201202395 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種固溶有銪（Eu)之点型 物之製造方法。 【先前技術】 組合有發出一次光的發光元件與吸收一 二次光的螢光體的發光裝置係作為可望達到 小型化、高輝度及廣泛色彩再現性的次世代 受嗎目’其研發正積極進行中。 例如’組合發出藍色至紫色的的短波長 導體發光元件與螢光體，並藉由半導體發光 的光與由螢光體轉換波長所得的光的混色來 的白色發光二極體（以下稱為白色LED)業 伴隨著白色LED的高輸出，對螢光體的 久性的要求亦增高。於此情況下，便矚目於 上升發光強度降低、結晶構造穩定之固溶有 矽鋁氮氧化物為代表的氮化物或氮氧化物螢 已知固溶有Eu2 +之召型矽鋁氮氧化物可 耳比混合氮化矽（SiJ4 );氮化鋁（A1N ) (Ειΐ2〇3 )寺光學活性元素化合物在moo 度進行燒成並粉碎所得之燒成物而獲得，其 之燒成粉體實施酸處理來製造（專利文獻1〕 又’已知以專利文獻1所述之方法製 Eu2 +之召型矽鋁氮氧化物其發光強度較低， 體的輝度而對粉體實施熱處理（專利文獻2 石夕紹氮氧化 次光並發出 低耗電化、 發光裝置而 可見光的半 元件所發出 獲得白色光 已實用化。 耐熱性、耐 以隨著溫度 Eu2 +之召型 光體。 由以既定莫 ;及氧化銪 °C附近的溫 後再對所得 I 〇 得的固溶有 為提高鸯光 • 4 - 201202395 先前技術文獻 專利文獻 專利文獻1 日本特開2005-255895號 專利文獻2 日本特開2005-255885號 專利文獻3 W02008/062781號 【發明内容】 [發明所欲解決之課題] 惟，專利文獻i及2的方法中，為製得高輝度< * 溶有Eu2 +之/3型矽鋁氮氧化物，則必需粉碎以燒$戶， 的凝聚體後進行熱處理，而有生產效率及作業性劣斤付 問題。 、化的 [用以解決課題之方式] 本發明為一種固溶有EU2 +之泠型矽鋁氮氧化物之製 造方法，其為一種以通式Si6-zAlz〇zN8 z ( 〇<z<4 2)表示 的β型矽鋁氮氧化物中固溶有Eu2 +之沒型矽鋁氮氧化物 之製造方法，其具有第一加熱步驟、第二加熱步驟及第 二加熱步驟後的酸處理步驟，且在同一加熱爐中進行第 一加熱步驟與第二加熱步驟，其中第一加熱步驟係對含 有Si、Al、Eu的原料混合粉末在氮氣環境中進行燒成； 第二加熱步驟則是對所得之燒成物在稀有氣體環境中或 真空中實施熱處理。 [發明之效果] 本發明之方法係在同一加熱爐中進行兩次加熱處 理，而不需在中途由加熱爐中取出燒成物，故作業效率 佳。又，可以不需將燒成後的加熱爐内溫度冷卻至室溫 -5- 201202395 附近而在同-加熱爐中連續實施第二 此可大幅縮短加埶處理所+ -人的加熱處理’因 …〜理所t的時間。 。 所得之螢光體的特性^ 又且’也不會損及 【實施方式】 [用以實施發明之形態] 以下對用以實施本發明之方式詳細 本發明固溶有Eu2 + ”型矽 丁說月 EU固溶…夕叙氮氧化物 =化物（以下稱為 第-加熱㈣1二加熱二方，的特徵為：具有 ^ ^ W ^ 驟及第—加熱步驟後對燒成 物貫把鲅處理的步驟，日户 〇 且在同—加熱爐中進行第一加埶 步驟與第二加熱步驟，发 /、Τ第一加熱步驟係對含有Si、201202395 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a spot type solid solution of Eu (Eu). [Prior Art] A light-emitting device in which a light-emitting element that emits primary light and a phosphor that absorbs primary light are combined is used as a next-generation generation that is expected to achieve miniaturization, high luminance, and wide color reproducibility. Actively in progress. For example, a combination of a short-wavelength light-emitting element that emits blue to purple light and a phosphor, and a white light-emitting diode that combines light of a semiconductor light and a light obtained by converting a wavelength of a phosphor (hereinafter referred to as The white LED industry is accompanied by the high output of white LEDs, and the demand for the longness of the phosphor is also increased. In this case, it is known that the nitride or oxynitride represented by the solid solution of lanthanum oxynitride is a solid solution in which the ascending luminescence intensity is lowered and the crystal structure is stable, and Eu2 + is called yttrium aluminum oxynitride. The erbium-doped mixed tantalum nitride (SiJ4); the aluminum nitride (A1N) (Ειΐ2〇3) temple optically active element compound is obtained by firing and pulverizing the obtained calcined product at moo degree, and the calcined powder is obtained. Manufactured by acid treatment (Patent Document 1) Further, it is known that the method of the method described in Patent Document 1 is used to produce Eu2 + - called yttrium aluminum oxynitride having a low luminous intensity and a heat treatment of the powder (Patent