!262212 九、發明說明 【發明所屬之技術領域】 本&月係有關☆種螢光粉體及其製造方法，特別是有 關於-種釔銘石榴石粉體及其製造方法。 【先前技術】 妙螢光材料及發光物質，可將激發它的能量轉換為光，雖 一不-定是可見光。其次，螢光材料被發現的歷史已久，例 女有些礦物本身在紫外光的照射下就會發光，可作為對礦物 的辨別。螢光材料的應用形式可為粉體或薄膜，而近來螢光 材料最熱門之應用領域為白光發光二極體（Light Emitting Diode，LED)。螢光材料應用在白光LED主要是以粉體的 幵:式。目前i要是採用冑光粉混合封裝材料，例如樹脂、石夕 膠’將其塗覆在晶片上，直接激發螢光粉。 ^自1967年由Blasse與Brill開始發展摻雜鈽之釔鋁石 才田石（YUrium Aluminum Garnet; YAG:Ce; Y3Al5〇12:ce)螢 光籾田時主要疋應用在陰極射線管。由於摻雜鈽之釔鋁石 榴石螢光粉會吸收藍光波段，在傳統照明上以其來增加色 溫° 自1996年曰亞（Nishia)公司發表白光[ED以來，曰亞 公司更於美國專利公告號第5,998,925號揭露應用在白光 LEC>之螢光粉，此螢光粉為摻雜鈽之釔鋁石榴石（Yttrium Ahnninum Garnet; YAG:Ce; Y3Al5〇i2:Ce)。至此釔紹石 權石也成為照明用螢光粉的主角之一。 6 1262212 紀銘石權石為熱穩定度相當高之物質，由於能隙大，本 身可發紫外光（即短波長區），經摻雜稀土（Rare Earth)元素之 ^，其發光波長便朝向可見光區（即長波長區）移動。舉例而 言，摻雜鈽之釔鋁石榴石可發黃光，掺雜铽之釔鋁石榴石可 發綠光，而摻雜銪之釔鋁石榴石可發紅光。 在習知技術中，釔鋁石榴石粉體一般係利用化學方法， 例如沉澱法、溶膠凝膠法（SGl_Gel MethGd)、水熱法及燃燒 法’或固相反應法來製造。傳統之@相反應法係㈣氧化紀 (Υ2〇3)及氧化鋁（Ai2〇3)為起始材料，添加劑亦以氧化物為 主。此起始材料必須在溫度約16〇〇t以上高溫煅燒2小時， 才形成釔鋁石榴石粉體。如欲降低煅燒溫度，則必須添加熔 鹽⑻ux)例如氟化鋇（BaF2)或氟化紀（YF3)等，可將锻燒溫度 降至测t並高溫锻燒2小時，以形成紀銘石權石粉體。 我國專利公告號第146047號揭露—種紀銘石權石微粒 子及㈣石權石系螢光體微粒子之製造方法，其特徵為阳 值1〇.〇以上鹼水溶液中，27(rc以上反應溫度下使釔化人 物之水解生成物或Μ，與純合物之水解生成物或銘鹽二 反，’ 呂石權石微粒子；以及在pHi ι〇 〇以上驗 水各液中，270。。以上反應溫度下，使釔化合物之水解生成 物或紀鹽，與純合物之水解生成物或㈣，與試化合物之 :解生成物或試鹽相反應，以製造紀銘石梅石系螢 子之方法。 & t國專利公告㈣4⑵85號揭露—種製㈣摻雜μ 乳石權石[(Y，Ce)3Al5〇i2型]為係f光粉粉末，係利用金屬鉗 1262212 :物/有錢凝膠法製備粉體，與—般使用固態反應法所完 成的微細粉末不同。此專利係以金屬氧化物或賴鹽為主要 原枓，形成4耳比& Y: Ce: A1分別為（3_χ): χ: $⑺％ 〇·”之水溶液，加入鉗合劑使金屬形成金屬鉗合物，再加入 有機鹼調整溶液的酸鹼值(ρΗ)至鹼性並形成稠狀溶液，於 80 c〜not加熱上述溶液，形成凝膠物，再將上述凝膠物 於1500 c熱結後，即可且均勻之具螢光性粉末。 我國專利公告號第538 1丨5號揭露一種具有 (υ3^χ)(αι5·Μ)〇ι2[以下簡稱蝴]之奈米級減氧石權 石(YAG)螢光粉體之製造方法，其中…及r2分別選自於由 稀土兀素及過渡金屬元素所組成之群，χ與y分別係介於〇 與1.5間之數值’該方法包含以下步驟：⑷形成_含有稀土 元素或過渡金屬元素離子、釔離子及鋁離子之水溶液，^) 形成一 PH值介於2至5之間的聚丙烯酸（pAA)水溶液，並 將之添加至步驟（a)之水溶液中，以形成一凝膠，（勾烘乾步 驟（b)之凝膠以獲得一乾燥膠體，（d)於介於75〇至13〇〇。〇之 溫度下燒結步驟（c)之產物，以獲得上述式（1)之奈米級釔鋁 氧石榴石螢光粉體。 表亍、έ之，上述習知固相反應法之合成溫度較高且製程時 間較長，液相反應法之合成溫度雖較低，但無可避免會排出 5午多廢水及廢液。據此，實有必要開發一種釔鋁石榴石粉體 及其製造方法，以改善習知固相反應法及液相反應法之種種 缺點。 1262212 ^ 2，以形成酸性漿料，其中上述酸性漿料之酸鹼值係小於或 等於3，且上述含鋁化合物可包括但不限於氧化鋁或氫氧化 、接著進行乾無步驟，以去除上述酸性漿料之水性溶劑。 _ 然後，進行高溫煅燒步驟，以於溫度實質上介於12〇〇χ：至 1 700 C之間形成釔鋁石榴石粉體。 應用上述方法製造釔鋁石榴石粉體時，由於利用酸性漿 籲料經乾燥步驟及實質上介於12〇〇。〇至170(rc之間的高溫二 燒步驟而形成。上述酸性漿料至少包含氧化釔、含鋁化合物 及水性溶劑。相較於習知固相反應法或液相反應法，本發明 之釔鋁石榴石粉體之合成溫度較低且製程時間縮短，因此不 僅能有效改善習知固相反應法之缺點，更降低液相反應法所 排出之廢水及廢液。 【實施方式】 本發明之釔鋁石榴石粉體係利用酸性漿料，經乾燥步驟 •及溫度實質上介於12〇〇°c至1700。。之間的高溫煅燒步驟而 形成。以下詳細說明本發明之釔鋁石榴石粉體及其製造方 法。 首先，將氧化紀以及含鋁化合物混合於水性溶劑中，例 如水，以形成漿料。接著，利用酸鹼值調整劑，例如無機酸 或有機酸，將上述漿料之酸鹼值調整至小於或等於3為宜， 以小於或等於2為較佳，而以小於或等於i為更佳，以形成 酸性漿料。適合的無機酸可例如硝酸（HN〇3)、硫酸（H2S〇4)、 磷酸（Η;Ρ〇4)或碳酸（Ηχο3)，適合的有機酸可例如醋酸 10 1262212 - 將重畺約1.1 4公克之氣化紀及重量約〇 · 8 6公克之氧化 鋁粉體混合於172毫升之水中，以形成漿料。然後，進行離 心乾燥步驟，以去除漿料之水性溶劑，而形成乾燥粉體。之 後，將前述所得之乾燥粉體進一步於9〇(rc煅燒1小時，而 所得的結果如第5圖所示。 凊參閱第5圖，其係顯示未經酸處理之混合粉體之X 射線繞射圖譜’其中縱轴表示強度（cps)，而橫軸則表示掃 描角度（2 β。）。由第5圖之結果得知，未經酸處理的混合粉 體經過900°C煅燒後，仍為氧化釔相（如圖例♦所示）。 列二 將重量約1.14公克之氧化釔及重量約〇·86公克之氧化 鋁粉體混合於172毫升之水中，以形成漿料。然後，進行離 心乾燥步驟，以去除漿料之水性溶劑，而形成乾燥粉體。之 後，將前述所得之乾燥粉體進一步於12〇〇t：緞燒i小時， 而所得的結果如第6圖所示。 、 4苓閱第6圖，其係顯示未經酸處理之混合粉體之χ射 線繞射圖譜，其中縱軸表示強度（eps)，而橫軸則表示掃描 角度（2 Θ。）。由第6圖之結果得知，未經酸處理的混合粉體 經過12〇〇〇C锻燒後，才會形成氧化紀（如圖例所示）以及 γΑΜ相（如圖例♦所示），但無釔鋁石榴石相形成。 ^簡g之，本發明之釔鋁石榴石粉體及其製造方法，其特 =於利用酸鹼值小於或特3之酸性漿料經乾燥步驟及 貝質上"於1200 C至1700。。之間的高溫緞燒步驟而形成。 14 1262212 由於本發明之釔鋁石 才留石粉體不限於摻雜之稀土元素種 類 因此可視實際需求添加各種稀土元素以提供具有不同螢 光光譜之釔鋁石榴石粉體。 之合成溫度較低且製程時間 再者’本發明之釔鋁石榴石粉體 縮短’不僅能有效改善習知固相 反應去之缺點’更降低液相反應法所排出之廢水及廢液，此 為習知製程所遠不及於本發明之處。