201217495 六、發明說明： 【發明所屬之技術領域】 本發明係關於將銪（Eu)固溶的β型矽鋁氮氧化物之 製造方法。 【先前技術】 在專利文獻1中係記載有以將Eu固溶的β型石夕銘氮 氧化物之製造方法而言，藉由使用氫氟酸與硝酸的混酸 溶液的酸處理’來使固溶有Eu的β型矽鋁氮氧化物的發 光強度提升的技術内容。但是，在專利文獻1中亦記載 有若混酸溶液的濃度較高時’螢光體會溶解，及若溫度 為6 0 °C以上時，螢光體會溶解的技術内容。 在專利文獻2中係揭示出為了使固溶有Eu的β型石夕 鋁氮氧化物的發光強度提升，將經粉碎的燒成物在氮氣 以外的惰性氣體中在13〇〇。〇〜1600。(：下進行再加熱後， 使用50%氫氟酸與70%硝酸的混酸溶液來進行酸處理的 技術。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2005-255885號公報 [專利文獻2]國際公開第2008/06278 1號小冊子 【發明内容】 [發明所欲解決之課題] 本發明之目的在提供一種可重現性佳地實現更高發 光效率之固溶有Eu的β型矽鋁氮氧化物之製造方法。 201217495 本發明係基於在酸處理步驟中在使用氫氟酸與硝酸 的混酸溶液的情形下，若降低混酸溶液濃度，所得瑩光 體的發光強度會變低’但是在較高溫度下，發光強度會 變高的新賴見解而得者。該見解係與專利文獻1所記載 之「右混酸溶液的濃度較tfj，固溶有Eu的β型石夕銘氮氧 化物會溶解’故較不理想」及「混酸處理溫度較低為佳 」的揭示呈相反的結果。 [解決課題之手段] 本發明係一種β型矽鋁氮氧化物之製造方法，係在 以通式· Si6_zAlzOzN8-z(0<zS4.2)所示之β型石夕铭氮氧 化物上固溶Ευ的β型石夕銘氮氧化物之製造方法，其具有 :將含有Si、Α卜Eu的原料混合粉末在氮氣環境中進行 燒成的第一加熱步驟；將所得的燒成物在惰性氣體環境 中或真空中進行熱處理的第二加熱步驟；及在第二加熱 步驟後’在鼠氟酸與確酸的混酸溶液中，以超過6〇〇c ' 1 0 0 C以下的溫度範圍進行酸處理的步驟。 [發明之效果] 藉由本發明之方法，可重現性佳地製造具有高發光 效率之將Eu固溶的β型矽鋁氮氧化物。 【實施方式】 [用以實施發明之形態] 本發明係一種將Eu固溶的ρ型矽鋁氮氧化物之製造 方法，其係包含：將含有Si、八卜Eu的原料混合粉末在 氮氣環境中進行燒成的第一加熱步驟；將所得的燒成物 在惰性氣體環境中或真空中進行熱處理的第二加熱步驟 201217495 的混睃溶液中 行酸處理的步 及在第二加熱步驟後，在氫氟酸與確酸 以超過60°C、i〇〇°c以下的溫度範圍進 驟 或 碳 含有Si、A1、Eu的原料混合粉末俜扣收与 个你知將氧化矽 氧化鋁、氮化矽、氮化鋁、選自銪的金屬 '氧化 酸鹽' 氮化物或氮氧化物的銪化合物物、 以混合的粉末 < 含有Si、Ai的原料係以滿足通式 ζ$4.2)的方式來進行掺合。201217495 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a β-type lanthanum aluminum oxynitride which solid-solves ruthenium (Eu). [Prior Art] Patent Document 1 describes a method for producing a β-type Shi Ximing oxynitride which is solid-dissolved with Eu, and is cured by acid treatment using a mixed acid solution of hydrofluoric acid and nitric acid. The technical content of the improvement of the luminescence intensity of β-type yttrium aluminum oxynitride in which Eu is dissolved. However, Patent Document 1 also discloses that when the concentration of the mixed acid solution is high, the phosphor is dissolved, and when the temperature is 60 ° C or higher, the phosphor is dissolved. In Patent Document 2, it is revealed that the pulverized burned product is 13 Torr in an inert gas other than nitrogen gas in order to increase the luminescence intensity of the β-type stellite aluminum oxynitride in which Eu is dissolved. 〇~1600. (A technique of performing acid treatment using a mixed acid solution of 50% hydrofluoric acid and 70% nitric acid after reheating. [Prior Art Document] [Patent Document] [Patent Document 1] JP-A-2005-255885 [Patent Document 2] International Publication No. 2008/06278 No. 1 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to provide a solid solution of Eu which is reproducible and achieves higher luminous efficiency. Method for producing β-type yttrium aluminum oxynitride 201217495 The present invention is based on the case where a mixed acid solution of hydrofluoric acid and nitric acid is used in the acid treatment step, and if the concentration of the mixed acid solution is lowered, the luminescence intensity of the obtained phosphor is changed. However, at a higher temperature, the luminescence intensity is higher, and the insight is the same as the "right mixed acid solution concentration in tfj described in Patent Document 1, and the β-type diarrhea in which Eu is dissolved. The disclosure that the NOx oxide dissolves is "less desirable" and