200848530 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種用以將光學薄膜形成在基材上之 蒸鍍材料及利用此蒸鍍材料而形成之光學薄膜，特別是關 於用以形成使可視及近紫外線域穿透且具有高折射率之光 學薄膜的蒸鍍材料及利用此蒸鍍材料而形成之光學薄膜。 【先前技術】 本説明書中之光學薄膜係指應用在具有光波長程度 之厚度的膜中所產生之光的干涉現象，賦予防止反射或ς 反射等功能而形成之薄膜。 曰 此種光學薄膜係藉由根據為了使顯現所希望之光學 功能而預先設計之膜構成，在基板上設置單層膜或二至^ 層左右之積層膜而形成者。因此，可對照相機鏡頭又 鏡片等光學構件賦予防止反射、增反射、窄波之光 制等之光學功能。該光學薄膜之形成方= 真工瘵鐘法及賤鐘法，但大吝播 得田μ吉* - 一大夕知用在成膜速度及成本方面 ‘兴的真空瘵錢法。在直办 電子束加教奪，“ 係藉由電阻加熱或 電子束加熱寻加熱手段在真空中將 器的蒸鍍材料予以教介，而牡# 一飞坩堝專谷 手段，直空;二:而在基材上形成膜。依據該加熱 w/、 亦進—步有區分為電阻加μ鐘法及雷 子束蒸鍍法之情形。复 一、鍍法及電 亦可將高融點或低_厂I =子束减法係由於在原理上 用。再者，之材料予以蒸鏟，因此經常被採 用冉者，m鍍材料係指在直* φ攸休 源，一般而言依據所 二 用於成膜之蒸鍍 據所形成之膜的折射率之高低程度，分類 5 320085 200848530 :成高=:料;中折射率材料及低折射率材料。 .藉由變更成膜條件特㈣射率材料時，亦可 之値，具體而言係可作：之艇的折射率設定為所希望 ng ,. 成為具有比材料更低之抽 即與中折射率相當，::二(：寬緻密性），所得之膜 t分，折射率之變動大真 時間。由於這點，膜之批如玄 八又動铋疋為止需要長 來決定，而伟忙、商木射率通常並非依成膜條件之設定 而係依適當之材料的選擇、組合來決定。 =折射率材料（特別是折射率為21以 形成讓可視光域穿透之膜T 鈕之氧化物、或由該耸… °巳知有由鈦、鈮或 鍅之二元純化*Γ、κ》構成之多元系氧化物、鈦及 俜指H 2、 再者，在本説明書中，「多元系氧化物」 或固溶體氧化物等屬凡素之混合氧化物、複合氧化物 光域=;τ、？或㈣之材料而形成之膜，在可視 收夫，牙、、上雖沒有問題，但在近紫外線波長域中吸 而難t適用在亦於近紫外線域中使用的光學構件。 可八Z、讀材料係依該材料所具有之融點及蒸氣壓’ 斜"M、、材料固體不經由溶融而直接氣化之（昇華性）材 η^後馬上就氣化之（半溶融性）材料、及經過溶融 過程成為最穩忿：:虫：：三種類。其中，可使蒸" ’、4融性材料。這是由於藉由因熔融而 6 320085 2OU848530 :形成將容器之内壁作為鑄 得平滑之蒸發面， 狀綠融池（pool)，即可獲 產生速度（基發逹Ϊ Μ發面而容易控制材料蒸氣之 上述欽及^^成均勾且均質之骐。 材料’使用該材料將難以形V勻半炫融性之 物添加在上述鈦、域不會吸收之添加 ，則有解決上述課題之可能性材抖而組成的多元系材料， 1 然而，多元系材料在採用直办一Μ 之蒸氣麼不同，—般而十合2/、二愁鍍法時，由於各成分 分之比）而蒸發之情形：：不按二其材料之組成（各成 與材料之电成ρ’經蒸發之蒸氣的組成未必 材料組成會變化，由此形成時間或蒸鑛次數，其 有難以連續多數-欠制作H膜組成亦會變化，因此大多 吃Λ夕要文一人裂作具有所希望 情形特別是在以下情形居多的^形。這種 之成膜操作時，必須要儘。=^慮2等之膜層數多 料，以儘可能減少材料之補仏次數一次之蒸鑛材 鑛，在;補給之前所進行之複數次的蒸 性材料，^若^ ='、、、錢」。此外，即使為熔融 變化的乂 會隨著蒸錢時間或蒸鑛次數而 夂化的多u㈣時，並不適合連續蒸鑛。 源並:屬：:元:：!之膜亦可藉由使用複數個加熱蒸發 /使屬於各7〇素成分之蒸鍍材料獨立蒸 条鍍)。然而，多元蒸鍍之用以獲得所希望之膜組成的= 320085 7 200848530 因此實際上幾乎不會使用 條件難以最適化，且成本亦高 在研究用途以外。 因此 μ学㈣之許多讀中雖例 糸膜，但在採用真空蒸鍍法時 ：°種之夕兀 來製作具有-定特性之多元系的^上難以猎由連續蒸鍰 季，：：來户f專利文獻1及2,，揭示有鈦及鑭之二元 :物，在專利文獻3中’揭示有鈦及釤之二元季氧化 / 為解決上述課題者，亦即為可形成在近= 吸收之膜且具_融性、可進行連續蒸鑛的高折 :::::然而，即使為上述之材料’在使用該材料而形 成之先學缚膜的特性、甚至在材料成膜時所示之動作方 面’仍有下述之課題。 _ I先，第1課題係在光學薄膜之特性方面，在專利文 :、之材料中’最大也只能形成2. j左右之折射率的膜， ^為高，射率材料之折射率並不可謂具有充分高之値。、再 、、，在從近紫外線（短波長）到可視光部及至近紅外線（長 波長）^皮長區域中雖無吸收（透明），但無唆收之最短^ 長係接近可視光部之約36〇nm。再者，在專利文獻2及3 之材料中，雖可形成折射率超過21之高折射率膜，但與 專，文獻1同様地，無吸收之最短波長係依然為接近可視 光P之約360nm，而無法充分地使近紫外線域之光穿透（無 ^收）。如此，用以形成折射率高達超過21程度、且不僅 I視光域，連近紫外線域之光亦能穿透之膜的蒸鍍材料至 今尚未為人所知。 8 320085 200848530 1 ★ &題係在材料成膜時所示之氣 .點，以下與成膜方法一併説明。即使在的問題 文獻1至3之蒸鍍材料亦皆係主要使用在電；：：’專利 用熔融性之蒸鍍材料之以 、電子束療鍍。使 而言係如以下所述進行。首先，：：:斤二行的成膜’―般 束加熱將蒸鍍材料予以 ,'，，、别处理，係藉由電子 電子束再度，昭射在二 形成溶融池。接著，藉由將 射在該融池並使材料蒸氣產生， =:。在成膜時將電子束連續照射在炫融池之/ ^ 同之材料，亦有以下2種材料:⑴由於因 “心射點適度地擴散至整個= 〇 ^ ^羔表面，因此可容易地控制蒸發速度，結果 =易地形，具有所希望特性之膜的材料；⑺由於^只 卞、ΐ射束…、射點附近且溶融池會隨著蒸鐘時間而變形成 Μ、等U保持平滑之蒸發面，因此難以進行墓發速 度之控制，且不得不進行頻繁之補給的材料。專利讀1 至3之材料皆係屬於後者（2)，若為了儘量減低材料之補 、、’S人數而連、，、|進行条鐘，為了避免熱之集中，必須要有在 蒸鐘操作中—邊適當地變更電子束之照射位置—邊進行成 膜等的特別對策。再者，即使採取了上述對策，賦予在熔 ㉔池之熱77佈狀悲亦容易變動，結果，難以控制蒸發速度。 如上所述’即使未施行電子束操作上之特別的對策亦可使 所希望之高折射率之膜容易形成的多元系蒸鍍材料，至今 尚未為人所知。 (專利文獻1)曰本專利2720959號公報 9 320085 200848530 : (專利文獻1日本特開2002-226967號公報 ， （專利文獻3)日本特開2__18_4號 【發明内容】 報 (發明所欲解決之課題） 使用該蒸鑛她^ 鐘，;子係具㈣性且可進行連續蒸 f使比以往更卢二士亦可容易地控制蒸發速度，可 便比Μ在更廣之波長範圍（ 且用以將呈右古 、 ”卜、:友域）之光穿透， ^、有同折射率之光學薄膜予以成膜的材料。 柄明人等係針對各種成分 研究之結果，而尋拈屮±^Ρ12 …、锻材科精〜 蒸鐘材料。再者，得知由：= 之：元系氧化物所構成的 生的蒸氣之組成，並不士：：：成之蒸刪所產 氣壓所決定，並發現藉由==習知之各成分之蒸 ^ m ^ 9 才寸&莉^圍之錕與鑭之组忐士 的蒸鍍材料及使用該等蒸鍍薄 =解決上述所有問題，而完成本發明。“祕， (解決課題之手段） 本發明係以下之發明。 1 · 種蒸鑛材料，係由銳及繃 _ 一 / 鈮及鑭之二元系气仆札n ·】之—兀系氧化物、或由 蒸物二二ΓΓ㈣銳及/或金屬鑭所構成者，該 %徵為·該洛鍍材料中 25 ·· 75至90 ·· 10。 十中之銳與鑭之莫耳比為 10 1 .如上述1所記载之蒸錢材料，其中，銳與鑭之莫耳 320085 200848530 :比為 35 ·· 65 至 60 : 40。 - 3·如上述1或2所記載之# 料為燒結體或熔融體。 “、、、x材料，其中，該蒸鍍材 4·如上述1至3中任一項 一 氧化鑭之含有率為5重量％以下。5载之条鑛材料，其中， 截η ^光予薄膜之製造方法，係採用上述1至4所記 載之条鍍材料’並藉由真空蒸鍍法而形成。 6·如上述5所記载之光學薄 空蒸鑛法係電子束蒸鍵法。 之衣&方法’其中’真 士 /.如上述6所記載之光學薄膜之製造方法，其中，在 成膜中固定電子束之照射位置。 /、 8· —種光學薄膜，係藉由卜 法所得者。由上迷5至7所記载之製造方 本發明之蒸鍍材料之特徵為：由鈮及斕之二元系氧化 物所構成’且該銳與鑭之莫耳比為25 : 75至9 / m鑭之"元系氧化物」係純化鈮純化鑭之混合 mr之複合氧化物、混合有2種以上該複合氧化物 ::二物、銳及氧化鑭之複合氧化物與氧化銳之混合物、 銳及鑭之複合氧化物與氧化鑭之混合物、銳與鑭之固溶體 軋化物等由鈮與鑭及氧所構成之所有物質。 化氧化鑭、氧⑽歧與鑭之複合氧化物係在氧 ^Cn)(La2〇3)^,trb(v)CNb2〇5)^ 二學;^最^ t LaNb5〇14'LaN⑽之通常環境氣體 中化予！ 生取疋之氧化物’除此之外，亦可為㈤之類的 320085 11 200848530 • 氧化亞鑭、Nb02、Nb203、NbO之氧化亞鈮或LaNb7012 之次氧化狀態的複合氧化物等次氧化物。該種次氧化物、 或包含次氧化物之蒸鍍材料（以下統稱「次氧化物蒸鍍材 料」）係含氧率更小之材料，因此在成膜時及作為其前處理 之熔融時不容易發生氧氣之脫離。因此，易於控制蒸鍍中 之蒸鍍裝置内的環境氣體壓力，且容易形成具有所希望特 性之膜。本發明之次氧化物蒸鑛材料係除了上述LaNbyO!2 以外，可例示 Nb0+LaNb04、Nb02+LaNb04 或 Nb02+ ’ La3Nb07+LaNb04之構成的二元系氧化物。 本發明之第2蒸鍍材料係由（a)鈮及鑭之二元系氧 化物、及（b)金屬鈮及/或金屬鑭所構成者，該蒸鍍材料之 特徵為：該蒸鍍材料中之鈮與鑭之莫耳比為25: 75至90 : 10。在此，「銳及鍚]之二元系氧化物」之定義為如上所述。 該種弟2条鍵材料之構成可例不· Nb+L a] Ο3、L a+Nb 20 5、 Nb+La+Nb205、Nb+LaO、Nb+LaNb04、Nb+LaNb7012、 I Nb+La3Nb07+ LaNb04、Nb+La3Nb07+LaNb7012、Nb+Nb02+ La3Nb09+LaNb04 或 Nb+Nb0+Nb02+La3Nb〇9+ LaNb04 o 再者，以下係將含有該金屬鈮及/或金屬鑭之蒸鍍材料稱為 「含有金屬之蒸鍍材料」。含有金屬之蒸鍍材料亦與次氧化 物蒸鍍材料同様地為含氧率較小之材料，因此由上述之理 由得知，易於形成具有所希望特性之膜。 再者，本發明之蒸鍍材料係只要是不損及前述之本發 明効果之程度、亦即相對於鈮及鑭之二元系氧化物至5mol %為止者，添加銳及鑭之氧化物以外的材料亦無妨。該種 12 320085 200848530 :材料可例示氧化叙、氧化亂、氧化錦、氧化鏡等。 , 鈮與鑭之莫耳比在25 ·· 75至90 · 1n — ^ 料，由於莫耳比之變化會隨編鑛時外的材 大，因此不適於連續_。數而變 莫耳％之材料難以充分地使近紫外線域之光0 面，低於25莫耳％之材料則 方 膜。 成充分鬲之折射率的 再者，若鈮與鑭之莫耳比為35·· 65至60: 4η , 連續蒸鍍逐次形成之膜的折射率 貝1由 且能以更長時間及更多次數製作具有 較為理想。特別是，折射率之變動可抑制在⑽左右口此 由二= 材料並無特別地限定其形態，但 成型體：狀:lit:看，較佳為作成顆粒物等 望之光學特性的膜。再者，::體 左右者時H以崎連續蒸料之材料的補給，因: 較為理想。此外，較佳為經由成型體之鍛燒 及:體或成型體之經由炫融而得之溶融體。未經 度：不大，因此體積會因蒸鑛時之材料 1者減厂而必須頻繁地進行材料之補給。 再者，本發明之蒸鑛材料較 鑭的含有率在5重量％以下。=;〇:仏〇之氧化 大，若入右安和、ft S舌曰 疋由於乳化鑭之吸濕性 大右3有千起過5重量％，則會與空氣令之水分產生反 320085 13 200848530 應而化學變化成更低密度之氫氧化鑭，若為成型體、燒結 體或熔融體時，會膨脹崩潰而成為粉狀。不僅是該粉狀， 若將包含較多氫氧化鑭之蒸鍍材料直接使用於蒸鍍時，在 加熱之際不但會產生材料之飛散，而且會產生顯著之水分 放出，會在所形成之膜產生物理性之缺陷，且由蒸鍍裝置 之維護之觀點來看並不理想。 本叙明之蒸鐘材料係可利用例如以下之方法製造。 r 若為燒結體，係採用氧化铌（v)及氧化銀Um)之 粉體作為起始原料，並以預定之比率混合氧化銳（V)及 ^化鑭（m)’將所得之混合物粉體予以造粒及/或成型， 猎此，成為0.1至10mm左右之尺寸的成型體後，可藉由 f =氣中、真空中或氬等惰性氣體中以預定之溫度鍛燒來 衣每再者，若為熔融體，則可藉由在預定之溫度下將混 體或其成型體予以熔融來製造。