262 211 211 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262 262. [Prior Art] The wonderful fluorescent material and the luminescent substance convert the energy that excites it into light, although it is not visible. Secondly, fluorescent materials have been discovered for a long time. Some minerals themselves emit light under ultraviolet light and can be used as a distinguishing mineral. Fluorescent materials can be applied in the form of powders or films. Recently, the most popular application area for fluorescent materials is the Light Emitting Diode (LED). The use of fluorescent materials in white LEDs is mainly in the form of powders. At present, i should directly coat the phosphor powder by using a calender powder mixed encapsulating material such as resin or sapphire. ^Since 1967, Blasse and Brill began to develop YUrium Aluminum Garnet (YAG:Ce; Y3Al5〇12:ce), which is mainly used in cathode ray tubes. Since the yttrium-doped yttrium aluminum garnet fluorescing powder absorbs the blue light band, it is used to increase the color temperature in traditional lighting. Since the publication of white light by Nishia in 1996, the company has been in the US Patent Publication No. No. 5,998,925 discloses a phosphor powder for use in white light LEC>, which is Yttrium Ahnninum Garnet (YAG: Ce; Y3Al5〇i2: Ce). At this point, Shi Shaoshi has become one of the protagonists of fluorescent powder for lighting. 6 1262212 纪铭石权石 is a material with relatively high thermal stability. Due to its large energy gap, it can emit ultraviolet light (ie, short-wavelength region). When it is doped with rare earth (Rare Earth) element, its light-emitting wavelength is toward the visible light region. (ie long wavelength zone) moves. For example, yttrium-doped yttrium aluminum garnet can emit yellow light, and yttrium-doped yttrium aluminum garnet can emit green light, while yttrium-doped yttrium aluminum garnet can emit red light. In the prior art, yttrium aluminum garnet powder is generally produced by a chemical method such as a precipitation method, a sol-gel method (SGl_Gel MethGd), a hydrothermal method, and a combustion method or a solid phase reaction method. The traditional @phase reaction system (4) Oxidation (Υ2〇3) and Alumina (Ai2〇3) are the starting materials, and the additives are mainly oxides. The starting material must be calcined at a temperature of about 16 〇〇t or higher for 2 hours to form yttrium aluminum garnet powder. If you want to reduce the calcination temperature, you must add molten salt (8) ux) such as barium fluoride (BaF2) or fluorinated (YF3), etc., can reduce the calcination temperature to t and high temperature calcination for 2 hours to form Jiming Shiquanshi Powder. China Patent Publication No. 146047 discloses a method for producing a kind of granules of Jiming Shiquanshi and (4) Shiquanshi phosphors, which are characterized by a positive value of 1 〇. The hydrolyzed product or hydrazine of the deuterated character, and the hydrolyzed product or the salt of the pure compound, 'Lv Shiquan stone microparticles; and in the water solution above pHi ι〇〇, 270. At the above reaction temperature, A method for