the "mixed acid treatment temperature is lower" is the opposite result. [Means for Solving the Problem] The present invention relates to a method for producing a β-type lanthanum aluminum oxynitride. In the pass A method for producing a β-type Shi Ximing oxynitride of a β-type Shi Ximing oxynitride on a β-type Shi Ximing oxynitride represented by Si6_zAlzOzN8-z (0<zS4.2), which has a Si, a bismuth a first heating step of firing the raw material mixed powder in a nitrogen atmosphere; a second heating step of heat-treating the obtained fired material in an inert gas atmosphere or in a vacuum; and after the second heating step 'in the rat fluoride In the mixed acid solution of acid and acid, the step of acid treatment is carried out at a temperature range of more than 6 〇〇c '1 0 0 C or less. [Effect of the Invention] By the method of the present invention, reproducibility is preferably high. The present invention is a method for producing a p-type lanthanum aluminum oxynitride which is solid-dissolved with Eu, and is a method for producing a p-type yttrium aluminum oxynitride which is solid-dissolved in Eu. The method includes: a first heating step of firing a raw material mixed powder containing Si and Babu Eu in a nitrogen atmosphere; and a second heating step of heat-treating the resulting burned material in an inert gas atmosphere or in a vacuum in 201217495 The step of acid treatment in the bismuth solution After the second heating step, the raw material mixed with the hydrofluoric acid and the acid at a temperature exceeding 60 ° C, i 〇〇 ° C or below, or the raw material mixed with carbon, Si, A1, Eu, Cerium oxide alumina, tantalum nitride, aluminum nitride, a ruthenium compound selected from the group consisting of ruthenium metal oxylates, nitrides or oxynitrides, mixed powders, and raw materials containing Si and Ai The formula is ζ$4.2) for blending.
Si6-zAl2〇2N8 z(〇 备Eu含量係以〇丨質量％以上3質量％以下的範圍為 若Eu含量在上述範圍内，可充分獲得發光亮度。 佳 混 溶 明 型 動 料 境 以 溫 若 中 若將含有Si、Al、Eu的原料混合時，係有進行乾式 合的方法·，在與原料各成分不會實質上起反應的惰性 媒中進行濕式混合後，將溶媒去除的方法等，在本發 中亦可適用任何方法。以混合裝置而言，係可使用v /¾合機、搖擺式混合機（R〇cking Mixer)、球磨機、振 磨機等。 將原料混合粉末視需要乾燥後，填充在至少將該原 所相接的面形成為氮化硼的坩堝等容器内，在氮氣環 中加熱。 將經混合的原料混合粉末在氮氣環境下，在丨8 2 〇。匸 上2200°C以下，較佳為在1 850°C以上2〇5(TC以下的 度範圍下加熱來進行燒成（以下稱為第一加熱步驟）。 加熱溫度較低，Eu無法進入至β型矽鋁氮氧化物結晶 ’若將加熱溫度加高至所需以上，則必須施加較高的 201217495 氮氣壓力來抑制Eu固溶β型石夕铭氮氧化物的分解。燒成 中的壓力條件係以0.5MPa以上lOMPa以下為佳。加熱 時間一般為1 0小時〜2 0小時。 以原料混合粉末而言，亦可為含有Si的金屬粉末來 取代使用氮化矽。此時，必須將含有Si的金屬粉末在第 一加熱步驟之前進行氮化處理。含有Si的金屬粉末的氮 化反應係在1400°C以上1 600°C的溫度下進行，因此在第 一加熱步驟之前將含有Si的金屬粉末在氮氣環境下，在 上述溫度範圍下加熱而將Si轉換為Si3N4。 接著，在第一加熱步驟之後，另外將所得的燒成物 在真空中或氮氣以外的氣體環境中加熱（以下稱為第二 加熱步驟）。該第二加熱步驟係用以使殘留在燒成物中的 低結晶性部分更加不安定的處理。因第二加熱步驟處理 而變得不安定的低結晶相係藉由後述的混酸溶液處理予 以去除。 為了使低結晶性部分不安定化，較佳為在儘量不含 有屬於構成低結晶性部分的元素的氮與氧的氣體環境中 將燒成物進行加熱處理。若將第二加熱步驟在氮氣以外 的氣體環境中進行時，在排氣步驟後，在加熱爐内填充 惰性氣體（以下稱為導入步驟）。惰性氣體係選自氦、氖 、氬、氪、氙、氡、氫的氣體，較佳為氬、氫。 在第二加熱步驟中，燒成物係在真空中在1 200°C以 上1 550°C以下的溫度範圍、或惰性氣體環境中在1 300°C 以上1 550°C以下的溫度範圍予以加熱。若加熱溫度在該 溫度範圍内，可抑制Eu固溶β型石夕铭氮氧化物的分解。 201217495 在第二加熱步驟後進至酸處理步驟。在該酸處理步 驟中，係將藉由第二加熱步驟所得的燒成物進行粉碎’ 使粉碎燒成物分散在氫氟酸與硝酸的混酸溶液中，在超 過6 0 °C的溫度範圍下進行授拌。酸處理步驟係藉由浸潰 在酸性液體中，來去除呈不安定化的低結晶性部分的步 驟0 酸處理的溫度係超過60。(：、1 〇〇°C以下的溫度範圍 。若為過度低溫，Eu固溶的β型矽鋁氮氧化物的發光強 度會降低。 氫氟酸與硝酸的混合溶液亦可為將約50%濃度的氫 氟酸與約7 0 %濃度的硝酸加以混合者（以下稱為混合原 液）或將該混合原液加以稀釋者（以下將混合原液經稀釋 者稱為混酸溶液）。將混合原液稀釋後的溶液的濃度係以 25%以上、未達100%為佳，更佳為25%以上5〇%。