再者，鍛燒溫度及 熔一溫度之最適溫度雖亦依構成蒸鍍材料之鈮與鑭的莫耳 同’但鍛燒溫度大致以9〇〇至17〇〇。。為佳，熔融溫 度大致以1350至190(rc為佳。 二，製造次氧化物蒸鍍材料時’除了使用氧化鈮 為起>=化鑭（m)外亦可使用金屬織/或金屬鑭來作 為i始材料。若為該種構成之 金屬與氧化物產生介風；^處 隹娵洗次‘融％可使 料。或者令 化予反應，而可製造次氧化物蒸鍍材 料，以取代氧化鈮，或次氧化鑭作為起始原 藉由將僅 )及/或氧化鑭（羾）。再者，亦可 曰、帛氧化銳（V)及氧化鑭（m)作為起始原料 320085 14 200848530 而製造之蒸鍍材料予以脫氧（de〇xygenate)來製造。脫氧 之方法係可縣在例如氫㈣元性氣體下的加熱處理。 再者在衣以含有金屬蒸鍍材料之情形下，起始原料 二化物蒸鏟材料之情形相同。然而，藉由應 物讀材料之情形不㈣製造條件（例如 鍛燒時將鍛燒溫度設定為鲂供 ★ _ ^ 為叙低，或將鍛燒時間設定為較 ^)，而在使金屬本身殘存之狀態完成製造。如此，可製造 / 含有金屬之蒸鍍材料。此外玄 # ° — 卜亦可猎由在銳及鑭之二元系 虱化物之瘵鍍材料添加金屬鈮及/或全屬_，ν 復進行锻燒或溶融來製造。^屬綱亚依情況不同 籍由使用以上所述本發明 薄膜，不僅可使整個可視光;料所形成的光學 360 & 光域牙透，亦可使近紫外線域（比 nm為紐之波長域）穿透、 折射率2 15 $ 7 ^ ^ 在波長450nm附近具有 率羊至2.35(較佳為心至2.35左右）之高折射 用本本發明之光學薄膜的製造方法之特徵為使 用本發明之療鍍材料，並藉由直 便 發明中之「直办亨棘、、t 一二…鍍法而形成者。在本 之補助手又/」亦包含在該方法追加成膜加工上 之補助手段的離子鍍覆法或離子、— 上 明之墓#材t +¾ μ & 、‘χ,。為了蒸錢像本發 ==的_材料，較佳為採用 :==。再者，即使採用電子束蒸鍍法，亦由 材枓，且歷經蒸鑛時間後亦保持平之 ’、月至正胜 易地控制蒸發速度“士月之《面’因此可容 '、口果可谷易地製造具有所希望特性 320085 15 200848530 之光學薄膜。再者，由於可更加降低 本發明之蒸錢材料時，即便在電子束操作上不需要特2 如即使在成膜中固定電子束之照射位 = 薄膜。此外，若將例如蒸鍵材料裝 器時’此時之電子束的照射位置較佳為 如此，即使採用電子炭蒗 、度且進行連Ρ束 可容易地控制蒸發速 时b及鑭之4技元素的組合來 構成条鍍材料而達成。 ^ 【實施方式】 (實本發明之實施例，但本發明並非限定於此。 ，重量比32.9·· 67](銳與鑭之莫耳比為π.5: 6 〜合氧化鈮（V)及氧化鑭（ .） 合物造粒成1至3mm之顆粒狀丨亚將該粉體混 顆粒狀，在大氣中以1300t鍛;ί:圭4 此獲得顆粒狀之蒸鑛材料。該材料係由第所 不之X線繞射圖案鑑別為以長〇7及L祕〇4。 將裝填有該蒸鍍材料之銅製㈣财 空蒸鑛裝置，並將裝置内排氣至】猶3pa後，藉 二加熱溶融蒸鐘材料，以形成溶融池。接著，導入氧= ，為1.。爲，再將電子束僅照射在炼融池之= =心氣產生，在預先安^裝置内且加熱至烟 c之基村上’以成膜逮& 〇.9細/秒成膜至物理性膜厚達 16 320085 200848530 • 250_為j。在僅交換基材且完全未補給蒸鑛材料下 .^該成膜。針對所得之各個膜’藉由分光光度計、: 長450nm之折射率，廿#丄、 出波 之莫耳比。將*要矣 成分析求出鈮與鑭 甘/示在第1表及第2表，不論成膜次數 ；；斤射率及莫耳比皆㈤，且所有之膜皆從285nm至可視 域沒有確認到吸收。如該285nm，將在使波長從 = !;Γ線域側變短時’開始產生膜之光吸收，且於分先 牙透¥開始急遽下降時之波長稱為「最短穿透波長」。另一 二，二2 述之成膜結束後之蒸物 九、、、片’侍知儘謂電子束僅照射在溶 亦保持平滑之蒸發面。 之中〜4， 再者+，波長450nm之折射率的算出方法係如下所述。 得分光曲1由市售之分光光度計來測量分光穿透率，以獲 折射率。利用該分光曲線及·Μ職之分散式來算出 折射率之二2ΕΙΧΜΕ服之分散式係以求出*之波長與 叮对早之關係為目的經常使用之公式，以 • n== SQRT [1+Α/(1+Β/λ 2)] ^ ^ t 在此，n為折射率，λ為波長，A與B孫冰—、、士 、共折射率之關係之係數。且「 亍、'、’、疋/ 部之平方根者。 」係表-叶算上式[] (’、施例2) 以重量比⑹：….0 (銳與鑭之莫耳比為6〇.〇: 320085 17 200848530 後〇)混合氧化鈮（v )及氧化 .並將該粉體混合物成刑A 1 5 q 主屬鈮之粉體， 锻燒4小日士 t 23麵之旋劑狀，在真空中以 ^ i χ % 才糟此獲侍錠劑狀之蒸鍍材料。哕材# 係由X線繞射圖案鐘別為LaNb〇4及Nb〇。/该材科 針對使用該蒸鍍材料並 成膜所得之各個膜，求出wy _1R桂之方法進行 波長、及銳盘綱之:^皮長450nm之折射率、最短穿透 不論成膜次數=耳率示在第1表… 3〇5_。 〃斤射革及莫耳比皆同’且最短穿透波長為 (實施例3) 以重量比80.3 : 19 7 ^ 混合氧化r 鑭之莫耳比為83·3: K7) 合物成型為\至3及乳化鋼（m)之粉體’並將該粉體混 小之錠劑狀，在大氣中以12_锻燒4 成膜例1同様之方法進行 不論成膜次數其折⑽ '表及Μ表， 330nm。 及旲耳比白同，且最短穿透波長為 (貫施例4 ) 混合氧化二^5.9.从1 (銳與鑭之莫耳比為30.0: 70.0) 合物造心！至3及氧化鑭（幻之粉體，並將該粉體混 ' mm之顆粒狀，在大氣中以1500°C鍛燒4 18 320085 200848530 .α 木 L 別為 La3Nb〇7 j LaNb〇4。 成膜:=:Γ蒸鍍材料並以與實施例1同様之方法進行 、t之各個膜’求出波長45〇_之 波長、及錕與鑭之莫耳比。將結果表示在第;及取第=透 不論成膜次數JL折鼾、玄1 h 乐1表及弟2表， 27〇麵。折射率及4耳比皆同’且最短穿透波長為 (實施例5 ) f 50 〇Γ、、^^44·3 : 54·3 : M (銳錢之莫耳比為 5〇.〇 : 並二：:乳化銳（V)、氧化鑭⑻及氧化紹之粉體， "將該“混合物造粒為U3mm 1500°C鍛燒4 /丨、护 —， 了狀在大虱中以 量而未被鑑別^者為LaNb〇4。此外，氧化㈣因微 成膜=使用該蒸鍍材料並以與實施们同様之方法進行 波長及銳與鑭之莫耳比。將結果表示在第牙透 2不9=膜次數其折射率及莫耳比皆同，且最短穿透波二 (實施例6 ) ：/·7 37.5 : 並將奸… 减鑭（皿）及金屬鈮之粉體， 猎此獲得錠劑狀之蒸鑛材料。該材料 320085 19 200848530 •係由x線繞射圖案梦为丨炎τ •針對使用7、LaNb0^Nb。 成膜所得之各個膜，施例1同様之方法進行 波長、及鈮與鑭之莫耳 取短牙透 不論成膜次數其折射率及^且\絲不在弟1表及第2表， 290nm。 及4耳比^同，且最短穿透波長為 (實施例7 ) 16 7)^比53.3:21.8:24.9 (銳與鑭之莫耳比為83.3: 上〇·7)爲合氧化鈮（V )、、 並將該粉體混合物成_ i if (m)及金屬銳之粉體， 130(TC锻燒3小日±以1至3麵之錠劑狀’在真空中以 俜由X㈣狀之鐘材料。該材料 ::線繞射圖案鐘別為LaNb3〇一⑽^ 成膜以與實施例1同様之方法進行 波長、及銳盘、苴且 0㈣之折射率、最短穿透 335nm 〇 ，、 莫耳比皆同，且最短穿透波長為 (比較例1) 、、曰入：重量比90.4: 9.6 (鈮與鑭之莫耳比為92 3 :7 7) 合：：(V)及氧化爛⑻之粉體，並將該靡 小日士 4為i至3 m m之顆粒狀，在大氣中以！綱。c锻燒4 圖：=獲得顆粒狀之蒸鍍材料。該材料係由X線繞射 圖案鐘別為。勘5014及Nb2〇5。 320085 20 200848530 •成膜鑛f料並以與實施例1同様之方法進行 波長、及鈮與鑭之莫耳：：長CO—之折射率、最短穿透 隨著成膜次數 最短穿透波長亦二折射率會降低，且莫耳比亦會變化， 之光穿透者。為365nm，不能説是能充分讓近紫外線域 (比較例2) :重量比从叫銳與鑭之莫耳比為2〇 、、曰 化鑭⑷之粉體™ ,± 5 J ^ mm之顆粒狀，在大氣中以15〇〇。〇鍛燒4 ^稭此獲得顆粒狀之蒸鐘材料。 量二但顆粒體並未崩潰。而且，由其增加質 ^出氧化鑭之含有率為2·5重量％。 針對使用該蒸鍍材料並以與實施例i同様之 2所得之各個膜，求出波長一折射率、最短;； :及銳與鑭之莫耳比。將結果表示在第！表及第2表丫 =牙透波長為260咖，雖能充分讓近紫外線域穿透，作 了者成膜讀之增加，折射率會增加，且莫耳比亦一 (比較例3) 匕。 以下，表示將本發明之蒸鍍材料的鈮原料以 取代時之比較例。 以重罝比29.3 : 68.2 : 2.5 (鈦與鑭之莫耳比為5〇 〇 . 5〇.〇)混合氧化鈦（IV)、氧化鑭（m)及金屬鈦之粉體，· 320085 21 200848530 並將該粉體混合物造粒為 17〇〇°C鍛燒5小時，藉麵狀，在真空中以 除了使用該蒸鑛==:蒸鍍材料。 施例1同様之方法進行成^數為1次以外，以與實 束後之蒸鐘材料的照片，由顯示上述之成膜結 有很大之凹陷。儘管只進行;電子束之位置 被深深地挖掘至將到達_之底部的程度 時之比車I例表不將本發明之蒸鑛材料的鑭以镱原料來取代 以重量比44·〇 : 56 〇 Γ如幽拉 — 混合氧化鈮（V)、氧化與镱之莫耳比為4G.f) 物造粒為i至3mm之顆:乂 )之粉體’並將該粉體混合 J ^ — 顆粒狀，在真空中以17001鍛燒4 小$，猎此獲得顆粒狀之蒸鍍材料。 ，了❹該蒸鍍材料且成膜次數為，以 進行成膜。第4圖係顯示上述之成膜結 :照片，由該照片得知，儘管只進行1次 」射電子束之位置有很大之凹陷，且掛禍之底 部分露出。與比較例3同様地，完全不能進行連續 (比較例5) 4同糕夕了，^中从12〇0。。鍛燒4小時以外，以與實施例 。' 後得㈣狀之蒸㈣料。崎料係由X線繞 320085 22 200848530 射圖〆：鑑別為LaNb〇4、La3Nb〇7及㈣。因吸濕看得 出質量之增力”顆粒體會在製作一日後崩潰而變化為粉 狀由其增加質量异出氧化鑭之含有率時為6·3重量％。 將裝填有該粉狀蒸鍍材料之銅製的坩堝安裝在市售 之^空蒸鐘裝置内，並將裝置内排氣至l.OxWPa後，^ 由电子束進行加熱時，由於材料會激烈飛散，因此造成成 膜中斷。 [第1表]200848530 IX. Description of the Invention: [Technical Field] The present invention relates to an evaporation material for forming an optical film on a substrate and an optical film formed by using the evaporation material, particularly for forming A vapor deposition material that allows an optical film that has a high refractive index to penetrate through the near ultraviolet region and an optical film that is formed using the vapor deposition material. [Prior Art] The optical film in the present specification refers to a film formed by applying an interference phenomenon of light generated in a film having a thickness of a light wavelength, and imparting functions such as prevention of reflection or reflection.形成 Such an optical film is formed by a film which is previously designed in order to exhibit a desired optical function, and a single layer film or a laminated film of two to two layers is formed on the substrate. Therefore, it is possible to impart an optical function of preventing reflection, reflection enhancement, and narrow-wave light to an optical member such as a camera lens or a lens. The formation of the optical film = the real work 瘵 clock method and the 贱 clock method, but the big 吝 得 得 得 得 μ 吉 - - - - - - - - - - - - - - - - - - 一大 一大 一大 一大 一大 一大 一大 一大 一大 一大 。 