producing a hydrolyzed product or a salt of a hydrazine compound, a hydrolyzed product of a pure compound or (4), a reaction product with a test compound, or a test salt to produce a gems of the gems. National Patent Announcement (4) 4 (2) No. 85 Revealed - Seed Production (4) Doped μ Milkstone Stone [(Y, Ce) 3Al5〇i2 Type] is a f-powder powder, which is prepared by metal pliers 1262212: material/rich gel method The body is different from the fine powder which is generally prepared by the solid state reaction method. The patent is based on a metal oxide or a lysine salt, and forms a 4 amp ratio & Y: Ce: A1 is (3 χ): χ: $(7)% 〇·” of an aqueous solution, adding a chelating agent to form a metal Is a tongs compound, then add the organic base to adjust the pH value of the solution to alkaline and form a thick solution, heat the above solution at 80 c~not to form a gel, and then the above gel at 1500 c After the hot junction, the fluorescent powder can be evenly and uniformly. Chinese Patent Publication No. 538 1丨5 discloses a nano-scale reduction with (υ3^χ)(αι5·Μ)〇ι2 [hereafter referred to as butterfly] A method for producing an oxygen stone weight (YAG) phosphor powder, wherein ... and r2 are respectively selected from the group consisting of rare earth elements and transition metal elements, and χ and y are respectively between 〇 and 1.5. The method comprises the steps of: (4) forming an aqueous solution containing rare earth elements or transition metal element ions, cerium ions and aluminum ions, and forming an aqueous solution of polyacrylic acid (pAA) having a pH between 2 and 5, and Adding to the aqueous solution of step (a) to form a gel (hook the gel of step (b) to obtain a dry colloid, (d) at a temperature of between 75 Torr and 13 Torr. The product of the step (c) is sintered to obtain the nano-grade yttrium aluminum oxygarite phosphor powder of the above formula (1). In addition, the above-mentioned solid phase reaction method has a high synthesis temperature and a long process time, and the synthesis temperature of the liquid phase reaction method is low, but it is inevitable that more than 5 noon wastewater and waste liquid will be discharged. It is necessary to develop a yttrium aluminum garnet powder and a manufacturing method thereof to improve various disadvantages of the conventional solid phase reaction method and the liquid phase reaction method. 1262212 ^ 2, to form an acidic slurry, wherein the acid of the above acidic slurry The base number is less than or equal to 3, and the above-mentioned aluminum-containing compound may include, but not limited to, alumina or hydrogen hydroxide, followed by a dry step to remove the aqueous solvent of the above acidic slurry. _ Then, a high-temperature calcination step is performed to The temperature is substantially between 12 〇〇χ: and 1 700 C to form yttrium aluminum garnet powder. When the yttrium aluminum garnet powder is produced by the above method, it is subjected to a drying step by using an acidic slurry and is substantially 12 Torr. Formed by a high temperature two-burning step between 170 and rc. The above acidic slurry contains at least cerium oxide, an aluminum-containing