cut rhyme film of the present invention has a (four) film thickness characteristic, and after processing 12 〇〇C, the thickness of the single-layer film can be u〇(±i〇) nm, and only needs to be crossed. The number of layers can control the film thickness, and it is suitable for display elements in various fields such as cathode ray tube, plasma display, field emission display, electroluminescence, etc. It also helps to develop this material for future large-area full-color display. Field emission display, and lighting equipment. In summary, the case is not only innovative in the low-temperature synthesis of single-phase enamel film and its spatial pattern, but also can meet the novelty and progressive legal patent requirements compared with the conventional products.爰According to the law and request, you are requested to approve the application for this invention patent, in order to invent invention, to the sense of virtue. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart of the preparation of a specific embodiment of the present invention. Figure 2 is an X-ray diffraction diagram of a specific embodiment of the present invention. Figure 3 is a fluorescence excitation spectrum of a specific embodiment of the present invention. Figure 4 is a graph showing changes in luminous intensity with heat treatment temperature and time in accordance with a specific embodiment of the present invention. 201020313 Figure 5 is a graph showing the relationship between doping concentration and luminescence intensity and decay time (afterglow) of a specific embodiment of the present invention. Figure 6 is a graph showing changes in luminous intensity as a function of the number of layers of a film in a specific embodiment of the present invention. [Main component symbol description] None
1717