。 。 In the direct operation of the electron beam plus teaching, "by means of resistance heating or electron beam heating to find heating means to vacuum the material in the vacuum, and the mud #一飞坩埚谷谷 means, straight sky; The film is formed on the substrate. According to the heating w/, the step is further divided into a resistance plus a clock method and a thunder beam evaporation method. The first method, the plating method and the electricity can also have a high melting point or Low_factor I = beamlet subtraction system is used in principle. Furthermore, the material is steamed shovel, so it is often used as a shovel, m-plated material refers to the source of direct φ攸, generally based on For the vapor deposition of film formation, according to the degree of refractive index of the film formed, classification 5 320085 200848530: high =: material; medium refractive index material and low refractive index material. By changing the film forming condition special (four) shot When the material is rate, it can also be used. Specifically, the refractive index of the boat can be set to the desired ng. It is equivalent to the lower refractive index of the material, and is equivalent to the medium refractive index. :: Two (: wide and dense) Sex), the obtained film t points, the refractive index changes greatly time. Because of this, the film batch is like a black and white疋 需要 需要 需要 需要 伟 伟 , , , , , , , , , , , , , , , , , , , , , , , , , , The oxide of the T-button of the film penetrated by the visible light field, or the multi-layer oxide composed of the binary purification of titanium, ruthenium or osmium, Γ, κ, and the H 2 Further, in the present specification, a film formed of a material such as a mixed oxide of a quinone, a composite oxide, or a material of a composite oxide, such as a "multi-component oxide" or a solid solution oxide, is formed by a material of τ, ?, or (4). Although there is no problem in the visible, teeth, and upper, it is difficult to absorb in the near-ultraviolet wavelength range. It is suitable for optical components that are also used in the near-ultraviolet field. The eight-Z and the reading materials are based on the material. Melting point and vapor pressure 'oblique', M, material solids that are not vaporized directly by melting (sublimation) material η^ immediately vaporized (semi-melt) material, and become the most stable after the melting process :: worm:: three kinds. Among them, steaming " ', 4 melting materials. This is because by the melting of 6 320085 2OU848530: forming the inner wall of the container as a smooth evaporation surface, a green pool, the speed can be obtained (the base hair Μ hair surface is easy to control the material The above-mentioned vapours of the vapours are homogenized and homogenized. The material 'use of this material to add the hard-to-shape V-semi-smooth material to the above titanium, the domain does not absorb the addition, there is a possibility to solve the above problems. A multi-component material composed of a trembling material, 1 However, the multi-component material is different in the use of a direct steam, as in the case of the ten-in-two/two-inch plating method, due to the ratio of the components. The situation: not according to the composition of the material (the composition of each material and the material ρ' vaporized vapor composition does not necessarily change the composition of the material, thereby forming the time or the number of steaming, which is difficult to continue the majority - underproduction The composition of the H film will also change, so most of them will be cut into a shape with a desired situation, especially in the following cases. This film forming operation must be done. =^Consider the number of layers of 2, etc., in order to reduce the number of times the material is replenished once, and to steam the ore material, in the multiple times before the replenishment, ^ if ^ = ', , money". In addition, even if the enthalpy of melting changes with the steaming time or the number of times of steaming, it is not suitable for continuous steaming. Source: The film of genus:: yuan::! can also be independently steamed by using a plurality of heating evaporation/vapor deposition materials belonging to each of the 7-component components. However, multi-evaporation is used to obtain the desired film composition = 320085 7 200848530. Therefore, it is practically difficult to optimize conditions, and the cost is also high. Therefore, many of the readings of μ (4) are enamel films, but when vacuum evaporation is used, it is difficult to hunt the continuous steaming season by using the scorpion of the species to produce a multi-system with a certain characteristic. Patent Document 1 and 2 disclose a binary material of titanium and tantalum, and in Patent Document 3, 'disclosed is a binary quaternary oxidation of titanium and lanthanum / for solving the above problem, that is, it can be formed in the vicinity = Absorbed film and _ fused, high-fold for continuous steaming::::: However, even for the above-mentioned materials, the properties of the precursors formed in the use of the material, even in the film formation of the material At the time of the action shown, there are still the following problems. _ I first, the first subject is in the characteristics of the optical