Document) 2 Shi Xishao oxidizes the secondary light and emits a low-power, light-emitting device, and the visible light is emitted from the half-element of the visible light. The heat resistance and the resistance to the light of the Eu2+ are set. Moss; and the temperature in the vicinity of the cerium oxide °C and then the solid solution of the obtained I 有 鸯 • • • • • • • • • • • • 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 2005-255885 Document 3 W02008/062781 [Summary of the Invention] [Problems to be Solved by the Invention] However, in the methods of Patent Documents i and 2, in order to obtain high luminance < * Eu 2 + /3 type lanthanum aluminum oxynitride In addition, it is necessary to pulverize and burn the aggregates, and then heat-treat, and there is a problem of production efficiency and workmanship. The method of solving the problem is as follows: The present invention is a solid solution of EU2 + A method for producing a ruthenium aluminum oxynitride, which is a type of ruthenium-doped ruthenium oxynitride represented by the general formula Si6-zAlz〇zN8 z (〇<z< a method for producing aluminum oxynitride, comprising: a first heating step, a second heating step, and an acid treatment step after the second heating step, and performing a first heating step and a second heating step in the same heating furnace, wherein the first The heating step is performed by baking a raw material mixed powder containing Si, Al, and Eu in a nitrogen atmosphere; and the second heating step is performing heat treatment on the obtained fired product in a rare gas atmosphere or in a vacuum. [Effect of the Invention] The method of the invention is carried out in the same furnace The secondary heat treatment does not need to take out the burned material in the heating furnace in the middle, so the work efficiency is good. Moreover, the temperature in the heating furnace after the firing can be cooled to room temperature -5 - 201202395 and the same - Continuously implementing the second in the heating furnace can greatly shorten the heating treatment of the +-man's heat treatment. The time of the obtained fluorescent material ^ and the 'will not be damaged' MODE FOR CARRYING OUT THE INVENTION The following is a detailed description of the mode for carrying out the present invention. The present invention is solid-solved with Eu2 + "type 矽 说 说 EU EU EU EU EU EU EU EU EU EU EU EU EU EU EU EU EU EU EU EU EU EU EU The heating (4) and the heating of the two sides are characterized by: a step of treating the fired material after the first heating step, and a first twisting step in the same heating furnace. And the second heating step, the first heating step of the hair/, Τ is containing Si,
