200835775 九、發明說明： 【發明所屬之技術領域】 本發明係關於在無機螢光體之製造上有用之II-VI族化 合物半導體粒子之製法；尤其關於控制由II-VI族化合物半 導體之一次粒子所形成之凝集體（二次粒子）之粒徑分布， 而製造粒徑均齊之螢光體先質粒子之方法，以及藉由該方 法所得到之螢光體先質粒子。 【先前技術】 II-VI族化合物半導體，例如以硫化鋅等爲主成分之化 合物半導體，若在其結晶構造中摻雜錳、銅、銀、铽、錶、 銪、氟等賦活元素後，再施行熱處理等，則可藉由光、電 子等之照射或電壓之外加而呈現發光現象。因此，上述化 合物半導體可做爲螢光體之母體材料，尤其以硫化鋅等爲 主成分之化合物半導體之粒狀物，可做爲用於製造電漿顯 示器、電致發光顯示器、電場放射型顯示器等顯示裝置所 用之螢光體之先質。 其中，「先質」之術語意指爲摻雜賦活劑之化合物半導 體，且係在施行熱處理等之前之階段者。亦即，摻雜賦活 劑之化合物半導體，由於藉由施行熱處理等才開始呈現做 爲螢光體之性質，因此爲螢光體前身之先質與螢光體本身 呈現嚴密的區別。 合成以硫化鋅做爲母體之螢光體先質之方法，有利用固 相反應之方法及利用液相中之反應之方法。 關於前者固相合成法，可使用將原料之硫化鋅粒子與稱 爲FLUX之無機鹽共同在800 °C〜1300 °C之非常高溫度下進 200835775 行第一次燒成，使微米大小之粒子成長，繼而在500〜1000 °C進行第二次燒成，得到螢光體粒子之方法（參照專利文獻 1〜3) °該方法中，由於在高溫下進行燒成，在固相反應進 行時難以將新成分添加於反應系統，因此，例如難以將賦 活劑或共賦活劑以在粒子內呈均質化濃度分布之方式摻雜 於粒子內部。因此，就固相合成法而言，在「藉由將賦活 劑摻雜於硫化鋅母體中以得到更高亮度之螢光體」上有所 限制。 ® 另一方面，藉由後者之液相合成法合成π-νι族螢光體 先質時，由於可在粒子之成長過程中一邊添加賦活劑或共 賦活劑一邊控制其量，因此與固相合成法不同，可使所製 得的螢光體粒子內部之賦活劑或共賦活劑之濃度分布均質 化。又，螢光體粒子雖係經由核形成及粒子成長二個過程 而形成，然而藉由控制該粒子成長中之過飽和度，可得到 粒徑分布狹窄且呈單分散之粒子生成物。 關於在液相中II-VI族螢光體先質之合成，揭示在水熱 • 條件下合成粒子之方法（例如，參照專利文獻4)，或粒徑分 布之控制方法（例如，參照專利文獻5)。 另一方面，揭示將螢光體之母體與含有賦活劑或共賦活 劑之構成元素之各原料成分溶液混合，使螢光體母體結 晶、賦活劑或共賦活劑共析出，製造螢光體之方法（參照專 利文獻6)。再者，II-VI族化合物半導體之製法方法，揭示 使含II族元素之化合物與如硫代乙醯胺之含VI族元素之 醯胺化合物在水熱條件下反應之方法（參照專利文獻7及非 專利文獻1)。 200835775 [專利文獻1]曰本特開平8_ 1 83954號公報 [專利文獻2]日本特開平7-62342號公報 [專利文獻3]日本特開平6-330035號公報 [專利文獻4]日本特開2005-306713號公報 [專利文獻5]曰本特開2005- 1 39372號公報 [專利文獻6]曰本特開2005_ 1 32947號公報 [專利文獻7]日本特表2004-520260號公報 [非專利文獻 1] J. Chem. Soc· Faraday Trans., ® 5 6 3 -570 ( 1 9 8 4) 【發明內容】 發明欲解決之課題 藉由專利文獻4〜7等所揭示之方法得到之螢光體 爲平均粒徑係約數奈米之微細一次粒子。該一次粒 凝集，可形成粒徑數百微米之二次粒子，另一方面 亦存在著粒徑達到約數奈米〜數十奈米之微小粒子， 廣粒徑分布之粒子生成物。粒徑參差不齊大之粒 ® 物，由於各粒子形狀亦不規則，沉降速度產生大差 粒子之回收及洗淨等必須有複雜之步驟，並且需要 之時間等，有操作不便之問題。因此，期望開發調 分布狹窄且呈單分散之螢光體先質粒子之方法。 解決課題用之手段 本發明人等專心硏究之結果，發現若在添加由特 鹽構成之電解質化合物之水性液相中，使含有II族 VI族元素之原料化合物彼此反應，生成II-VI族化 導體之一次粒子，則該一次粒子再凝集，形成粒徑 1 (80) 粒子， 子互相 ，由於 產生寬 子生成 異，在 非常長 製粒徑 定金屬 元素及 合物半 均齊之 200835775 二次粒子，因此完成本發明。 亦即，本發明係提供一種II-VI族螢光體先質之製法， 其特徵爲在包括由典型金屬之無機酸鹽或有機酸鹽所構成 之電解質化合物及含II族元素化合物之水性液相中，添加 含VI族元素之醯胺化合物，以生成II-VI族化合物半導體 之粒子。 藉由本發明所得到之II-VI族化合物半導體之粒子，不 限於藉由添加含VI族元素之醯胺化合物後立即與含II族 • 元素化合物反應所生成之一次粒子，並且包括該一次粒子 進一步於液相中凝集所生成之二次粒子（凝集體）。因此， 本發明之其他態樣爲一種凝集體，爲II-VI族化合物半導體 之凝集體，其特徵爲以所表示之平均粒徑爲8〜30 μ m 且標準偏差爲0.01〜0.2。 [發明之效果] 若依照本發明之方法，可得到粒度分布被控制成單分散 之II-VI族化合物半導體粒子。因此，若使用依照本發明所 • 得到之螢光體先質粒子，可期望顯著地改善粒子之洗淨、 回收操作等步驟之效率，並達成螢光體之製造流程全體之 效率化。 【實施方式】 本申請書所使用之「II-VI族化合物半導體」之術語， 爲由II族元素（Be、Mg、Zn、Cd、Hg)及VI族元素（〇、s、 Se、Te)所構成之二元化合物半導體及其混晶半導體之總 稱。本發明所使用之II-VI族化合物半導體之實例，可爲硫 化鋅、硒化鋅、硫化鎘、硒化鎘等，此等亦可如下述，被 200835775 秦 成爲發光中心之各種金屬、非金屬離子（賦活劑或共賦活劑） 取代一部分。 本發明中所使甩之含II族元素之化合物，並無特別限 定，可使用氯化鋅、硝酸鋅、硫酸鋅、氯化鎘、硝酸鎘、 硫酸鎘等無機酸鹽；乙酸鋅、丙酸鋅、草酸鋅、乙酸鎘、 丙酸鎘、草酸鎘等有機酸鹽。此等化合物可單獨使用，亦 可將複數種混合使用。本化合物雖可以任何濃度使用，然 而若濃度過高，II-VI族化合物半導體之生成速度變快，.如 ® 賦活劑之其他離子無法均勻地導入，另一方面，若濃度過 低’由於粒子成長速度慢，不只容積效率降低，且電解質 之效果變得稀薄，粒度分布之控制變得困難，因此不佳。 慮及此等點，在本發明中含II族元素之化合物以〇. 〇 1莫耳 /公升〜5莫耳/公升之濃度使用，較佳以0.1莫耳/公升〜2莫 耳/公升之濃度使用。 本發明所使用之含VI族元素之醯胺化合物，可使用硫 代甲醯胺、硫代乙醯胺、硫代丙醯胺等硫醯胺類。此等可 ® 單獨使用，亦可將複數種混合使用，然而從經濟性、取得 容易性之觀點而言，以使用硫代乙醯胺爲較佳。關於硫醯 胺類之使用量，考慮反應效率、容積效率，相對於含II族 元素之化合物之莫耳數，使用1.0〜100倍（較佳爲 1.7〜30 倍，更佳爲1.9〜5倍）莫耳數之量。 本發明中所使用之液相溶劑，雖然典型地爲水，然而在 未使下述之添加劑（電解質）之溶解性明顯降低之範圍內， 可進一步含有極性有機化合物（例如甲醇、乙醇等醇類）。 本發明中，除含II族元素之化合物及含VI族元素之醯 200835775 月女外’藉由添加含有可在水性液相中成爲發光中心之賦活 劑或共賦活劑元素之化合物，可將該元素之離子摻雜於所 生成之母材結晶中。可使用做爲發光中心之元素，可擧出 錳、銅、銀、金、銥等過渡金屬；氯、碘、溴等鹵素；鈽、 銥、鐯、銨、釤、銪、釓、铽、鏑、鈥、餌、錶、鏡等稀 土類。又，視需要’對於做爲受體之過渡金屬、稀土類而 言，可擧出使用做爲施體之鋁、鎵、銦及氟、氯、溴、碘 等鹵素等。此等元素可藉由使用氯化物、溴化物、碘化物 ^ 等鹵化物；甲酸、乙酸、丙酸等有機酸鹽；乙醯基丙酮酸 鹽等錯鹽等而導入。此等化合物可單獨使用，亦可將複數 種混合而使用。再者，可使其與吡啶、膦等配位性化合物 共存。上述化合物之使用量，通常相對於生成之II-VI族化 合物半導體10 0重量份而言，導入之離子在0.0001重量份 〜20重量份之範圍，然而考慮取代之達成效果及經濟性， 以0.0 0 02重量份〜1Q重量份之範圍爲較佳。 本發明中藉由上述含II族或VI族元素之化合物之反 Φ 應，生成II-VI族螢光體之粒子。該螢光體粒子之一次粒子 雖爲數nm至3Onm粒徑之微細粒子’然而在溶解有電解質 化合物之水性液相中再度凝集’形成適當大小之二次粒 子。藉由本發明所得到之二次粒子之粒徑分布狹窄且呈現 單分散性。得到之凝集體之平均粒徑通常未達3 Ο μ m且標 準偏差未達0.2。以凝集體之平均粒徑爲8〜3〇 M m且標準偏 差爲0.01〜0.2爲較佳。 再者，其中使用之「粒徑」之術語，若非特別預先限定’ 意指藉由從粒度分布曲線求取中心粒徑D 5 °所得到之平均 -10 - 200835775 粒徑。 在本發明中，可使水性液相中生成之一次粒子進一步凝 集之添加劑（凝集劑），只要爲可溶解於水性液相中之電解 質化合物將無特別限定，不過以不會混入II-VI族螢光體先 質者爲較佳。此係由於電解質溶解於液相時所生成之離子 若混入螢光體先質，則做爲螢光體之性能將變差，亮度亦 將降低。從此種觀點而言，作爲使用於本發明之較佳添加 劑爲可擧出典型金屬之無機酸或有機酸鹽，而以鹼土糈金 ® 屬之無機酸鹽或有機酸鹽爲更佳。作爲典型金屬，可列舉 如鎂、鈣、鋇等金屬元素，特佳之金屬爲鎂及鈣。含此等 金屬之添加劑化合物，雖可使用氫氧化物；硫酸鹽；硝酸 鹽；氯化物、溴化物等鹵化物；甲酸、乙酸或丙酸等之有 機酸鹽，然而以使用氫氧化物或硫酸鹽爲特佳。本發明可 藉由將上述化合物以任何量與含II族元素之化合物一起預 先添加於液相中，再添加含VI族元素之醯胺化合物而實 施。添加劑化合物之添加量，相對於II-IV族化合物半導體 • 100重量份而言，通常在0.0001重量份〜20重量份之範圍， 然而從凝集效果及經濟性之觀點而言，以在0.0002重量份 〜1 0重量份之範圍爲較佳。又，從「控制生成之凝集體之 粒度分布，避免混入生成物中」之觀點而言，較佳之添加 量，以所用之含II族元素之化合物之莫耳量爲基準，在 0.5〜40莫耳％之範圍，而以0.8〜30莫耳％之範圍爲特佳。 本發明中可藉由批次式或連續式製造II-VI族螢光體先 質。又，液相之溫度只要在不損及反應之進行及粒子之凝 集效果之範圍內，將無特別限定，不過可隨液相中所含成 -11- 200835775 § 分之種類及量（濃度）而變動。通常，液相之溫度可調節成 爲20°C〜120°C之範圍。液相之溫度調節雖可從反應容器之 外部使用慣用之可控制溫度之加熱裝置而實施，然而亦可 設置在液相內能控制溫度之加熱裝置而實施。但是，反應 溫度低時，由於粒子之成長遲緩，反應需要長時間，每小 時之生產性變低，因此從經濟性之觀點而言不佳。又，從 操作性之觀點而言，若溫度過低則液體整體之黏度變高， 在相等流速下較難使反應液擴散，操作性降低；另一方面， β 若溫度過高，則蒸氣化氣體所造成之刺激變強，操作性變 差。考慮此等觀點，本發明之方法以在60 °C〜100 °C之範圍 實施爲較佳，而以在65 °C〜90°C之範圍實施爲更佳。 本發明之方法中，從開始至結束時，亦即從剛將各成份 添加於液相中前之時點至剛回收螢光體先質之粒子生成物 前之時點爲止，在其一部分或全部期間，可持續地或間歇 地以任何攪拌速度實施攪拌。 