film, in the patent: material, the largest can only form a film with a refractive index of about 2. j, ^ is high, the refractive index of the material of the rate Can not be said to have a full height. , and again, there is no absorption (transparency) in the area from near ultraviolet (short wavelength) to visible light and to near infrared (long wavelength). However, the shortest length is not close to the visible light. About 36〇nm. Further, in the materials of Patent Documents 2 and 3, a high refractive index film having a refractive index of more than 21 can be formed, but in the same manner as in the literature 1, the shortest wavelength system without absorption is still about 360 nm close to the visible light P. , but can not fully penetrate the light in the near ultraviolet region (nothing). Thus, an evaporation material for forming a film having a refractive index of more than 21 degrees and which is not only in the optical field but also in the vicinity of the ultraviolet ray is not known. 8 320085 200848530 1 ★ & The title is the gas shown in the film formation. The point is described below together with the film formation method. Even in the problems, the vapor-deposited materials of documents 1 to 3 are mainly used in electricity;::' patents use fusible vapor deposition materials for electron beam plating. This is done as described below. First, the ::: filming of the two rows of the film "--bundle heating, the vapor deposition material is given, ',,, and other treatments, by the electron beam again, the first shot forms a molten pool. Next, by firing in the bath and causing the material vapor to be generated, =:. At the time of film formation, the electron beam is continuously irradiated to the same material in the smelting pool. There are also the following two materials: (1) It can be easily controlled because the "spotting point spreads moderately to the entire surface of the =^^^ Evaporation rate, result = easy to topography, material with the desired characteristics of the film; (7) due to ^ 卞, ΐ beam ..., near the shooting point and the melting pool will become Μ with the steaming time, etc. U keeps smooth Evaporation surface, it is difficult to control the speed of the tomb, and has to make frequent replenishment materials. The materials of patent readings 1 to 3 belong to the latter (2), in order to minimize the amount of material, the number of 'S In order to avoid the concentration of heat, it is necessary to carry out special measures such as film formation in the steaming operation while appropriately changing the irradiation position of the electron beam. Furthermore, even if the above is taken The countermeasures are given to the heat in the pool 24, and the cloth sorrow is also easy to change. As a result, it is difficult to control the evaporation speed. As described above, the film having the desired high refractive index can be easily made even if the special countermeasure for the electron beam operation is not performed. form A multi-component vapor deposition material has not been known until now. (Patent Document 1) Japanese Patent No. 2720959, No. JP-A-2002-226967 (Patent Document 3) Japanese Patent Laid-Open No. 2-_18_4 No. [Summary of the Invention] The report (the subject to be solved by the invention) uses the steamed mine to make it a clock, and the sub-system has a (four) nature and can be continuously steamed to make it easier to control the evaporation rate than the former. It is a material that is formed by filming optical films with the same refractive index in a wider wavelength range (and used to penetrate light from the right, "Bu", "Friends". For the results of various component studies, we search for ±^Ρ12 ..., forging materials - steaming materials. Furthermore, we know that the composition of raw vapors consisting of: =: meta-oxides is not士::: determined by the pressure of the steam produced by the steaming, and found that by the == conventional ingredients of the steam ^ m ^ 9 寸 amp 莉 ^ ^ 围 锟 锟 锟 锟 锟 及 及 及 及The use of these vapor deposition thin = solve all the above problems, and complete the present invention. "Secret, (solving class The present invention is the invention of the following: 1 · A kind of steamed ore material, which is composed of a sharp and stretched _ _ / 铌 镧 二元 n n 】 】 】 】 】 】 】 】 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物ΓΓ (4) Sharp and / or metal 镧 constitute, the % levy is ~ · 75 ~ 90 · · 10 in the Luo plating material. The ratio of the sharpness of the ten to the 莫 莫 is 10 1 . As noted above The steamed money material, wherein, the sharp and the squirrel 320085 200848530: the ratio is 35 ·· 65 to 60: 40. - 3 · The material described in the above 1 or 2 is a sintered body or a melt. The material of the vapor deposition material 4, wherein the content of ruthenium oxide according to any one of the above 1 to 3 is 5% by weight or less. A five-strand ore material, wherein the method of producing a film is carried out by using a strip plating material as described in the above 1 to 4 and formed by a vacuum evaporation method. 