亦可 非為將高濃度的氫氟酸及硝酸的混合溶液加以稀釋，而 疋將經稀釋的低濃度的氫氟酸及硝酸加以混合。 氫氣酸與硝酸的混合比若為將約50%濃度的 从氣酸 一为70%濃度的硝酸加以混合的情形，係以1〜9 : 9〜 的比率為佳，特佳為3〜7 : 7〜3。 〜1 前述混合溶液係以將濃氩氟酸及濃硝酸混合者 濃虱氟酸係指其濃度為4 〇 %以上6 0 %以下，濃崎二 才曰其}辰度為5 5 %以上7 5 %以下者。 _ •係 [實施例1 ] 以下關於本發明之實施例，一面參照表丨，—^ 加說明。表1係顯示後述實施例丨〜7及比較例〖、面砰 處理條件與發光特性者。 2的 201217495 [表i] 混酸溶液 — 酸處理條件 發光特七 HF ： HN〇3 液比 HF (ml) HN〇3 (ml) 蒸館水 (ml) 原液 濃度 (%) 液量 (ml) 溫度 CC) 時間 (分鐘） β粉 投入 (g) 光吸 收率 内部量 子效率 外部量 子效率 實施例1 5:5 25 25 150 25 200 70 60 5 72.5% 69.9% 50.7% 實施例2 5:5 25 25 150 25 200 80 60 5 71.8% 71.4% 51.2% 實施例3 5:5 25 25 150 25 200 90 60 5 71.2% 72.0% 51.3% 實施例4 3:7 15 35 150 25 200 80 60 5 71.6% 70.9% 50.8% 實施例5 7:3 . 35 15 150 25 200 80 60 5 71.7% 71.3% 51.1% 實施例6 5:5 50 50 100 50 200 80 卜60 5 74.7% 70.0% 52.3% 實施例7 5:5 50 50 0 100 100 80 60 5 72.9% 72.6% 52.9% 比較例1 5:5 25 25 150 25 200 60 60 5 72.0% 69.2% 49.8% 比較例2 5:5 50 50 卜0 100 100 35 60 5 73.6% 68.8% 50.6% 摻合α型氮化矽粉末（宇部興產公司製SN-E10級， 氧含量1.1質量％、β相含量4.5質量％)95.4質量％、氮 化鋁粉末（Tokuyama公司製F級，氧含量ο』質量％)3 〇 質量％、氧化鋁粉末（大明化學公司製TM-DAR級）0.74 質量％、氧化銪粉末（信越化學工業公司製RU級）〇 71質 置％ ’而付原料混合物6 0 0 g。 藉由搖擺式混合機（愛知電機公司製RM_丨0)，以60 分鐘乾式混合所得的原料混合物，另外全部通過筛孔 1 5 Ομιη的不銹鋼製篩，而得原料粉末。 將所得的原料粉末填充i 7〇g在以内寸計為直徑 lOcmx高度9cmx厚度〇.5cm之附蓋的圓筒型氣化侧繫 器(電氣化學工業公司製W級),在礙加熱器的電= ，作為第一加熱步驟而在〇.9MPa的加壓氮氣環境中，在 1950 C下進行15小時的燒成。將所得的燒成物裂解，通 過篩孔45 μηι的篩而得粉末。 將所得粉末填充20g在以内寸計為直徑6cmx高度 3.5cmx厚度〇.5cm之附蓋的圓筒型氮化硼製容器（電氡= 201217495 學工業公司製Ν-l級 加熱步驟而在真空中 理。 )’以碳加熱器的電氣爐，作為第二 在1 400 c下進行8小時的加熱處 將 50%濃度的氣氣酸Ώ 亂〜（HF)25ml及70%濃度的硝酸 (HN03)25ml混合而形成氧 '、日人、产 丄 ) 战馬犯合原液。在混合原液中添加 蒸館水15〇nU，將混合原液的濃度稀釋纟25%，來調整 HF + HN〇3水溶液20〇mi。於入楚_ t . mi技入第二加熱步驟後的粉末 5g’ -面將HF+HNOj溶液保持纟㈣，一面進行ι 小時的酸處理。 酸處理後的粉末係、以蒸鶴水將酸充分地沖洗過滤， 使其乾燥後，通過筛孔45μιη的筛而得實施W丄的勞光 體粉末。 接著’對實施例1的螢光體粉末，使用積分球來進 订全光束發光光譜測定（參考文獻：照明學會誌第83 卷，第2 5虎，平成1 1年（2000年），p87_93、NBS標準螢 光體之里子效率的測定，大久保和明等著）。激發光係使 用經分光的氙燈光源。 所製造的β型矽鋁氮氧化物的評估係如表丨所示， 以光吸收率、内部量子效率、外部量子效率的發光特性 來進行。 在進行該評估時，在試料部安置反射率為99%的標 準反射板（Labsphere公司，Spectralon(註冊商標））來測定 激發光的光谱，若激發波長為455nm時，由〜 的波長範圍的光譜來計算出激發光光子數（Qex)，接著， 在試料部安置螢光體，由所得的光譜數據來計算出激發 201217495 反射光光子數（Qref)及螢光光子數（Qem)，由所得的三種 光子數，來求出光吸收率（=(Qex_Qref)xl〇〇)、内部量子 效率（=Qem/(Qex-Qref)xl〇〇)及外部量子效率（= Qem/Qexx 1 00)。激發反射光光子數係在與激發光光子數 相同的波長範圍内’螢光光子數係若激發光為455nm時 ，在465〜800nm的範圍内計算出。 貫施例1中的發光特性係光吸收率7 2 5 〇/〇、内部量 子效率6 9.9 %、外部量子效率$ 〇. 7 %。 [實施例2] 實施例2的β型矽鋁氮氧化物之製造方法係除了將 酸處理的溫度設為80。(：以外，係與實施例1為相同的條 件，光吸收率71.8%、内部量子效率71.4%、外部量子 5 1.2%。 [實施例3] 實施例3的β型矽鋁氮氧化物之製造方法係除了將 酸處理的溫度設為90°c以外，係與實施例1為相〜 J的條 件，光吸收率71.2%、内部量子效率72.0%、外部量 51.3%。 [實施例4] 實施例4係將酸處理步驟，以將5〇%濃度的氣氣奶 (HF)15ml及70°/。濃度的硝酸（HN〇3)35ml混合而形成為 混合原液’在混合原液中添加蒸餾水1 5 〇 m 1，將入 匕δ原 液稀釋而使濃度成為25%的方式調整HF+HN〇3水溶液 200ml。除了投入第二加熱步驟後的粉末5g，—面將 + HNO3水溶液保持在8(rc 一面進行i小時的酸處理以 -10- 201217495 外，係與實施例1同樣地進行。若為實施例4的情形， 光吸收率7 1 · 6 %、内部量子效率7 〇 9、外部量子效率 5 0 _ 8 %。 [實施例5 ] 貫施例5係將5 0 %濃度的氫氟酸3 5 m 1及7 〇 %濃度的 硝酸15ml混合而形成為混合原液以外，係與實施例4為 相同條件之製造方法。若為實施例5的情形光吸收率 71.7%、内部量子效率71.3%、外部量子效率51 1%。 [實施例6 ] 實施例6係將50%濃度的氫氟酸5〇ml& 7〇%濃度的 硝酸5 0 m丨混合而形成為混合原液。在混合原液中添加蒸 餾水100HU’將混合原液稀釋’調整濃度成為鄉的Ηρ HN〇3水洛液200ml。除了投入第二加熱步驟後的粉末 5g，—面將HF+ ΗΝ03水溶液保持在8〇〇c，一面進行i 小時的酸處理以外，係為相同者。若為實施例6的情形 ’光吸收率74.7%、内部量子效率70.0%、外部量子效率 52.3。/0。 [貫施例7 ] 貫知例7係未在實施例6的酸處理中的酸使用蒸傑 ^ 除了使用1 〇〇ml的原液濃度1 00%者以外，係與實施 同樣地進行。在實施例7中，光吸收率7 2.9 °/〇、内 量子效率72 6%、外部量子效率52 9%。 (比較例1 ) 比較例1除了將酸處理溫度設為6(TC以外，係設成 與實施例1相同條件。光吸收率為72.0%、内部量子效 -11 - 201217495 率為69.2%、外部量子效率A 49.8。/。。 (比較例2) —比車又例2係除了將酸處理溫度設為35。(：以外’以與 施例6相同的條件進行。