本發明之方法之實施所需要之時間，從事此業者可根據 ® 實施之規模、裝置等之條件，觀察反應進行之狀況及凝集 粒子生成之程度而適宜地選擇，然而通常可實施1〜20小時 反應，而以實施3〜1 0小時反應爲較佳。 [實施例] 以下舉出實施例更詳細地說明本發明，然而本發明並不 以本實施例爲限，不用說在不超脫本發明之技術思想之範 圍內’，當然可對實施例施加適宜修正及變更而實施。 在以下之實施例中，對於粒子生成物之粒度分布，係使 用島津製作所製之SALD-2100，藉由雷射折射散射法進行 -12- 200835775 m 測定，並使用附屬於該裝置之解析軟體SALD-2100，求取 中數直徑（median diameter)D5〇，並藉此評估分布之廣度。 又，SEM觀察係使用日立製作所製S4000，於加速電壓 爲5 kV之條件下實施。 實施例硫化鋅粒子之製造 (A)於電解質中使用硫酸鎂之情形 在裝有攪拌機、溫度計、冷凝器之容量500ml三口燒瓶 中，將硝酸鋅六水合物37.2g( 125毫莫耳）溶於水250ml中， ® 添加硝酸〇.5g，調整pH至2。於其中添加硫酸鎂0.75 2g(6.25 毫莫耳，相當於硝酸鋅之莫耳量之5莫耳％)，一邊攪拌一 邊升溫至70°C。將溶液升溫至70°C後，添加硫代乙醯胺 18.8 g(250毫莫耳）。將其以原樣攪拌2小時後，將氮氣以 200ml/分鐘導入燒瓶中，除去溶存之硫化氫。從得到之漿 液藉由離心分離而分離粒子生成物，用水洗淨，得到硫化 鋅11.8g (產率爲97%)。平均粒徑爲18.8//m。關於粒子生 成物所得到之粒徑分布曲線如第1圖所示，又，SEM觀察 •照片如第2圖所示。 (B)於電解質中使用硫酸鈣之情.形 除在上述（A)中添加硫酸鈣0.85g(6.25毫莫耳）以代替硫 酸鎂之外，以與上述（A)同樣之步驟，得到硫化鋅1 1.8 g (產 率97%)。平均粒徑爲18.0// m。 實施例2 除使實施例1 (A)中硫酸鎂之使用量成爲 3.0 g (； 2 5 _冑 耳，相當於硝酸鋅之莫耳量之20莫耳％)之外，以與實施例 1 (A)同樣之步驟，得到硫化鋅1 1 · 9 g (產率9 8 %)。平均粒徑 -13· 200835775 爲24·3从m。 竇施例3 . 除使實施例1(A)中之硫酸鎂之使用量成爲〇.3g(2.5毫莫 耳，相當於硝酸鋅之2莫耳％)之外，以與實施例1(A)同樣 之步驟，得到硫化鋅11.3 g (產率93%)。平均粒徑爲8.2// m。 實施例4 除使實施例1(A)中之硫酸鎂改爲氯化鎂六水合物2.54g (12.5毫莫耳，相當於硝酸鋅之莫耳量之10莫耳％)之外， • 以與實施例1(A)同樣之方式進行，得到硫化鋅10.9g(產率 89%)。平均粒徑爲18.8 // m。 實施例5 :錳摻雜硫化鋅粒子之製造 在裝有攪拌機、溫度計、冷凝器之容量500ml三口燒瓶 中，將硝酸鋅六水合物37.2g( 125毫莫耳）溶於水250ml中， 添加硝酸0.5g，調整pH至2。於該硝酸鋅水溶液中添加硫 酸錳0.0‘12g(0.125毫莫耳）及硫酸鎂0.7 5 2g(6.25毫莫耳，相 當於硝酸鋅之莫耳量之5莫耳％)，一邊攪拌一邊升溫至 • 7〇°C。確認溶液升溫至70°C後，以一次添加硫代乙醯胺 18.8g (250毫莫耳）。將其以原樣攪拌2小時後，將氮氣以 200ml/分鐘導入燒瓶，除去溶存之硫化氫。藉由離心分離 從得到之漿液分離出粒子生成物，用水洗淨，得到摻雜錳 之硫化鋅11.7g(產率爲96%)。平均粒徑爲17.6/zm。 實一細例_$·丨爹雜銅-錄之硫化辞粒子之製浩 在裝有攪拌機、溫度計、冷凝器之容量2公升之三口燒 瓶中’添加硝酸鋅六水合物223.2g(750毫莫耳）、硫酸鎂 4.5 g(37.5毫莫耳，相當於硝酸鋅之5莫耳％)、硫酸銅三水 -14- 200835775 合物1.39g(5.75毫莫耳）、硝酸鎵六水合物670mg(1.84毫莫 耳）及水75Qml並攪拌，添加硝酸1.5g’進一步一邊攪泮一 邊升溫至90°C。升溫後，添加硫代乙醯胺84.5g(1125毫莫 耳），並攪拌2小時。冷卻至室溫’將氮氣以200ml/分鐘導 入，除去溶存之硫化氫。藉由離心分離機從得到之漿液分 離出粒子，用水洗淨，得到摻雜銅-鎵之硫化鋅70.9g(產率 爲9 7 % )。平均粒徑爲1 0.6从m。 實施例7 :撩雜銅-鎵之硫化鋅粒子之製造 ^ 在裝有攪拌機、溫度計、冷凝器之容量500ml三口燒瓶 中，添加硝酸鋅六水合物 74.4g(250毫莫耳）、硫酸鎂 1 . 5 g (3 7.5毫莫耳，相當於硝酸鋅之莫耳量之5莫耳％ )、硝 酸銅三水合物 462mg(1.91毫莫耳）、硝酸鎵六水合物 224mg(0.61毫莫耳）、水250ml並攪拌，添加硝酸0.3g，進 一步一邊攪拌一邊升溫至90°C。升溫後，添加硫代尿素 2 8.5 g (375毫莫耳），並攪拌2小時。冷卻至室溫，將氮氣以 200ml/分鐘導入，除去溶存之硫化氫。藉由離心分離機從 ® 得到之漿液分離出粒子，用水洗淨，得到摻雜銅-鎵之硫化 鋅23.9g(產率爲98%)。平均粒徑爲12.3//m。 實施例8 :摻雜銀-鎵之硫化鋅粒子之製_造 在裝有攪拌機、溫度計、冷凝器之容量2公升之三口燒 瓶中，添加硝酸鋅六水合物298 g(l莫耳）、硫酸鎂6.0g(50 毫莫耳，相當於硝酸鋅之莫耳量之5莫耳％)、硝酸銀92mg (0 · 5 4毫莫耳）、硝酸鎵六水合物 5 5 m g (0 · 1 5毫莫耳）、水 1 000ml並攪拌，添加硝酸2g，一邊攪拌一邊升溫至90°C。 升溫後，添加硫代乙醯胺1 1 3 g (1. 5莫耳），並攪拌2小時。 -15- 200835775 冷卻至室溫’將氮氣以200ml/分鐘導入，除去溶存之硫化 氫。藉由離心分離機從得到之漿液分離出粒子，用水洗淨， 得到摻雜銀-鎵之硫化鋅94.lg(產率爲97%)。平均粒徑爲 9 · 6 /z m 〇 比較例 1 除在實施例1(A)中不使用硫酸鎂以外，以與實施例1(A) 同樣之方式進行，得到硫化鋅11.8 g (產率97%)。平均粒徑 爲3 9.7 M m。粒子生成物所得到之粒度分布曲線如第9圖所 • 示，又SEM觀察照片如第10圖所示。 比較例2 在裝有攪拌機、溫度計、冷凝器之容量5 00ml三口燒瓶 中，添加硝酸鋅六水合物 37.2g(125毫莫耳）、硫酸鎂 〇.〇8g(〇.125毫莫耳，相當於硝酸鋅之莫耳量之〇」莫耳％) 及水25 0 ml並攪拌，添加硝酸0.5g，然後一邊攪拌一邊升 溫至90°C。升溫後，添加硫代乙醯胺18.8g(250莫耳），並 攪拌2小時。冷卻至室溫，將氮氣以200ml/分鐘導入，除 ® 去溶存之硫化氫。藉由離心分離機從得到之漿液分離出粒 子，用水洗淨，得到硫化鋅11.6g(產率爲94%)。平均粒徑 爲 5.7 /z m。 將實施例及比較例之結果整理並示於表1 ° -16- 200835775 [表1] 實施例 產率 (%) 粒度分布 Ds〇( β m) 標準偏差 實施例1(A) 97 18.8 0.16 實施例1(B) 97 18.0 0.15 實施例2 98 24.3 0.09 實施例3 93 8.2 0.13 實施例4 89 18.8 0.11 實施例5 96 17.6 0.12 實施例6 97 10.6 0.10 實施例7 98 12.3 0.03 實施例8 97 9.6 0.18 比較例1 97 39.7 0.61 比較例2 94 5.7 0.4 表1中之粒度分布及標準偏差係基於實施例及比較例所 得到之粒度分布曲線而求得。實施例與比較例之間生成物 之產率雖未發現明顯差異，然而關於粒度分布及標準偏 差，實施例（1〜8)與比較例（1、2)之間出現明顯不同。實施 例所得到之粒子之平均粒徑，未如比較例所得到之極端大 的値或極端小的値，而集中在8〜30/zm之範圍內。又，實 施例中任一項標準差均不到〇. 2，可知生成之粒子之粒徑參 差不齊少。此種粒度分布之不同，從第1圖、第3至9圖 及第1 1圖之粒度分布曲線之形狀可更爲明白。尤其，從相 當於本發明之實施例結果之第1圖及第3至8圖，可確認 本發明之實施例所得到之粒子粒徑呈單分散性。 -17- 200835775 再者，若根據從實施例1(A)得到之粒子生成物之SEM 照片（第2圖），可知粒子生成物彼此凝集之微小粒子結合 或融合，形成一個外觀更大之粒子，其粒徑看起來約略均 一化，各粒子之外形亦無太大差異。另一方面，根據從比 較例1得到之粒子生成物之SEM照片（第1 0圖），可確認爲 具有不規則外形之不定形物集合之狀態，並未形成如實施 例1(A)之外觀上均一之粒子。 [產業上之可利用性] ® 本發明係提供爲無機螢光體之先質化合物之II-VI族化 合物半導體之粒度分布狹窄且呈單分散之粒子生成物之製 法。若依照本發明之製法，可有效地製造工業製程中操作 容易之無機螢光體先質粒子。再者，由於本發明之方法係 基於液相合成法之製法，因此能將可成爲發光中心之賦活 劑或共賦活劑元素均質地導入母材化合物中，而可用於高 亮度螢光體之製造。 【圖式簡單說明】 ® [第1圖]藉由實施例1(A)得到之螢光體先質粒子之粒度 分布。 [第2圖]藉由實施例i(A)得到之螢光體先質粒子之SEM 照片。 (上方照片：標尺1〇从m，倍率3000倍；下方照片：標 尺60/zm，倍率60倍） [第3圖]實施例2所得到之螢光體先質粒子之粒度分布。 [第4圖]實施例3所得到之螢光體先質粒子之粒度分布。 •[第5圖]實施例4所得到之螢光體先質粒子之粒度分布。 -18- 200835775 [第6圖]實施例6所得到之螢光體先質粒子之粒度分布。 [第7圖]實施例7所得到之螢光體先質粒于之粒度分布。 [第8圖]實施例8所得到之螢光體先質粒子之粒度分布。 [第9圖]比較例1所得到之螢光體先質粒子之粒度分布。 [第10圖]比較例1所得到之螢光體先質粒子之SEM照 片。 (標尺6 μ m，倍率5000倍） [第1 1圖]比較例2所得到之螢光體先質粒子之粒度分 布。 