6. The optical thin steaming method electron beam steaming method according to the above 5. The method of producing an optical film according to the above 6, wherein the irradiation position of the electron beam is fixed in the film formation. /, 8 · - an optical film, obtained by the method. The vapor-deposited material of the present invention is characterized by the fact that the vapor-deposited material of the present invention is composed of a binary oxide of cerium and lanthanum and the molar ratio of the sharp and the yttrium is 25:75 to 9. / m镧之"Meta-based oxide is a composite oxide of a mixed mr purified and purified, and two or more kinds of the composite oxide are mixed: a composite oxide of two substances, sharp and yttrium oxide, and a oxidized sharp A mixture of a mixture of cerium and lanthanum and oxygen, such as a mixture of a composite oxide of lanthanum and cerium and cerium oxide, a solid solution of a sharp and cerium. The complex oxides of yttrium oxide, oxygen (10) and yttrium are in the general environment of oxygen (Cn) (La2〇3)^, trb(v)CNb2〇5)^, and ^^^^^^^^^^^^^^^^^^ Gas neutralization! In addition to the above, it may also be 320085 11 200848530 such as (5) • Oxide oxide, Nb02, Nb203, NbO oxide, or LaNb7012, secondary oxidation oxide, etc. . This sub-oxide or a vapor-deposited material containing a suboxide (hereinafter collectively referred to as "sub-oxide evaporation material") is a material having a smaller oxygen content, and therefore is not formed at the time of film formation and as a pretreatment thereof. Oxygen detachment is prone to occur. Therefore, it is easy to control the pressure of the ambient gas in the vapor deposition device in the vapor deposition, and it is easy to form a film having desired characteristics. The secondary oxide vapor-smelting material of the present invention may be a binary oxide of Nb0+LaNb04, Nb02+LaNb04 or Nb02+'La3Nb07+LaNb04 in addition to the above-mentioned LaNbyO!2. The second vapor deposition material of the present invention is composed of (a) a binary oxide of ruthenium and osmium, and (b) a metal ruthenium and/or a metal ruthenium, and the vapor deposition material is characterized by the vapor deposition material. The molar ratio of 中 铌 and 镧 is 25: 75 to 90: 10. Here, the definition of the binary oxide of "sharp and 钖" is as described above. The composition of the two key materials of the younger brother can be Nb+L a] Ο3, L a+Nb 20 5, Nb+La+Nb205, Nb+LaO, Nb+LaNb04, Nb+LaNb7012, I Nb+La3Nb07+ LaNb04 , Nb+La3Nb07+LaNb7012, Nb+Nb02+ La3Nb09+LaNb04 or Nb+Nb0+Nb02+La3Nb〇9+ LaNb04 o Furthermore, the following vapor deposition materials containing the metal ruthenium and/or metal ruthenium are referred to as “containing metals”. The evaporation material". The vapor-deposited material containing metal is also a material having a small oxygen content in the same manner as the sub-oxide vapor deposition material. Therefore, it is known from the above that a film having desired characteristics is easily formed. In addition, the vapor deposition material of the present invention is not limited to the extent of the effects of the present invention described above, that is, to 5 mol% of the binary oxide of cerium and lanthanum, and addition of oxides of sharp and cerium. The material is fine. This species 12 320085 200848530: The material can be exemplified by oxidation, oxidation, oxidation, oxidation, and the like. The molar ratio of 铌 and 在 is 25 ·· 75 to 90 · 1n — ^, because the change of the molar ratio will be large with the material outside the ore-making, so it is not suitable for continuous _. The number of materials of Mox% is difficult to sufficiently make the light in the near ultraviolet region 0, and the material below 25 mol% is the square film. In addition to the refractive index of the full 鬲, if the molar ratio of 铌 to 镧 is 35·· 65 to 60: 4η, the refractive index of the successively formed films of continuous vapor deposition is 1 and can be longer and more The number of times is ideal. In particular, the change in the refractive index can be suppressed to the left and right mouths of (10). The shape of the material is not particularly limited. However, the molded body: shape: it is preferable to form a film having optical properties such as a particulate matter. Furthermore, :: When the body is around, H is supplied with the material of the continuous steaming material, because: It is ideal. Further, it is preferably a calcined body obtained by calcination of a molded body or a body or a molded body. No degree: not large, so the volume will be replenished frequently due to the material in the case of steaming. Further, the content of the steamed ore material of the present invention is 5% by weight or less. =; 〇: 氧化 氧化 氧化 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 200848530 It should be chemically changed to a lower density of barium hydroxide. If it is a molded body, a sintered body or a melt, it will expand and collapse and become powdery. In addition to the powder, if a vapor deposition material containing a large amount of barium hydroxide is used as it is, it will not only cause scattering of the material but also cause significant water release, which will occur in the formed film. Physical defects are produced and are not ideal from the viewpoint of maintenance of the vapor deposition device. The steam bell material of the present description can be produced, for example, by the following method. r If it is a sintered body, a powder of cerium oxide (v) and silver oxide Um) is used as a starting material, and the obtained mixture powder is mixed with a predetermined ratio of oxidized sharp (V) and cerium (m). After the body is granulated and/or formed, it can be calcined at a predetermined temperature by inert gas such as f = gas, vacuum or argon. In the case of a melt, it can be produced by melting a mixture or a molded body thereof at a predetermined temperature. Further, the optimum temperature for the calcination temperature and the melting temperature is also the same as that of the vapor deposition material, but the calcination temperature is approximately 9 to 17 Torr. . Preferably, the melting temperature is approximately 1350 to 190 (rc is preferred. 