Al、Eu的原料混合粉末在 不任H亂％扰中進行燒成；第二加 熱步驟則是對所得之煻成 "°成物在稀有氣體環境中或真空中 實施熱處理。 含有Si、八卜Eu的原料混合粉末係指混合有氧化石夕 及/或，化1呂；氮化發；氮化紹；及選自㈣金屬、氧化 物碳3文鹽、氮化物或氮氧化物之銪化合物的粉末。 含有si、AI的原料係以滿足通式Si6 zA1z〇zn8 z ( 〇 <ζ<4·2)的方式摻合。 為了以本發明製造沒型矽鋁氮氧化物，係對原料混 合粉末在氮氣環境下、182(rc以上22〇〇<t以下，較佳為 18 50°C以上205CTC以下的溫度範圍進行加熱燒成（以下 稱為第一加熱步驟）。加熱溫度若為1 820T：以上，Eu2 + 便可嵌入/?型矽鋁氮氧化物結晶中。溫度若為2〇5〇t以 下’則不需施加高氮氣麼力來抑制Eu固溶型石夕紹氮氧 -6 - 201202395 化物的分解，亦無需有特殊之裝置故特佳。庐 — 氣環境的壓力條件較佳為〇 5MPa 的氮 UMPa以下。Λ .、'、時間一般為1 〇小時〜2 〇小時。 σ 此外，亦可使用含有Si的金屬粉末來取代氮化 此時，需對含有si的金屬粉末在第一加熱步驟前實2 。 化處理《含有Si的金屬粉末的氮化反應係於14㈧它以Γ 16〇〇°C以下的溫度下進行，故在第一加熱步驟前對 心的金屬粉末在氮氣環境下，上述溫度範圍進行加埶 將Si轉換為si3N〆 …、 以往為改善螢光體的發光強度，係在第一加熱步驟 後進行·所得之燒成物的冷卻、燒成物的粉碎、粉碎物 在真空中或氮氣以外之氣體環境中的加熱。對此，本發 明方法中並未進行燒成物冷卻、由加熱爐取出、粉碎的 各種作業，而是由第一加熱步驟起連續對燒成物在真空 中或氮氣以外之氣體環境中進一步進行加熱。 對燒成物在真空中或氮氣以外之氣體環境中進行加 熱的步驟（以下稱為第二加熱步驟）為用以使殘存於燒 成物中之低結晶性部分更加不穩定的處理。 此外’因第二加熱步驟處理而不穩定化的低結晶部 分係由後述酸處理或鹼溶液處理而去除。 為使低結晶性部分不穩定化，係以在儘量未含作為 構成低結晶性部分之元素的氮與氧的氣體環境中對燒成 物實施加熱處理為佳。因此，於第二加熱步驟前需預先 由加熱爐内除去氮及氧等氣體成分。為此，而於第一加 熱步驟結束後由加熱爐内排出氣體成分，並使加熱爐内 201202395 的氣體環境降至大氣壓附近之後，以真空泵等將加熱 内減壓（以下稱為排氣步驟）。減壓條件只要是5pa以 lOOPa以下的真空度即可。 在氮氣以外的氣體環境中進行第二加熱步驟時， 於排氣步驟後，對加熱爐内填充稀有氣體（以下稱為 有氣體導入步驟）。稀有氣體為選自氦、氖、氬、氪、岛 乳的鈍氣，較佳為氬。 排氣步驟及/或稀有氣體導入步驟中，係將爐内溫 、准持於500 C以上1 250度以下之範圍。於此溫度範圍 由於會對第二加熱步驟的作業性造成影響而不佳。 第二加熱步驟中，燒成物係於真空中丨2 〇 〇以 155〇C以下之溫度範圍或於稀有氣體環境中13〇〇。〇以 155〇C以下之溫度範圍加熱。加熱溫度若為155〇它 下則可抑制Eu固溶万型；ε夕铭氮氧化物的分解。 第一加熱步驟後將燒成物粉碎，並使所得之粉懸 =黾或鹼溶液中來進行處理。藉此處理，不穩定化之 为便由結晶中溶解、除去。酸特佳使用氫氟酸與硝酸 現酸溶液。 如以上所述，採用本發明方法可在同一加熱爐中 進仃原料粉末的第一加熱步驟與第二加熱步驟。 此，便可在未降低Eu固溶万型矽鋁氮氧化物的發光強 的情況下縮短製造時間。 實施例1 ^以V型混合機（筒井理化學器械公司製s — 3 )混 S所7^之含有Si、Ab EU的化合物，再使其全部通 k 250 y m的篩網以除去凝集，即製得原料混合粉本 爐 上 係 稀 度 外 上 上 以 浮 部 的 連 由 度 合 過 201202395 [混合原料的成分] • «型氮化矽粉末（宇部興產公司製SN — E 1 〇等級， 含氧量1.2質量。/。）95.64質量％ ; •氮化I呂（T OKU YAM Α公司製F級’含氧量0.8質 量 ％) 3.35 質量。/。； •氧化紹粉末（住友化學公司製AKP — 3 0等級）〇. 1 8 質量％ •，及 •氧化銪粉末（信越化學工業公司製RU等級）〇, 8 4 質量％ » 此外’該摻合比為在除氧化銪以外的原料中，將氮 化矽粉末與氮化鋁粉末的雜質氧分別假設為二氧化矽及 氧化紹時’可計算成万型矽鋁氮氧化物通式The raw material mixed powder of Al and Eu is fired in the absence of H. The second heating step is to heat-treat the obtained composition into a rare gas atmosphere or in a vacuum. The raw material mixed powder containing Si and Babu Eu refers to a mixture of oxidized stone and/or lanthanum; nitriding; nitriding; and (4) metal, oxide carbon 3 salt, nitride or nitrogen A powder of an antimony compound. The raw materials containing si and AI were blended in such a manner as to satisfy the general formula Si6 zA1z〇zn8 z (〇 <ζ<4·2). In order to produce the ruthenium-free aluminum oxynitride according to the present invention, the raw material mixed powder is heated in a nitrogen atmosphere at a temperature range of 182 (rc or more, 22 Å < t or less, preferably 18 50 ° C or more and 205 CTC or less). Firing (hereinafter referred to as the first heating step). If the heating temperature is 1 820 T: or more, Eu 2 + can be embedded in the ?? type aluminum oxynitride crystal. If the temperature is 2 〇 5 〇 or less ' The high nitrogen pressure is applied to suppress the decomposition of the Eu solid solution type Shi Xishao nitrogen oxide-6 - 201202395, and it is not necessary to have a special device. The pressure condition of the gas environment is preferably 〇5MPa nitrogen UMPa or less. Λ ., ', the time is generally 1 〜 hours ~ 2 〇 hours. σ In addition, metal powder containing Si can also be used instead of nitriding. At this time, the