compound, and an aqueous solvent. Compared with the conventional solid phase reaction method or liquid phase reaction method, the ruthenium of the present invention The aluminum garnet powder has a low synthesis temperature and a short processing time, so that not only the disadvantages of the conventional solid phase reaction method can be effectively improved, but also the wastewater and waste liquid discharged by the liquid phase reaction method are further reduced. The yttrium aluminum garnet powder system is formed by using an acidic slurry, a drying step, and a temperature substantially between 12 ° C and 1700. The yttrium aluminum garnet powder of the present invention is described in detail below. And a method for producing the same. First, an oxidized group and an aluminum-containing compound are mixed in an aqueous solvent such as water to form a slurry. Next, an acid of the above slurry is used using a pH adjuster such as a mineral acid or an organic acid. The base number is preferably adjusted to less than or equal to 3, preferably less than or equal to 2, and more preferably less than or equal to i to form an acidic slurry. Suitable inorganic acids may be, for example, nitric acid (HN〇3), sulfur. Acid (H2S〇4), phosphoric acid (Η; Ρ〇4) or carbonic acid (Ηχο3), suitable organic acids such as acetic acid 10 1262212 - will weigh about 1.1 4 grams of gasification and weight about 〇 · 8 6 grams The alumina powder is mixed in 172 ml of water to form a slurry. Then, a centrifugal drying step is performed to remove the aqueous solvent of the slurry to form a dry powder. Thereafter, the dried powder obtained above is further dried. 〇(rc was calcined for 1 hour, and the results obtained are shown in Fig. 5. 凊 Refer to Fig. 5, which shows the X-ray diffraction pattern of the mixed powder without acid treatment, where the vertical axis represents the intensity (cps) The horizontal axis indicates the scanning angle (2 β.). As can be seen from the results of Fig. 5, the un-treated mixed powder is still yttria-phase after calcination at 900 ° C (as shown in Figure ♦). Column 2 combines about 1.14 grams of cerium oxide and about 0.7 gram of alumina powder in 172 milliliters of water to form a slurry. Then, a centrifugal drying step is performed to remove the aqueous solvent of the slurry. And forming a dry powder. After that, the aforementioned dried The dry powder was further fired at 12 〇〇t: satin for 1 hour, and the obtained result is shown in Fig. 6. 4, Fig. 6 shows the ray diffraction of the mixed powder without acid treatment. The map, in which the vertical axis represents the intensity (eps), and the horizontal axis represents the scanning angle (2 Θ.). From the results of Fig. 6, it is known that the untreated acid powder is calcined after 12 〇〇〇C. Oxidation (as shown in the figure) and γ ΑΜ phase (as shown in the example ♦), but no yttrium aluminum garnet phase is formed. ^ Jane, the yttrium aluminum garnet powder of the present invention and its manufacturing method It is formed by using a high-temperature satin burning step between the acidic slurry having a pH value of less than or special 3 and a drying step and a high-temperature satin burning step between 1200 C and 1700. 