2. When the secondary oxide evaporation material is produced, a metal woven metal or metal ruthenium may be used in addition to yttrium oxide (m). It is used as the starting material of the material. If the metal and the oxide of the kind of composition form a medium, the material can be washed or melted, or the secondary oxide evaporation material can be produced. Instead of ruthenium oxide, or ruthenium oxyhydroxide as a starting point, it will only be) and/or ruthenium oxide (羾). Further, the vapor deposition material produced by using ruthenium, rhodium oxide (V) and ruthenium oxide (m) as a starting material 320085 14 200848530 may be produced by deoxidation. The deoxidation method is a heat treatment of a county under a hydrogen (tetra) elemental gas. Further, in the case where the clothes contain a metal evaporation material, the case of the starting material distillate shovel material is the same. However, the condition of reading the material by the object is not (4) the manufacturing conditions (for example, when the calcining temperature is set to 鲂 ★ _ ^ for the calcination, or the calcination time is set to be ^), while the metal itself is The state of surviving is completed. In this way, a metal-containing vapor deposition material can be produced. In addition, Xuan #° - 卜 can also be made by adding metal bismuth and/or all _, ν, to calcination or melting in the bismuth plating material of the binary and bismuth telluride. The use of the film of the invention described above can not only make the entire visible light; the optical 360 & optical domain formed by the material, but also the near ultraviolet region (the wavelength of nm Domain) penetration, refractive index 2 15 $ 7 ^ ^ high refractive index with a ratio of sheep to 2.35 (preferably center to 2.35) at a wavelength of 450 nm. The method for producing an optical film of the present invention is characterized by using the present invention. The therapeutic material is formed by the "direct support of the thorns, the t-two... plating method in the invention of the invention. The subsidy is also included in the present invention." Ion plating method or ion, - the tomb of Shangming # material t +3⁄4 μ &, 'χ,. In order to steam the money like the hair of the ==, it is better to use :==. In addition, even if the electron beam evaporation method is used, it is also made of materials, and it has been kept flat after the steaming time, and the monthly to positive control of the evaporation rate is "the face of the moon", so it can be accommodated. It is easy to manufacture an optical film having the desired characteristics 320085 15 200848530. Furthermore, since the steaming material of the present invention can be further reduced, there is no need for special electron beam operation, such as fixing electrons even in film formation. The irradiation position of the beam = film. Further, if the irradiation position of the electron beam at this time is preferably such as, for example, the evaporation of the material is used, the evaporation rate can be easily controlled even by using the electron anthracene and the degree of the bundle. The combination of the four elements of b and 镧 is to form a strip plating material. [Embodiment] (An embodiment of the present invention, but the present invention is not limited thereto. The weight ratio is 32.9··67] (sharp and The molar ratio of 镧 is π.5: 6 ～ 铌 铌 V V V V . . 造 造 造 1 1 1 1 1 1 1 1 1 1 1 1 1300 1300 1300 1300 1300 1300 1300 1300 1300 1300 1300 1300 1300 1300 1300 1300 1300 1300 1300 1300 1300 Forging; ί: 圭4 This obtains a granular steamed ore material. The X-ray diffraction pattern is identified as the long 〇7 and L 〇4. The copper (4) financial smelting device filled with the vapor deposition material, and the device is vented to the 犹3pa, Heating and melting the steaming material to form a molten pool. Then, introducing oxygen = , is 1. After that, the electron beam is irradiated only to the smelting pool = = heart gas is generated, and is heated in the device to the smoke in advance. On the village, 'filming catches & 〇.9 fine / sec film to physical film thickness up to 16 320085 200848530 • 250_ is j. Under the exchange of only the substrate and completely unfilled with steamed material. ^ The film For each of the obtained films' by spectrophotometer, the refractive index of 450 nm, 廿#丄, and the molar ratio of the wave. The * is to be analyzed and found to be 铌 and 镧 Gan / shown in the first table and Table 2, regardless of the number of film formations;; the rate of shots and the molar ratio (5), and all the films are not confirmed to absorb from 285 nm to the visible field. If the 285 nm, the wavelength will be from =! When the side becomes short, the light absorption of the film begins to occur, and the wavelength at which the first tooth rush begins to drop sharply is called the "shortest penetration wavelength." (2) The steamed material after the film formation is finished, and the film 'sends the electron beam to be irradiated only on the evaporation surface which is kept smooth. Among them, ~4, and then +, the calculation of the refractive index at a wavelength of 450 nm The method is as follows: Score Light 1 is measured by a spectrophotometer commercially available to obtain a refractive index to obtain a refractive index. The dispersion curve and the dispersion of the job are used to calculate the dispersion of the refractive index. The formula is often used to find the relationship between the wavelength of * and the early relationship of 叮, to n == SQRT [1 + Α / (1 + Β / λ 2)] ^ ^ t Here, n is the refraction Rate, λ is the wavelength, the coefficient of the relationship between A and B Sun Bing,,, and the refractive index. And " 亍, ', ', 疋 / the square root of the section." Department table - leaf calculation of the above formula [] (', example 2) by weight ratio (6): .... 