【主要元件符號說明】 Μ 〇 -19 -200835775 IX. Description of the Invention: [Technical Field] The present invention relates to a process for producing II-VI compound semiconductor particles useful in the manufacture of inorganic phosphors; in particular, for controlling primary particles of a II-VI compound semiconductor A particle size distribution of the formed aggregates (secondary particles), a method of producing a phosphor particle-first particle having a uniform particle size, and a phosphor precursor particle obtained by the method. [Prior Art] A II-VI compound semiconductor, for example, a compound semiconductor containing zinc sulfide or the like as a main component, if a crystal structure is doped with a living element such as manganese, copper, silver, ruthenium, rhodium, iridium or fluorine, When heat treatment or the like is performed, the luminescence phenomenon can be exhibited by irradiation of light, electrons, or the like. Therefore, the above compound semiconductor can be used as a matrix material of a phosphor, in particular, a granular material of a compound semiconductor mainly composed of zinc sulfide, etc., and can be used for manufacturing a plasma display, an electroluminescence display, and an electric field radiation type display. The precursor of the phosphor used in the display device. Here, the term "precursor" means a compound semiconductor which is doped with an activator, and is a stage before heat treatment or the like. That is, since the compound semiconductor doped with the activator starts to exhibit the properties as a phosphor by performing heat treatment or the like, the precursor of the phosphor precursor is closely distinguished from the phosphor itself. A method of synthesizing a phosphor precursor using zinc sulfide as a precursor has a method of using a solid phase reaction and a method of utilizing a reaction in a liquid phase. For the former solid phase synthesis method, the zinc sulfide particles of the raw material and the inorganic salt called FLUX can be used together for the first firing at 200835775 at a very high temperature of 800 ° C to 1300 ° C to make micron-sized particles. Growth method, followed by a second firing at 500 to 1000 ° C to obtain a phosphor particle (see Patent Documents 1 to 3). In this method, since the solid phase reaction is carried out by baking at a high temperature Since it is difficult to add a new component to the reaction system, for example, it is difficult to dope the activator or the co-activator into the inside of the particle so as to have a homogenous concentration distribution in the particle. Therefore, as for the solid phase synthesis method, there is a limitation in "a fluorescent body which is doped with a zinc sulfide precursor to obtain a higher brightness". ® On the other hand, when the π-νι phosphor precursor is synthesized by the latter liquid phase synthesis method, since the amount of the activator or the co-activator can be added while the particles are growing, the solid phase is controlled. Different in the synthesis method, the concentration distribution of the activator or co-activator inside the obtained phosphor particles can be homogenized. Further, although the phosphor particles are formed by two processes of nucleation formation and particle growth, by controlling the supersaturation during growth of the particles, a particle product having a narrow particle size distribution and being monodispersed can be obtained. Regarding the synthesis of II-VI phosphor precursors in the liquid phase, a method of synthesizing particles under hydrothermal conditions (for example, refer to Patent Document 4), or a method of controlling particle size distribution (for example, refer to patent documents) 5). On the other hand, it is disclosed that a precursor of a phosphor and a raw material component solution containing a constituent element of an activator or a co-activator are mixed, and a phosphor precursor crystal, an activator or a co-activator is co-precipitated to produce a phosphor. Method (refer to Patent Document 6). Further, the method for producing a II-VI compound semiconductor discloses a method of reacting a compound containing a group II element with a quinone compound containing a group VI element such as thioacetamide under hydrothermal conditions (refer to Patent Document 7). Non-patent document 1). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. 1] J. Chem. Soc. Faraday Trans., ® 5 6 3 - 570 (1 9 8 4) SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The phosphor obtained by the method disclosed in Patent Documents 4 to 7 and the like It is a fine primary particle having an average particle diameter of about several nanometers. The primary particle agglomerates to form secondary particles having a particle diameter of several hundred micrometers, and on the other hand, there are fine particles having a particle diameter of about several nanometers to several tens of nanometers, and a particle product having a broad particle size distribution. Since the particle size is irregular, the shape of the particles is irregular, and the sedimentation speed is greatly deteriorated. The recovery and washing of the particles must have complicated steps, and the time required, etc., may cause inconvenience in operation. Therefore, it is desirable to develop a method of modulating a narrowly distributed and monodisperse phosphor precursor particle. Means for Solving the