若為比較例2的情形，光吸 收率為73.6%、内部量子效率為68篇、外部量子效率為 50.6%。 由實施例1、2、3與比較例1可知藉由提升酸處 理的脈度，光吸收率、内部量子效率以及外部量子效率 均會提升。處理溫度若為超過6〇t、i〇(rc以下即可， 以7 0 C以上9 0。(：以下為佳。 由貝施例1〜5與比較例2可知，即使酸處理步驟中 的混I心液的浪度較稀，尤其將混合原液稀釋而使濃度 為25 /〇以上5〇%的範圍内，相較於作為習知例的比較例 2 β其光吸收率、内部量子效率、外部量子效率的任一者 句提升由比杈例1及2可知，若使混酸溶液濃度變稀 時’發光特性會降低。 [實施例8] 雖在表中未顯示，製作出將摻合有在實施例及比較 例中所使用# β型矽鋁氮氧化物的矽酮密封樹脂層積在 LED的發光面的發光裝置。若使用實施例丨〜7的ρ型矽 鋁氮氧化物，在使其發光之後，即使以8〇t χ濕度4〇% 的高溫放置2小時後，亦未發現發光特性降低。相對於 此，在使用比較例1及2的β型矽鋁氮氧化物的發光裝 置中，發現發光特性降低。 -12- 201217495 [產業上可利用性] 本發明之β型矽鋁氮氧化物若作為螢光體加以使用 時，以紫外至藍色光的範圍寬廣的波長予以激發，而呈 現高亮度的綠色發光，因此可適於使用作為以藍色或紫 外光為光源的白色LED的螢光體，而可適於使用在照明 器具、圖像顯示裝置等。 【圖式簡單說明】 無。 【主要元件符號說明】 無0 -13-Si6-zAl2〇2N8 z (the Eu content in the range of 〇丨% by mass or more and 3% by mass or less is such that the Eu content is within the above range, and the luminescent brightness can be sufficiently obtained. When the raw materials containing Si, Al, and Eu are mixed, a method of performing dry mixing, a method of removing the solvent after performing wet mixing in an inert medium that does not substantially react with each component of the raw material, etc. Any method can be applied to the hair. For the mixing device, a v / 3⁄4 mixer, a rocking mixer (R〇cking Mixer), a ball mill, a vibrating machine, etc. can be used. After the raw material mixed powder is dried as needed, The mixture is filled in a container such as a crucible in which at least the surface to which the original surface is formed is formed of boron nitride, and heated in a nitrogen gas ring. The mixed raw material mixed powder is placed in a nitrogen atmosphere at 丨8 2 〇. C is preferably calcined at a temperature of 1 850 ° C or more and 2 〇 5 (degrees below TC (hereinafter referred to as a first heating step). The heating temperature is low, and Eu cannot enter the β-type yttrium aluminum. Nitrogen oxide crystals If the degree is increased above the required level, a high nitrogen pressure of 201217495 must be applied to suppress the decomposition of the Eu-solution β-type Shi Ximing nitrogen oxide. The pressure conditions in the firing are preferably 0.5 MPa or more and 10 MPa or less. The time is generally from 10 hours to 20 hours. In the case of the raw material mixed powder, it is also possible to use a metal powder containing Si instead of using tantalum nitride. In this case, the metal powder containing Si must be subjected to the first heating step. Nitriding treatment. The nitridation reaction of the metal powder containing Si is performed at a temperature of 1400 ° C or higher and 1 600 ° C. Therefore, the metal powder containing Si is subjected to a nitrogen atmosphere at the above temperature range before the first heating step. Heating is performed to convert Si into Si3N4. Next, after the first heating step, the obtained fired product is additionally heated in a vacuum or a gas atmosphere other than nitrogen (hereinafter referred to as a second heating step). The step is a treatment for making the low crystalline portion remaining in the fired material more unstable. The low crystalline phase which becomes unstable due to the second heating step is treated by the mixed acid solution described later. In order to make the low crystallinity portion unstable, it is preferred to heat-treat the fired product in a