0 (sharp and 镧 molar ratio of 6 〇.〇: 320085 17 200848530 〇) mixed cerium oxide (v) and oxidized. And the powder mixture is a powder of the main genus A 1 5 q, calcined 4 small Japanese t 23 side spinner In the form of a vacuum in the form of ^ i χ %, the vapor-deposited material in the form of a tablet is obtained. Coffin # is a line of X-ray diffraction patterns for LaNb〇4 and Nb〇. / This material is used for the film obtained by using the vapor deposition material and formed into a film, and the method of determining the wavelength of wy _1R, and the sharp disk: the refractive index of 450 nm, the shortest penetration regardless of the number of film formations = The ear rate is shown in the first table... 3〇5_. 〃 射 及 及 及 及 及 及 及 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且To 3 and the powder of the emulsified steel (m) and mix the powder in a small form, and in the atmosphere, 12_ calcined 4 to form a film of the same example, the method of folding the film (10) And the table, 330nm. And the ear is the same as the white, and the shortest penetration wavelength is (Cheng Shi 4) mixed oxidation II ^ 5.9. From 1 (sharp and 镧 molar ratio of 30.0: 70.0) compound heart! To 3 and yttrium oxide (magic powder, and mix the powder in a 'mm particle shape, calcined in the atmosphere at 1500 ° C 4 18 320085 200848530. α wood L is La3Nb〇7 j LaNb〇4. Film formation: =: Γ vapor deposition material was carried out in the same manner as in Example 1, and the respective films of t were determined to have a wavelength of 45 Å and a molar ratio of 锟 to 镧. The results are shown in the first; Take the first = no matter the number of film formation JL fold, Xuan 1 h Le 1 and brother 2, 27 face. The refractive index and 4 ears are the same 'and the shortest penetration wavelength is (Example 5) f 50 〇 Γ,,^^44·3 : 54·3 : M (The molar ratio of sharp money is 5〇.〇: and two:: emulsified sharp (V), yttrium oxide (8) and oxidized powder, " The "mixture granulation is U3mm 1500 °C calcination 4 / 丨, 护 -, the shape is not identified in the sputum, the amount is not identified as LaNb 〇 4. In addition, oxidation (four) due to microfilming = use of the steam The material is plated and the molar ratio of the wavelength and the sharpness to the enthalpy is carried out in the same manner as the embodiment. The results are shown in the second tooth. The refractive index and the molar ratio are the same, and the shortest penetration wave is the same. (Example 6) :/·7 37.5 : and will rape ... reduce the powder of the bowl and the metal crucible, and obtain the steamed ore material in the form of a lozenge. The material is 320085 19 200848530 • It is made up of x-ray diffraction pattern dreams of 丨 τ τ • for use 7, LaNb0^Nb The film obtained by film formation, the method of the same example, the wavelength of the same method, and the molars of 铌 and 莫 短 牙 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 不论 。 。 290 290 290 290 And 4 ears are the same, and the shortest penetration wavelength is (Example 7) 16 7)^ ratio 53.3:21.8:24.9 (the molar ratio of sharp to 镧 is 83.3: upper 〇·7) is yttrium oxide (V) ), and the powder mixture is made into _i if (m) and metal sharp powder, 130 (TC calcined for 3 days ± in the form of a tablet of 1 to 3 sides in a vacuum in the form of X (four) The material of the clock: the material of the line: the diffraction pattern of the line is LaNb3〇(10)^ film formation, the wavelength of the same method as in the first embodiment, and the refractive index of the sharp disk, 苴 and 0 (four), the shortest penetration of 335 nm 〇, Mohr is the same, and the shortest penetration wavelength is (Comparative Example 1), Intrusion: Weight ratio 90.4: 9.6 (The molar ratio of 铌 and 莫 is 92 3 : 7 7) Combine::(V) and Oxidized rotten (8) powder And the 靡小日士4 is a granular shape of i to 3 mm, and is calcined in the atmosphere in the atmosphere. Figure 4: Obtaining a granular vapor-deposited material. The material is patterned by X-ray diffraction pattern. For surveying 5014 and Nb2〇5. 