Problem As a result of intensive investigations by the present inventors, it has been found that when an aqueous liquid phase containing an electrolyte compound composed of a specific salt is added, a raw material compound containing a Group II VI element is reacted with each other to form a II-VI group. When the primary particles of the conductor are re-aggregated, the primary particles are agglomerated to form particles of particle size 1 (80), and the sub-particles are mutually different, and the metal elements and the compound are semi-equalized in a very long particle size. Secondary particles, thus completing the present invention. That is, the present invention provides a method for preparing a Group II-VI phosphor precursor, which is characterized by comprising an electrolyte compound composed of a mineral acid or an organic acid salt of a typical metal and an aqueous liquid containing a Group II element compound. In the phase, a quinone compound containing a group VI element is added to form particles of a group II-VI compound semiconductor. The particles of the II-VI compound semiconductor obtained by the present invention are not limited to the primary particles generated by reacting the group II element-containing compound immediately after the addition of the group VI-containing guanamine compound, and further including the primary particle. The generated secondary particles (aggregates) are aggregated in the liquid phase. Accordingly, another aspect of the present invention is an aggregate which is an agglomerate of a Group II-VI compound semiconductor characterized by having an average particle diameter of 8 to 30 μm and a standard deviation of 0.01 to 0.2. [Effect of the Invention] According to the method of the present invention, a Group II-VI compound semiconductor particle whose particle size distribution is controlled to be monodispersed can be obtained. Therefore, by using the phosphor precursor particles obtained according to the present invention, it is expected to remarkably improve the efficiency of the steps of washing and recovering the particles, and to achieve the efficiency of the entire production process of the phosphor. [Embodiment] The term "II-VI compound semiconductor" used in this application is composed of Group II elements (Be, Mg, Zn, Cd, Hg) and Group VI elements (〇, s, Se, Te). A generic term for a binary compound semiconductor and a mixed crystal semiconductor thereof. Examples of the II-VI compound semiconductor used in the present invention may be zinc sulfide, zinc selenide, cadmium sulfide, cadmium selenide, etc., etc., as described below, by 200835775, Qin becomes a metal, non-metal of the luminescent center. The ion (activator or co-activator) replaces a part. The compound containing a Group II element of the ruthenium in the present invention is not particularly limited, and inorganic acid salts such as zinc chloride, zinc nitrate, zinc sulfate, cadmium chloride, cadmium nitrate, and cadmium sulfate; zinc acetate and propionic acid can be used. Organic acid salts such as zinc, zinc oxalate, cadmium acetate, cadmium propionate, and cadmium oxalate. These compounds may be used singly or in combination of plural kinds. Although the compound can be used in any concentration, if the concentration is too high, the formation rate of the II-VI compound semiconductor becomes faster, and other ions such as the ® activator cannot be uniformly introduced, and if the concentration is too low, The growth rate is slow, not only the volumetric efficiency is lowered, but also the effect of the electrolyte becomes thin, and the control of the particle size distribution becomes difficult, which is not preferable. With the consideration of the above, the compound containing a Group II element in the present invention is used in a concentration of 〇1 mol / liter ~ 5 m / liter, preferably 0.1 m / liter ~ 2 m / liter Concentration is used. As the quinone compound containing a group VI element used in the present invention, thioguanamine such as thiocarbamide, thioacetamide or thiopropionamide can be used. These may be used singly or in combination of plural kinds. However, from the viewpoint of economy and ease of use, it is preferred to use thioacetamide. Regarding the amount of thioindole used, considering the reaction efficiency and volumetric efficiency, 1.0 to 100 times (preferably 1.7 to 30 times, more preferably 1.9 to 5 times) is used with respect to the molar number of the compound containing a Group II element. The amount of moles. The liquid phase solvent used in the present invention, although typically water, may further contain a polar organic compound (for example, an alcohol such as methanol or ethanol) insofar as the solubility of the additive (electrolyte) described below is not significantly lowered. ). In the present