gas atmosphere in which nitrogen and oxygen belonging to the element constituting the low crystalline portion are not contained as much as possible. When it is carried out in a gas atmosphere other than nitrogen, after the exhausting step, the heating furnace is filled with an inert gas (hereinafter referred to as an introduction step). The inert gas system is selected from the group consisting of ruthenium, rhodium, argon, krypton, xenon, krypton, and hydrogen. The gas is preferably argon or hydrogen. In the second heating step, the fired material is in a temperature range of 1 200 ° C or more and 1 550 ° C or less in a vacuum, or 1 300 ° C or more in an inert gas atmosphere. It is heated in a temperature range of 550 ° C or lower. If the heating temperature is within this temperature range, the decomposition of the Eu-solution β-type Shi Ximing nitrogen oxide can be suppressed. 201217495 Advance to the acid treatment step after the second heating step. In the acid treatment step, the fired product obtained by the second heating step is pulverized. The pulverized fired product is dispersed in a mixed acid solution of hydrofluoric acid and nitric acid at a temperature exceeding 60 ° C. Carry out the mixing. The acid treatment step is carried out by immersing in an acidic liquid to remove the unstabilized low crystalline portion. The temperature of the acid treatment exceeds 60. (:, 1 〇〇 °C below the temperature range. If it is excessively low temperature, the luminous intensity of Eu-soluble β-type lanthanum aluminum oxynitride will decrease. The mixed solution of hydrofluoric acid and nitric acid may also be about 50%. The concentration of hydrofluoric acid is mixed with about 70% of the concentration of nitric acid (hereinafter referred to as the mixed stock solution) or the mixed stock solution is diluted (hereinafter, the mixed stock solution is referred to as a mixed acid solution by dilution). After the mixed stock solution is diluted The concentration of the solution is preferably 25% or more, less than 100%, more preferably 25% or more and 5% by weight. It may not be diluted with a high concentration of a mixed solution of hydrofluoric acid and nitric acid. The diluted low concentration of hydrofluoric acid and nitric acid are mixed. If the mixing ratio of hydrogen acid and nitric acid is about 50% of the concentration of nitric acid from a gas acid of 70%, the ratio is 1~9:9. The ratio of ~ is preferably 3~7: 7~3. 〜1 The above mixed solution is a mixture of concentrated argon fluoride and concentrated nitric acid. The concentration of fluoric acid is 4% or more and 60%. In the following, the concentration of the Kawasaki II is 5 5 % or more and 7 5 % or less. _ • [Example 1] The examples of the present invention will be described with reference to the accompanying drawings. Table 1 shows the examples 丨 to 7 and the comparative examples described below, the surface treatment conditions and the light-emitting characteristics. 