metal powder containing si needs to be before the first heating step. The nitridation reaction of the metal powder containing Si is carried out at 14 (eight), which is carried out at a temperature below 〇〇 16 ° C, so that the metal powder of the core before the first heating step is in a nitrogen atmosphere, the above temperature range Perform twisting to convert Si to si3N〆... In order to improve the luminous intensity of the phosphor, the obtained calcined product is cooled, the calcined product is pulverized, and the pulverized material is heated in a vacuum or a gas atmosphere other than nitrogen after the first heating step. In the method of the present invention, various operations such as cooling of the fired product, taking out and pulverizing the heating furnace are not performed, and the fired product is continuously heated in a vacuum or a gas atmosphere other than nitrogen from the first heating step. The step of heating the burned material in a vacuum or a gas atmosphere other than nitrogen (hereinafter referred to as a second heating step) is a treatment for making the low crystalline portion remaining in the fired material more unstable. The low-crystalline portion which is destabilized by the second heating step is removed by an acid treatment or an alkali solution treatment to be described later. In order to destabilize the low crystallinity portion, it is contained as an element which does not contain a low crystallinity portion as much as possible. It is preferable to heat-treat the fired material in a gas atmosphere of nitrogen and oxygen. Therefore, it is necessary to remove a gas component such as nitrogen and oxygen from the heating furnace before the second heating step. After the first heating step is completed, the gas component is discharged from the heating furnace, and the gas atmosphere of the 201202395 in the heating furnace is lowered to the vicinity of the atmospheric pressure, and then the internal pressure is reduced by a vacuum pump or the like (hereinafter referred to as an exhausting step). The pressure condition may be 5 Pa or less and a vacuum of 100 Pa or less. When the second heating step is performed in a gas atmosphere other than nitrogen, the furnace is filled with a rare gas (hereinafter referred to as a gas introduction step) after the exhaust step. The rare gas is an inert gas selected from the group consisting of ruthenium, osmium, argon, krypton and island milk, preferably argon. In the venting step and/or the introduction step of the rare gas, the temperature inside the furnace is maintained at 500 C or more. A range of 250 degrees or less. This temperature range is not preferable because it affects the workability of the second heating step. In the second heating step, the fired material is in a vacuum of 丨2 〇 〇 in a temperature range of 155 〇C or less or 13 于 in a rare gas atmosphere. 