invention, in addition to the compound containing a Group II element and the group VI-containing element, by adding a compound containing an activator or co-activator element which can become a luminescent center in an aqueous liquid phase, The ions of the element are doped in the crystal of the parent metal formed. As the element of the luminescent center, a transition metal such as manganese, copper, silver, gold or ruthenium; a halogen such as chlorine, iodine or bromine; ruthenium, osmium, iridium, ammonium, osmium, iridium, osmium, iridium, osmium, iridium; , bismuth, bait, watch, mirror and other rare earths. Further, as the transition metal or rare earth as the acceptor, a halogen such as aluminum, gallium, indium or fluorine, chlorine, bromine or iodine which is used as a donor may be used. These elements can be introduced by using a halide such as chloride, bromide or iodide; an organic acid salt such as formic acid, acetic acid or propionic acid; or a salt such as acetylsulfate. These compounds may be used singly or in combination of plural kinds. Further, it can be coexisted with a complex compound such as pyridine or phosphine. The amount of the above compound to be used is usually in the range of 0.0001 part by weight to 20 parts by weight based on 100 parts by weight of the II-VI compound semiconductor to be formed, but considering the effect of substitution and economy, 0.0 A range of 0 02 parts by weight to 1 part by weight is preferred. In the present invention, particles of the Group II-VI phosphor are formed by the inverse Φ of the above-mentioned Group II or Group VI-containing compound. The primary particles of the phosphor particles are fine particles having a particle diameter of several nm to 3 Onm. However, they are reaggregated in an aqueous liquid phase in which the electrolyte compound is dissolved to form secondary particles of an appropriate size. The secondary particles obtained by the present invention have a narrow particle size distribution and exhibit monodispersity. The average particle size of the resulting aggregate is usually less than 3 Ο μ m and the standard deviation is less than 0.2. It is preferred that the average particle diameter of the aggregate is 8 to 3 〇 M m and the standard deviation is 0.01 to 0.2. Further, the term "particle size" used therein, unless specifically defined in advance, means an average particle diameter of -10 - 200835775 obtained by obtaining a center particle diameter D 5 ° from a particle size distribution curve. In the present invention, the additive (aggregating agent) which can further agglomerate the primary particles formed in the aqueous liquid phase is not particularly limited as long as it is an electrolyte compound which is soluble in the aqueous liquid phase, but does not mix into the II-VI group. Phosphor precursors are preferred. When the ions generated when the electrolyte is dissolved in the liquid phase are mixed with the precursor of the phosphor, the performance as a phosphor will be deteriorated, and the brightness will also be lowered. From such a viewpoint, as a preferred additive to be used in the present invention, a mineral acid or an organic acid salt of a typical metal may be mentioned, and an inorganic acid salt or an organic acid salt of the genus Alkaline Gold® is more preferable. As a typical metal, a metal element such as magnesium, calcium or barium may be mentioned, and a particularly preferable metal is magnesium and calcium. As the additive compound containing these metals, hydroxides, sulfates, nitrates, halides such as chlorides and bromides, organic acid salts of formic acid, acetic acid or propionic acid, etc., but hydroxide or sulfuric acid may be used. Salt is especially good. The present invention can be carried out by previously adding the above compound to a liquid phase together with a compound containing a Group II element in any amount, and further adding a guanamine compound containing a Group VI element. The amount of the additive compound to be added is usually in the range of 0.0001 part by weight to 20 parts by weight based on 100 parts by weight of the group II-IV compound semiconductor, but is 0.0002 part by weight from the viewpoint of agglutination effect and economy. A range of ~10 parts by weight is preferred. Further, from the viewpoint of "controlling the particle size distribution of the aggregate formed to avoid mixing into the product", the preferred addition amount is based on the molar amount of the compound containing the group II element used, and is 0.5 to 40 moles. The range of the ear % is particularly good in the range of 0.8 to 30 mol%. In the present invention, a Group II-VI phosphor precursor can be produced by batch or continuous. Further, the temperature of the liquid phase is not particularly limited as long as