2 201217495 [Table i] Mixed acid solution — Acid treatment conditions Luminous special HF: HN〇3 liquid ratio HF (ml) HN〇3 (ml) Steaming water (ml) stock solution concentration (%) Liquid volume (ml) Temperature CC) Time (minutes) β powder input (g) Light absorption rate Internal quantum efficiency External quantum efficiency Example 1 5:5 25 25 150 25 200 70 60 5 72.5% 69.9% 50.7% Example 2 5:5 25 25 150 25 200 80 60 5 71.8% 71.4% 51.2% Example 3 5:5 25 25 150 25 200 90 60 5 71.2% 72.0% 51.3% Example 4 3:7 15 35 150 25 200 80 60 5 71.6% 70.9% 50.8% Example 5 7:3 . 15 150 25 200 80 60 5 71.7% 71.3% 51.1% Example 6 5:5 50 50 100 50 200 80 Bu 60 5 74.7% 70.0% 52.3% Example 7 5:5 50 50 0 100 100 80 60 5 72.9% 72.6% 52.9% Comparative Example 1 5:5 25 25 150 25 200 60 60 5 72.0% 69.2% 49.8% Comparative Example 2 5:5 50 50 Bu 0 100 100 35 60 5 73.6% 68.8% 50.6% Blending α-type nitrogen Huayu Powder (Ube Industries) SN-E10 grade, oxygen content 1.1% by mass, β phase content 4.5% by mass) 95.4% by mass, aluminum nitride powder (F grade of Tokuyama company, oxygen content ο 』 mass%) 3 〇 mass%, alumina powder (TM-DAR grade manufactured by Daming Chemical Co., Ltd.) 0.74% by mass, yttrium oxide powder (RU grade manufactured by Shin-Etsu Chemical Co., Ltd.) 〇71 texture %' and the raw material mixture was 600 g. The raw material mixture obtained by dry mixing for 60 minutes by a rocking mixer (RM_丨0, manufactured by Aichi Electric Co., Ltd.) was passed through a stainless steel sieve having a mesh size of 15 μm to obtain a raw material powder. The obtained raw material powder was filled with a cylindrical gasification side system (W grade of Electric Chemical Industry Co., Ltd.) having a diameter of 10 cm and a height of 9 cm x 〇.5 cm in terms of internal dimensions, in the case of the heater Electric =, as a first heating step, was fired at 1950 C for 15 hours in a pressurized nitrogen atmosphere of 〇9 MPa. The obtained burned product was cleaved, and sieved through a sieve of 45 μm to obtain a powder. The obtained powder was filled with 20 g of a cylindrical boron nitride container having a diameter of 6 cm x a height of 3.5 cm x a thickness of 5 5 cm (electric 氡 = 201217495 工业 -1 grade heating step in vacuum .) 'The electric furnace with carbon heater, as the second heating at 1 400 c for 8 hours, the 50% concentration of gas and gas is smashed ~ (HF) 25ml and 70% concentration of nitric acid (HN03) 25ml mixed to form oxygen ', Japanese, calving. Add 15 〇 nU of steaming water to the mixed stock solution, and dilute the concentration of the mixed stock solution to 25% to adjust the HF + HN〇3 aqueous solution to 20 〇mi. The HF+HNOj solution was kept on the 5g'-side of the powder after the second heating step, and the acid treatment was carried out for 1 hour. After the acid treatment, the acid was sufficiently washed with a steamed crane water, filtered, dried, and passed through a sieve having a mesh size of 45 μm to obtain a W劳 working powder. Then, for the phosphor powder of Example 1, the integrating sphere was used to determine the full-beam luminescence spectrometry (Reference: Journal of Illumination Society, Vol. 83, No. 2 5, Heisei 1 (2000), p87_93, Determination of the efficiency of the lining of the NBS standard phosphor, Okubo and Akira). The excitation light system uses a split xenon light source. The evaluation of the produced β-type lanthanum aluminum oxynitride was carried out as shown in Table ,, and the luminescence characteristics of the light absorptivity, the internal