320085 20 200848530 • Film-forming ore-bearing material and carrying out the same wavelength as in Example 1, and the molars of 铌 and 镧:: long CO—the refractive index, the shortest penetration The shortest penetration wavelength of the film formation and the second refractive index will decrease, and the molar ratio will also change, and the light penetrates. It is 365 nm, it can not be said that it can fully make the near-ultraviolet field (Comparative Example 2): the weight ratio is 2 〇 from the sharp and 镧, the powder TM of 曰化镧(4), the particle of ± 5 J ^ mm Shape, 15 在 in the atmosphere. The crucible is simmered and the crucible is obtained. Volume 2 but the granules did not collapse. Further, the content of the cerium oxide added thereto was 2.5% by weight. With respect to each of the films obtained by using the vapor deposition material and the same as in Example i, the wavelength-refractive index and the shortest ratio were obtained: and the molar ratio of sharp and 镧 was obtained. Show the results in the first! Table and Table 2 = tooth-wavelength is 260 coffee, although it can fully penetrate the near-ultraviolet region, the film formation read increases, the refractive index increases, and the molar ratio is also one (Comparative Example 3) . Hereinafter, a comparative example in which the ruthenium raw material of the vapor deposition material of the present invention is substituted will be described. Mixing titanium oxide (IV), cerium oxide (m) and titanium powder with a weight ratio of 29.3 : 68.2 : 2.5 (the molar ratio of titanium to lanthanum is 5 〇〇. 5 〇. 〇), 320085 21 200848530 The powder mixture was granulated and calcined at 17 ° C for 5 hours, in the form of a surface, in addition to the use of the distilled mineral ==: evaporation material. In the case of the first embodiment, the method of the same method was carried out, and the photo of the vapor-cured material after the solid beam was shown to have a large depression. Although only carried out; the position of the electron beam is deeply excavated to the extent that it will reach the bottom of the _, the case of the car I does not replace the sputum of the steamed mineral material of the present invention with the bismuth raw material by the weight ratio of 44 〇: 56 幽如幽拉— Mixed yttrium oxide (V), oxidation and enthalpy molar ratio is 4G.f) granulation is a powder of i to 3mm: 乂) powder and mix the powder with J ^ — Granular, calcined at 17001 in vacuum for 4 small $, to obtain a granular vapor-deposited material. The vapor deposition material was formed and the number of film formations was set to form a film. Fig. 4 shows the above-mentioned film-forming junction: photograph, which is known from the photograph, although the position of the electron beam is largely sag, and the bottom portion of the catastrophe is exposed. In the same manner as in Comparative Example 3, it was impossible to carry out at all (Comparative Example 5) 4 with the same cake, and ^ from 12〇0. . The calcination was carried out for 4 hours, in addition to the examples. ' After the (four) shape of steam (four) material. The bake material is wound by X-ray 320085 22 200848530. 〆: It is identified as LaNb〇4, La3Nb〇7 and (4). The increase in mass due to moisture absorption" The granules will collapse after one day of production and change to a powdery form. The content of the yttrium oxide is increased by 6.3 wt%. The powdery vapor deposition will be loaded. The copper crucible of the material is installed in a commercially available air purifier device, and after exhausting the device to l.OxWPa, when the electron beam is heated, the material is severely scattered, thereby causing the film formation to be interrupted. Table 1]
—一 - —丨 - 折射率入 = 4 5 0 nm 成膜次數 1 2 3 4 1 —1- 2. 23 一 丨 — 2· 23 2. 24 2. 23 實 2 2.30 2,29 2,30 2.29 3 2· 35 2. 33 2· 34 2,32 施 4 U6 2. 19 2.18 2· 17 例 5 2.26 2· 27 2.27 2.26 6 2. 25 2· 25 2.24 2· 25 7 2, 33 2· 34 2· 35 2· 32 比 較 1 2.45 2.40 2.37 2· 37 2 2. 06 2. 09 2· 13 2· 12 3 不能連續蒸著 例 4 不能連續蒸著 r- 0 _因材料飛散而造成成膜中斷 23 320085 200848530 [第2表] f—一———丨—refractive index in = 4 5 0 nm Film formation times 1 2 3 4 1 —1. 2. 23 一丨— 2· 23 2. 24 2. 23 Real 2 2.30 2,29 2,30 2.29 3 2· 35 2. 33 2· 34 2,32 Shi 4 U6 2. 19 2.18 2· 17 Example 5 2.26 2· 27 2.27 2.26 6 2. 25 2· 25 2.24 2· 25 7 2, 33 2· 34 2 · 35 2· 32 Comparison 1 2.45 2.40 2.37 2· 37 2 2. 06 2. 09 2· 13 2· 12 3 Cannot be continuously steamed Example 4 Cannot continuously steam r- 0 _The film formation is interrupted due to scattering of material 23 320085 200848530 [Table 2] f
(產業上之利用可能性） 根據本發明，可楹 — 使用該蒸鑛材料而得之光@ 下特徵之蒸鐘材料、 法，該蒸物之C膜及該光學薄膜之製造方 L具熔融性且可進行連續蒸鍍。 2亦即^採用電子束蒸鑛法亦可容易地控制蒸發速 =亦即’由於因射束所產生之熱會從射束照射點適度地 擴放至整㈣融池而保持平滑之蒸發面，因此可容易㈣ 制蒸發速度，結果可容易地形成具有均—的所希望特性之 320085 24 200848530 膜 3·可使比以往更廣之波長範圍（特別 之光穿透。 是近絷 外線域 以成膜 4·可將具有高折射率之光學薄膜予 【圖式簡單說明】 第1圖係由實施例1所得之蒸鍍材 〇 m ^ π抖之X線繞射圖案。 圖係頦不貫施例1中之成膜結束 態的照片。 不俊之4融池之狀 第3圖係顯示比較例3中之成膜 融池之 恶的照片。 熊的；：圖係-不比較例4中之成膜結束後之熔融池之狀 【主要元件符號説明】 無。 25 320085(Industrial Applicability) According to the present invention, it is possible to use a steaming material and a method of using the vaporized material to obtain a vapor film, a method, a film C of the vapor, and a manufacturing method of the optical film L. Continuous vapor deposition is also possible. 2 That is, the electron beam evaporation method can also be used to easily control the evaporation rate = that is, because the heat generated by the beam will be moderately expanded from the beam irradiation point to the entire (four) pool to maintain a smooth evaporation surface. Therefore, the evaporation rate can be easily (4), and as a result, 320085 24 200848530 film having a desired characteristic can be easily formed. 3. The wavelength range can be made wider than in the past (especially light penetration. Film formation 4· An optical film having a high refractive index can be referred to as a simple description of the drawing. Fig. 1 is an X-ray diffraction pattern of the vapor deposition material obtained in Example 1 by ^m ^ π shaking. Photograph of the film formation end state in Example 1. Fig. 3 shows the photo of the film formation melt in Comparative Example 3. Fig. 3: Fig. Shape of the molten pool after the end of the film [Key element symbol description] None. 25 320085