it does not impair the progress of the reaction and the agglomeration effect of the particles, but may vary depending on the type and amount (concentration) of the -11-200835775 § in the liquid phase. And change. Usually, the temperature of the liquid phase can be adjusted to be in the range of 20 ° C to 120 ° C. The temperature adjustment of the liquid phase can be carried out by using a conventional temperature-controlled heating device outside the reaction vessel, but it can also be carried out by providing a heating device capable of controlling the temperature in the liquid phase. However, when the reaction temperature is low, the growth of the particles is slow, the reaction takes a long time, and the productivity per hour becomes low, which is not preferable from the viewpoint of economy. Further, from the viewpoint of operability, if the temperature is too low, the viscosity of the entire liquid becomes high, and it is difficult to diffuse the reaction liquid at an equal flow rate, and the workability is lowered. On the other hand, if the temperature is too high, the vaporization is performed. The irritation caused by the gas becomes strong, and the operability is deteriorated. In view of these points, the method of the present invention is preferably carried out in the range of 60 ° C to 100 ° C, and more preferably in the range of 65 ° C to 90 ° C. In the method of the present invention, from the beginning to the end, that is, from the point immediately before the addition of each component to the liquid phase to the point immediately before the generation of the particle precursor of the phosphor precursor, during some or all of the period Stirring is carried out continuously or intermittently at any agitation speed. The time required for the implementation of the method of the present invention can be appropriately selected according to the conditions of the scale, the apparatus, and the like, and the degree of formation of the agglomerated particles and the degree of formation of aggregated particles, but usually can be carried out for 1 to 20 hours. The reaction is preferably carried out by performing a reaction of 3 to 10 hours. [Examples] Hereinafter, the present invention will be described in more detail by way of Examples. However, the present invention is not limited to the examples, and it is not intended to be in the scope of the technical idea of the present invention. Implemented with amendments and changes. In the following examples, for the particle size distribution of the particle product, SALD-2100 manufactured by Shimadzu Corporation was used, and the -12-200835775 m measurement was performed by the laser refraction scattering method, and the analytical software SALD attached to the device was used. -2100, the median diameter D5〇 is obtained, and the breadth of the distribution is evaluated thereby. Further, the SEM observation was carried out using an S4000 manufactured by Hitachi, Ltd. under the conditions of an acceleration voltage of 5 kV. EXAMPLES Production of Zinc Sulfide Particles (A) In the case of using magnesium sulfate in an electrolyte, zinc nitrate hexahydrate 37.2 g (125 mmol) was dissolved in a 500 ml three-necked flask equipped with a stirrer, a thermometer, and a condenser. In 250 ml of water, ® added bismuth nitrate. 5g and adjust the pH to 2. 0.75 2 g of magnesium sulfate (6.25 mmol, which corresponds to 5 mol% of the molar amount of zinc nitrate) was added thereto, and the temperature was raised to 70 °C while stirring. After the solution was warmed to 70 ° C, 18.8 g (250 mmol) of thioacetamide was added. After stirring for 2 hours as it was, nitrogen gas was introduced into the flask at 200 ml/min to remove the dissolved hydrogen sulfide. The particle product was separated from the obtained slurry by centrifugation, and washed with water to obtain 11.8 g of zinc sulfide (yield 97%). The average particle size was 18.8 / / m. The particle size distribution curve obtained for the particle product is shown in Fig. 1, and the SEM observation is shown in Fig. 2. (B) In the case of using calcium sulfate in the electrolyte, in the same manner as in the above (A), vulcanization was carried out except that 0.85 g (6.25 mmol) of calcium sulfate was added to the above (A) instead of magnesium sulfate. Zinc 1 1.8 g (yield 97%). The average particle size was 18.0 // m. Example 2 except that the amount of magnesium sulfate used in Example 1 (A) was 3.0 g (; 25 胄 胄 ear, which corresponds to 20 mol % of the molar amount of zinc nitrate), and Example 1 (A) In the same procedure, zinc sulfide 1 1 · 9 g (yield 98%) was obtained. The average particle size -13· 200835775 is 24.3 from m. Sinus application 3. In addition to the use of magnesium sulfate in Example 1 (A), 〇.3g (2.5 millimolar, equivalent to 2 mole % of zinc nitrate), and Example 1 (A In the same procedure, 11.3 g of zinc sulfide was obtained (yield 93%). The average particle size is 8.2 / / m. Example 4 In addition to changing the magnesium sulfate in Example 1 (A) to 2.54 g of magnesium chloride hexahydrate (12.5 mmol, which corresponds to 10 mol% of the molar amount of zinc nitrate), In the same manner as in Example 1 (A), 10.9 g of zinc sulfide was obtained (yield 89%). The average particle size is 18.8 // m. Example 5: Production of Manganese-Doped Zinc Sulfide Particles In a 500 ml three-necked flask equipped with a stirrer, a thermometer, and a condenser, 37.2 g (125 mmol) of zinc nitrate hexahydrate was dissolved in 250 ml of water, and nitric acid was added. 