〇 Heat in a temperature range of 155 ° C or less. If the heating temperature is 155 〇, it can suppress the Eu-solid solution; After the first heating step, the fired product is pulverized, and the obtained powder is suspended in a hydrazine or an alkali solution for treatment. By this treatment, the destabilization is dissolved and removed from the crystal. The acid is preferably used as a solution of hydrofluoric acid and nitric acid. As described above, the first heating step and the second heating step of the raw material powder can be introduced into the same heating furnace by the method of the present invention. Therefore, the manufacturing time can be shortened without lowering the luminous intensity of the Eu-solid lanthanum aluminum oxynitride. Example 1 ^ A compound containing Si and Ab EU was mixed with a V-type mixer (manufactured by Tsutsui Kogyo Chemical Co., Ltd.), and all of them were passed through a screen of k 250 μm to remove agglomeration, that is, The raw material mixture powder is prepared on the furnace and the upper part of the furnace is connected with the floating part. 201202395 [Ingredients of mixed raw materials] • «Type tantalum nitride powder (SN-E 1 〇 grade by Ube Industries Co., Ltd., including The amount of oxygen is 1.2 mass%. 95.64% by mass; • Nitrile I (T-state U-made by T OKU YAM Co., Ltd. 'Oxygen content 0.8% by mass) 3.35 Mass. /. • Oxidized powder (AKP - 30 grade) manufactured by Sumitomo Chemical Co., Ltd. 1. 1 8 mass% •, and • yttrium oxide powder (RU grade by Shin-Etsu Chemical Co., Ltd.) 〇, 8 4% by mass » In addition In the raw materials other than cerium oxide, the impurity oxygen of the tantalum nitride powder and the aluminum nitride powder is assumed to be cerium oxide and oxidized, respectively.
Si6 —ζΑ1ζ〇ζΝ8·ζ ( z= 0.24)者。 將原料混合粉末填充於附有蓋之圓筒型氮化硼製容 器（電氣化學工業公司製N— 1等級）中，對圓筒型氮化 硼製谷器以石墨電阻加熱式電爐（有效尺寸3〇〇χ3〇〇χ 60 0mm )進行加熱。此外，電爐中配設有油旋轉真空泵' 及將氮氣或稀有氣體導入電爐内的氣體管線（gas Une )。 加熱處理係首先以油旋轉真空泵與機械升壓器 (mechanical booster)使燒成氣體環境成為真空，室溫 起至1000C以母分鐘l(Tc的速度加熱，在1〇〇它下導入 氮氣並使氣體壓力為O.SMPa，在氣壓一定之丁以每分鐘 10°C昇溫至2000。(：，並保持於2000。(：下1〇小時。 加熱處理後’以每分鐘10t將加熱爐内溫度冷卻至 1200°C。在將加熱爐内溫度保持於12〇(rc的狀態下由爐 201202395 内排出氮氣’當爐内氣體環境壓力降低至大氣壓附近 後’以油旋轉真空泵排出氣體成分至爐内的真空度成為 10Pa’接著導入氬氣以使爐内的氣體壓力為大氣壓。 以每分鐘10°c升溫至l5〇OeC，並於l5〇(TC下保持6 小時。其後’以每分鐘丨0 t將加熱爐内溫度冷卻至i 2〇〇 C ’並將燒成物以爐内冷卻（furnace cooling)由1200 C以下起冷卻至室溫附近。以氧化鋁研鉢及杵將所得的 深、綠色塊狀合成物粗粉碎至可全部通過孔徑1 5 〇 “ m的 筛網’進一步使其通過孔徑45 V m的篩網來去除45 V m 以上的粒子。 在10%氫氟酸與15%硝酸的混酸液中、75〇c下對所 得之粉末實施加熱處理，冷卻後除去上澄液，進一步重 複進行添加蒸館水、攪拌、除去上澄液的傾析至懸浮液 的pH呈中性。其後，將懸浮液過濾、乾燥即製得實施例 的螢光體粉末》 [比較例] 對與實施例1同樣的原料混合粉末在與實施例1相 同的條件下進行第一加熱步驟的加熱處理。 其後，以每分鐘1(TC將加熱爐内溫度冷卻至1200 C ’再將燒成物以爐内冷卻由丨2〇〇。(：以下起冷卻至室溫 附近。冷卻至1 2 0 〇 以下則需約6小時。所得之合成物 為綠色的塊狀物。使用氧化鋁研缽及杵，將其粗粉碎至 可全部通過孔徑1 50 " m的筛網，進一步使其通過孔徑 45βηι的師網來去除45ym以上的粒子。 -10- 201202395 將所得之粉末再次填充於附有蓋之圓筒型氮化硼製 容器中，並使用與第一次加熱處理相同的電爐來進行第 二次的加熱處理。採用與第一次加熱處理相同的方法在 真空中加熱至l〇〇〇°C，於1000°C下導入氬氣以使氣體壓 力為大氣壓，再以每分鐘10°c升溫至1500°c，並於1500 °C下保持6小時。其後，以每分鐘10 °C將加熱爐内溫度 冷卻至1200。(：，並將燒成物以爐内冷卻由1200°c以下起 冷卻至室溫附近。所得之粉末雖變為深綠色，但未發生 固化而保持粉末狀。 使進行二次加熱處理後的粉末懸浮於1 〇 %氫默酸與 1 5 % >6肖酸的混酸中，並於7 5 °C實施加熱處理，冷卻後除 去上澄液。進一步重複進行添加蒸餾水、搜拌、除去上 澄液的傾析操作至懸浮液的pH呈中性。其後，將懸浮液 過濾、乾燥。 