14 1262212 Since the bismuth-free stone powder of the present invention is not limited to the doped rare earth element species, various rare earth elements may be added according to actual needs to provide yttrium aluminum garnet powder having different fluorescence spectra. The synthesis temperature is lower and the process time is further reduced. 'The shortening of the yttrium aluminum garnet powder of the present invention can not only effectively improve the shortcomings of the conventional solid phase reaction, but also reduce the waste water and waste liquid discharged by the liquid phase reaction method. It is far from being inferior to the present invention for the conventional process.
、〜由上述本發明車交佳實施例可知，應用本發明之紀铭石權 石步刀體及其製造方法，其優點在於利用酸性漿料經乾燥步驟 、夤上；丨於1200C至17〇〇°c之間的高溫緞燒步驟而形 成。上述酸性漿料至少包含氧化釔、含紹化合物及水性溶 劑’而酸性漿料之酸鹼值係小於或等於3。相較於習知固相 ，應法或液相反應法’本發明之釔鋁石榴石粉體之合成溫度 較低且製㈣間縮短’因此不僅能有效改善習知固相反應法 之缺點’更降低液相反應法所排出之廢水及廢液。 、2 J本發明已以數個較佳實施例揭露如上，然其並非用 以限定本發明，惟此技術領域中任何具有通常知識者，在不 '本^月之精神㈣巳目内，當可作各種之更動與潤飾，因 本^月之保濩範圍當視後附之申請專利範圍所界定者 【圖式簡單說明】 所得之粉體之 所得之粉體之 第1圖係顯示根據本發明實施例一 線繞射圖譜； 第2圖係顯示根據本發明實施例二 15 1262212 線繞射圖譜； 第3圖係顯示根據本發明實施例三所得之粉體之螢光 光譜， 第4圖係顯示根據本發明實施例四所得之粉體之X射 線繞射圖譜； 第5圖係顯示未經酸處理之混合粉體之X射線繞射圖 譜；以及 第6圖係顯示未經酸處理之混合粉體之X射線繞射圖 譜。 16It can be seen from the above-mentioned embodiment of the present invention that the application of the invention is based on the method of using the acidic slurry through the drying step and the crucible; 丨 1200C to 17〇〇° A high temperature satin burning step between c is formed. The acidic slurry contains at least cerium oxide, a compound and an aqueous solvent, and the acidic slurry has a pH of less than or equal to 3. Compared with the conventional solid phase, the yttrium aluminum garnet powder of the present invention has a lower synthesis temperature and a shortened ratio between the four layers, so that it can not only effectively improve the shortcomings of the conventional solid phase reaction method. The wastewater and waste liquid discharged by the liquid phase reaction method are further reduced. The present invention has been disclosed in several preferred embodiments as above, but it is not intended to limit the invention, but any person having ordinary knowledge in the technical field is not in the spirit of (the fourth month) It can be used for various changes and refinements, as the scope of the warranty for this month is defined by the scope of the patent application attached to the following [Simplified description of the drawings] The first image of the obtained powder is shown in accordance with this Inventive embodiment, a line diffraction pattern; Fig. 2 shows a line diffraction pattern according to an embodiment of the present invention, 15 1262212; and Fig. 3 shows a fluorescence spectrum of the powder obtained according to the third embodiment of the present invention, Fig. 4 An X-ray diffraction pattern of the powder obtained according to Example 4 of the present invention is shown; Figure 5 is an X-ray diffraction pattern showing a mixed powder which is not acid-treated; and Figure 6 is a mixture showing an acid-free treatment. X-ray diffraction pattern of powder. 16