0.5 g, adjust the pH to 2. To the zinc nitrate aqueous solution, 0.0'12 g (0.125 mmol) of manganese sulfate and 0.752 g of magnesium sulfate (6.25 mmol, which corresponds to 5 mol% of the molar amount of zinc nitrate) were added, and the temperature was raised while stirring. • 7〇°C. After confirming that the solution was warmed to 70 ° C, 18.8 g (250 mmol) of thioacetamide was added in one portion. After stirring for 2 hours as it was, nitrogen gas was introduced into the flask at 200 ml/min to remove the dissolved hydrogen sulfide. The particle product was separated from the obtained slurry by centrifugation, and washed with water to obtain 11.7 g of manganese-doped zinc sulfide (yield 96%). The average particle size was 17.6/zm. A fine example _$· 丨爹 铜 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Ear), magnesium sulfate 4.5 g (37.5 mmol, equivalent to 5 mol% of zinc nitrate), copper sulfate trihydrate-14-200835775 compound 1.39 g (5.75 mmol), gallium nitrate hexahydrate 670 mg ( 1.84 mmol) and 75 Qml of water were stirred, and 1.5 g of nitric acid was added. Further, the temperature was raised to 90 ° C while stirring. After the temperature was raised, 84.5 g (1125 mmol) of thioacetamide was added and stirred for 2 hours. Cooling to room temperature was carried out by introducing nitrogen gas at 200 ml/min to remove dissolved hydrogen sulfide. The particles were separated from the obtained slurry by a centrifugal separator, and washed with water to obtain 70.9 g of copper-gallium-doped zinc sulfide (yield of 97%). The average particle size is from 1 0.6 to m. Example 7: Preparation of zinc sulfide particles of doped copper-gallium ^ In a 500 ml three-necked flask equipped with a stirrer, a thermometer, and a condenser, 74.4 g (250 mmol) of magnesium nitrate hexahydrate was added, and magnesium sulfate 1 was added. 5 g (3 7.5 millimolar, equivalent to 5 mole % of zinc nitrate), copper nitrate trihydrate 462 mg (1.91 mmol), gallium nitrate hexahydrate 224 mg (0.61 mmol) 250 ml of water was stirred and added, and 0.3 g of nitric acid was added, and the temperature was further raised to 90 ° C while stirring. After warming up, thiourea 2 8.5 g (375 mmol) was added and stirred for 2 hours. After cooling to room temperature, nitrogen gas was introduced at 200 ml/min to remove dissolved hydrogen sulfide. The particles were separated from the slurry obtained by the centrifugal separator by a centrifugal separator, and washed with water to obtain 23.9 g of copper-doped zinc sulfide (yield 98%). The average particle size was 12.3/m. Example 8: Preparation of silver-gallium-doped zinc sulfide particles _ Zn hexahydrate 298 g (l mole), sulfuric acid was added to a three-liter three-liter flask equipped with a stirrer, a thermometer, and a condenser. Magnesium 6.0g (50 millimolar, equivalent to 5 mole % of zinc nitrate), silver nitrate 92mg (0 · 5 4 millimolar), gallium nitrate hexahydrate 5 5 mg (0 · 1 5 milli 1 ml of water and stirring, and 2 g of nitric acid was added, and the temperature was raised to 90 ° C while stirring. After warming up, thiacetamide 1 1 3 g (1.5 mol) was added and stirred for 2 hours. -15- 200835775 Cooling to room temperature 'Nitrogen gas was introduced at 200 ml/min to remove dissolved hydrogen sulfide. The particles were separated from the obtained slurry by a centrifugal separator, and washed with water to obtain silver sulfide-doped zinc sulfide 94.lg (yield 97%). The average particle diameter was 9 · 6 /zm. 