quantum efficiency, and the external quantum efficiency. At the time of this evaluation, a standard reflection plate (Labsphere, Spectralon (registered trademark)) having a reflectance of 99% was placed in the sample portion to measure the spectrum of the excitation light, and if the excitation wavelength was 455 nm, the spectrum of the wavelength range from ~ was The number of excitation photons (Qex) is calculated, and then the phosphor is placed in the sample portion, and the obtained spectral data is used to calculate the photon number (Qref) and the photon number (Qem) of the reflected light of 201217495. The three kinds of photons are used to determine the light absorption rate (=(Qex_Qref)xl〇〇), the internal quantum efficiency (=Qem/(Qex-Qref)xl〇〇), and the external quantum efficiency (=Qem/Qexx 1 00). The number of excitation-reflected photons is in the same wavelength range as the number of photons of the excitation light. The number of fluorescent photons is calculated in the range of 465 to 800 nm when the excitation light is 455 nm. The luminescence characteristics in Example 1 were a light absorption rate of 7 2 5 〇/〇, an internal quantum efficiency of 6.9 %, and an external quantum efficiency of 〇. 7 %. [Example 2] The method for producing the ?-type lanthanum aluminum oxynitride of Example 2 was carried out except that the temperature of the acid treatment was 80. The conditions were the same as in Example 1, and the light absorption rate was 71.8%, the internal quantum efficiency was 71.4%, and the external quantum 5 was 1.2%. [Example 3] Production of β-type lanthanum aluminum oxynitride of Example 3 The method was the same as in Example 1 except that the temperature of the acid treatment was 90 ° C, and the light absorptance was 71.2%, the internal quantum efficiency was 72.0%, and the external amount was 51.3%. [Example 4] Example 4 is an acid treatment step of mixing 15 ml of a gas emulsion (HF) at a concentration of 5% by weight and 35 ml of a nitric acid (HN〇3) at a concentration of 70 °/ to form a mixed stock solution. Adding distilled water to the mixed stock solution 1 5 〇m 1, adjust the HF+HN〇3 aqueous solution 200ml by diluting the 匕δ raw solution to a concentration of 25%. In addition to the powder 5g after the second heating step, the +HNO3 aqueous solution is maintained at 8 (rc) The acid treatment at i hour was performed in the same manner as in Example 1 except that the treatment was carried out for one hour to -10-201217495. In the case of Example 4, the light absorption rate was 71.6%, the internal quantum efficiency was 7 〇9, and the external quantum efficiency was obtained. 5 0 _ 8 %. [Example 5] Example 5 is a concentration of 50% hydrofluoric acid 3 5 m 1 and 7 〇% In the case of Example 5, the light absorption rate was 71.7%, the internal quantum efficiency was 71.3%, and the external quantum efficiency was 51%, except that 15 ml of nitric acid was mixed to form a mixed stock solution. Example 6 Example 6 was prepared by mixing 50% of hydrofluoric acid 5 〇 ml & 7 〇% of nitric acid 50 m 丨 to form a mixed stock solution. Distilled water 100HU' was added to the mixed stock solution to dilute the mixed stock solution. The concentration was adjusted to 200 ml of Ηρ HN〇3 