對實施例及比較例中所得之Eu固溶；5型石夕铭氮氧 化物的螢光特性，使用螢光分光光度計（Hitachi High-Technol〇gies公司製F — 7000 )測定其激發波長 450nm下的螢光光譜。此外’發光強度係以將yAg : Ce (KASEI OPTONIX公司製P46Y3 )的發光強度定為1〇〇% 的相對峰值強度（％)來表示。 將原料粉置入加熱爐之後到第二次加熱處理結束後 由加熱爐回收加熱處理品為止的時間（稱之為加熱處理 夺門）以及各個所得之勞光體的螢光強度與螢光峰值波 長係示於表1。 201202395 表1 加熱處理時間 螢光強度 螢光峰值波長 實施例 29小時40分 201% 542.5nm 比較例 44小時20分 200% 542.1nm 已知藉由連續進行加熱處理可縮短約3 5 %的加熱處 理時間，並可獲得具有與習知方法所得者相同之特性的 Eu固溶/3型石夕I呂氮氧化物。 【圖式簡單說明】 ί» 〇Si6 —ζΑ1ζ〇ζΝ8·ζ ( z= 0.24). The raw material mixed powder is filled in a cylindrical boron nitride container (N-1 grade manufactured by Electric Chemical Industry Co., Ltd.) with a lid, and a graphite resistance heating electric furnace is used for the cylindrical boron nitride grainer (effective size 3) 〇〇χ3〇〇χ 60 0mm) for heating. In addition, an electric rotary vacuum pump is provided in the electric furnace and a gas line (gas Une) for introducing nitrogen or a rare gas into the electric furnace. In the heat treatment, the firing gas atmosphere is first vacuumed by an oil rotary vacuum pump and a mechanical booster, and heated at room temperature to 1000 C at a rate of 1 minute (Tc), and nitrogen gas is introduced under 1 Torr. The gas pressure is O.SMPa, and the temperature is raised at a constant pressure of 10 ° C per minute to 2000. (:, and maintained at 2000. (: 1 hour after the heating. After heating treatment, the furnace temperature is 10t per minute) Cool to 1200 ° C. After the temperature in the furnace is maintained at 12 〇 (the state of the furnace is discharged from the furnace 201202395 in the state of rc), when the gas pressure in the furnace is lowered to near atmospheric pressure, the gas component is discharged from the vacuum pump to the furnace. The degree of vacuum became 10 Pa' and then argon gas was introduced to bring the gas pressure in the furnace to atmospheric pressure. The temperature was raised to 10 〇 OeC at 10 ° C per minute and maintained at 15 ° C for 6 hours. 0 t The temperature in the heating furnace is cooled to i 2〇〇C ' and the fired product is cooled to below room temperature by cooling in the furnace from 1200 C or less. The depth of the alumina is obtained by mortar and pestle. , green block composite coarsely pulverized to The part is further passed through a screen with a pore size of 15 〇 "m" to remove particles above 45 V m through a sieve with a pore size of 45 V m. In a mixed acid solution of 10% hydrofluoric acid and 15% nitric acid, 75 〇c The obtained powder is subjected to heat treatment, and after cooling, the supernatant liquid is removed, and the pH of the suspension is further repeated by adding the steaming water, stirring, and removing the supernatant liquid until the pH of the suspension is neutral. Thereafter, the suspension is filtered. The phosphor powder of the example was prepared by drying. [Comparative Example] The same raw material mixed powder as in Example 1 was subjected to heat treatment in the first heating step under the same conditions as in Example 1. Thereafter, per minute 1 (TC cools the temperature in the heating furnace