〇Comparative Example 1 In the same manner as in Example 1 (A) except that magnesium sulfate was not used in Example 1 (A), zinc sulfide (11.8 g) was obtained (yield 97). %). The average particle size is 3 9.7 M m. The particle size distribution curve obtained by the particle product is shown in Fig. 9, and the SEM observation photograph is shown in Fig. 10. Comparative Example 2 Zinc nitrate hexahydrate 37.2 g (125 mmol), magnesium sulfate 〇. After 5% of the molar amount of zinc nitrate, "mol%" and 25 ml of water were stirred, and 0.5 g of nitric acid was added thereto, and the temperature was raised to 90 ° C while stirring. After the temperature was raised, 18.8 g (250 m) of thioacetamide was added and stirred for 2 hours. Cool to room temperature and introduce nitrogen at 200 ml/min to remove hydrogen sulfide from the solution. The particles were separated from the obtained slurry by a centrifugal separator and washed with water to obtain 11.6 g of zinc sulfide (yield 94%). The average particle size is 5.7 /z m. The results of the examples and comparative examples are summarized and shown in Table 1 ° -16 - 200835775 [Table 1] Example Yield (%) Particle size distribution Ds 〇 (β m) Standard deviation Example 1 (A) 97 18.8 0.16 Implementation Example 1 (B) 97 18.0 0.15 Example 2 98 24.3 0.09 Example 3 93 8.2 0.13 Example 4 89 18.8 0.11 Example 5 96 17.6 0.12 Example 6 97 10.6 0.10 Example 7 98 12.3 0.03 Example 8 97 9.6 0.18 Comparative Example 1 97 39.7 0.61 Comparative Example 2 94 5.7 0.4 The particle size distribution and standard deviation in Table 1 were determined based on the particle size distribution curves obtained in the examples and comparative examples. Although no significant difference was found in the yield of the product between the examples and the comparative examples, there were significant differences between the examples (1 to 8) and the comparative examples (1, 2) regarding the particle size distribution and the standard deviation. The average particle diameter of the particles obtained in the examples was not as large as that of the comparative example or extremely small enthalpy, but concentrated in the range of 8 to 30/zm. Further, in any of the examples, the standard deviation was less than 〇. 2, and it was found that the particle diameter of the generated particles was small. The shape of the particle size distribution curve from Fig. 1, Fig. 3 to Fig. 9, and Fig. 11 can be more clearly understood. In particular, it can be confirmed from the first and third to eighth graphs which are equivalent to the results of the examples of the present invention that the particle diameters of the particles obtained in the examples of the present invention are monodisperse. -17- 200835775 According to the SEM photograph (Fig. 2) of the particle product obtained in Example 1 (A), it is understood that the fine particles in which the particle products are agglomerated are combined or fused to form a larger-looking particle. The particle size appears to be approximately uniform, and the shape of each particle does not differ much. On the other hand, according to the SEM photograph (Fig. 10) of the particle product obtained in Comparative Example 1, it was confirmed that the amorphous material had an irregular shape and was not formed as in Example 1 (A). Uniform particles in appearance. [Industrial Applicability] ® The present invention provides a method for producing a particle product having a narrow particle size distribution and a monodisperse particle size distribution of a Group II-VI compound semiconductor which is a precursor of an inorganic phosphor. According to the process of the present invention, inorganic phosphor precursor particles which are easy to handle in an industrial process can be efficiently produced. Furthermore, since the method of the present invention is based on a liquid phase synthesis method, an activator or a coactivator element which can serve as a luminescent center can be uniformly introduced into a base material compound, and can be used for the manufacture of a high-luminance phosphor. . BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] The particle size distribution of the phosphor precursor particles obtained in Example 1 (A). [Fig. 2] SEM photograph of the phosphor precursor particle obtained by the example i (A). (Top photograph: scale 1 〇 from m, magnification 3000 times; lower photograph: scale 60/zm, magnification 60 times) [Fig. 3] The particle size distribution of the phosphor precursor particles obtained in Example 2. [Fig. 4] The particle size distribution of the phosphor precursor particles obtained in Example 3. • [Fig. 5] The particle size distribution of the phosphor precursor particles obtained in Example 4. -18- 200835775 [Fig. 6] The particle size distribution of the phosphor precursor particles obtained in Example 6. [Fig. 7] The particle size distribution of the phosphor obtained in Example 7 was first prepared. [Fig. 8] The particle size distribution of the phosphor precursor particles obtained in Example 8. [Fig. 9] The particle size distribution of the phosphor precursor particles obtained in Comparative Example 1. [Fig. 10] SEM photograph of the phosphor precursor particle obtained in Comparative Example 1. (Scale 6 μ m, magnification 5000 times) [Fig. 1 1] The particle size distribution of the phosphor precursor particles obtained in Comparative Example 2. [Main component symbol description] Μ 〇 -19 -