water solution of the township. In addition to the powder 5g after the second heating step, the HF+ ΗΝ03 aqueous solution was maintained at 8 〇〇c, and the acid treatment was performed for i hours. In the case of Example 6, the light absorption rate was 74.7%, the internal quantum efficiency was 70.0%, and the external quantum efficiency was 52.3%. [Comprehensive Example 7] The known Example 7 was not in the acid treatment of Example 6. In the same manner as in the above, the acid absorption rate was 1.9 °/〇, and the internal quantum efficiency was 72%, except that the concentration of the stock solution of 1 〇〇ml was 100%. The external quantum efficiency was 52%. (Comparative Example 1) Comparative Example 1 except The acid treatment temperature was set to 6 (except TC, and was set to the same conditions as in Example 1. The light absorptance was 72.0%, the internal quantum effect -11 - 201217495 rate was 69.2%, and the external quantum efficiency A was 49.8%. Example 2) - Example 2 is the case except that the acid treatment temperature is set to 35. (Beyond:: was carried out under the same conditions as in Example 6. In the case of Comparative Example 2, the light absorptance was 73.6%, the internal quantum efficiency was 68, and the external quantum efficiency was 50.6%. From Examples 1, 2, 3 and Comparative Example 1 show that by increasing the acidity of the acid treatment, the light absorption rate, the internal quantum efficiency, and the external quantum efficiency are all increased. If the processing temperature is more than 6 〇t, i 〇 (rc below, 7 0 C is above 90. (: The following is preferred. It can be seen from the examples 1 to 5 and the comparative example 2 that even if the wave of the mixed I solution in the acid treatment step is thin, the mixed solution is diluted to a concentration of 25 In the range of 〇 〇 〇 〇 , , 任一 比较 比较 比较 比较 比较 β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β When the concentration of the mixed acid solution is diluted, the luminescence property is lowered. [Example 8] Although not shown in the table, an anthrone which is doped with #β-type lanthanum aluminum oxynitride used in the examples and the comparative examples was prepared. A light-emitting device in which a sealing resin is laminated on a light-emitting surface of an LED. If ρ of the embodiment 丨~7 is used After the aluminum oxynitride was allowed to emit light, even after being left at a high temperature of 8 〇t χ humidity of 4 〇% for 2 hours, no decrease in luminescence characteristics was observed. On the other hand, the β type of Comparative Examples 1 and 2 was used. In the light-emitting device of yttrium aluminum oxynitride, it is found that the luminescent property is lowered. -12- 201217495 [Industrial Applicability] When the β-type lanthanum aluminum oxynitride of the present invention is used as a phosphor, ultraviolet to blue light is used. A wide range of wavelengths is excited to exhibit high-brightness green light, so it can be suitably used as a phosphor of a white LED using blue or ultraviolet light as a light source, and can be suitably used in lighting fixtures, image displays. Device, etc. [Simple description of the diagram] No. [Description of main component symbols] No 0 -13-