to 1200 C' and then cools the burned material in the furnace by 丨2〇〇. (: Cooling to near room temperature below. It takes about 6 hours to cool below 1 2 〇. The obtained composition is a green mass. The alumina mortar and pestle are used, and coarsely pulverized to a sieve which can pass through the pore diameter of 1 50 " m, and further passed through the mesh of the pore size 45βηι to remove 45 μm. Above the particles. -10- 201202395 will get the powder again Filled in a cylindrical boron nitride container with a lid, and subjected to a second heat treatment using the same electric furnace as the first heat treatment. Heating in a vacuum in the same manner as the first heat treatment l 〇〇〇 ° C, argon gas was introduced at 1000 ° C to make the gas pressure to atmospheric pressure, and then heated to 1500 ° C at 10 ° C per minute, and maintained at 1500 ° C for 6 hours. Thereafter, each The temperature in the heating furnace was cooled to 1200 at 10 ° C in minutes (:, and the fired product was cooled in the furnace from 1200 ° C or less to near room temperature. Although the obtained powder turned dark green, it did not solidify and remained in a powder form. The powder subjected to the secondary heat treatment was suspended in a mixed acid of 1 〇 % of hydrogen peroxide and 15 % of > 6 octanoic acid, and heat-treated at 75 ° C. After cooling, the supernatant was removed. The decantation operation of adding distilled water, mixing, and removing the supernatant was further repeated until the pH of the suspension was neutral. Thereafter, the suspension was filtered and dried. For the Eu-solid solution obtained in the examples and the comparative examples, the fluorescence characteristics of the type 5 Shi Ximing oxynitride were measured using a fluorescence spectrophotometer (F-7000, manufactured by Hitachi High-Technol Co., Ltd.) to determine the excitation wavelength of 450 nm. Under the fluorescent spectrum. Further, the luminescence intensity is represented by a relative peak intensity (%) in which the luminescence intensity of yAg: Ce (P46Y3 manufactured by KASEI OPTONIX Co., Ltd.) is set to 1% by weight. The time until the heat-treated product is recovered by the heating furnace after the raw material powder is placed in the heating furnace and after the second heat treatment is completed (referred to as heat treatment), and the fluorescence intensity and fluorescence peak of each of the obtained labor bodies The wavelengths are shown in Table 1. 201202395 Table 1 Heat treatment time Fluorescence intensity Fluorescence peak wavelength Example 29 hours 40 minutes 201% 542.5 nm Comparative example 44 hours 20 minutes 200% 542.1 nm It is known that heat treatment can be shortened by about 35 % by continuous heat treatment Time, and Eu-solution/type 3 Shixi Ilu oxynitride having the same characteristics as those obtained by the conventional method can be obtained. [Simple diagram] ί» 〇
»、、N 【主要元件符號說明】 無。 -12-»,,N [Description of main component symbols] None. -12-