200533773 (1) 九、發明說明 【發明所屬之技術領域】 本發明是有關以物理蒸著法與化學蒸著法形成薄膜， 尤其是金屬化合物膜之薄膜形成裝置及使用該裝置之薄膜 形成方法。 【先前技術】 g 先前，利用濺鍍法形成金屬化合物薄膜之方法有在濺 鍍氣氛中導入反應氣體（例如氧氣、氮氣、氟氣等）之反 應性濺鍍法。要利用該方法形成具有與整體（bulk )相同 之組成之金屬化合物薄膜時，必須提升富於反應性之反應 氣體之分壓，但是也有未反應之反應氣體與靶（target ) 表面反應而形成化合物，並且顯著降低薄膜形成速度之問 題。 爲解決該問題，有人提出濺鍍薄膜形成裝置（參照專 Φ 利文獻1 )係夾持隔板鄰接設置濺鍍手段，用於對基板進 行濺鍍處理以形成薄膜，以及照射手段，用於對該濺鍍手 段所形成之薄膜照射反應氣體以形成化合物薄膜，而重複 進行利用濺鍍手段之薄膜形成工程，與利用照射手段之反 應工程。 另外，也有人提出一種濺鍍薄膜形成裝置（參照專利 文獻2與專利文獻3 )，係在真空槽內設有將基板保持於（ 外周旋轉之圓筒狀之旋轉鼓；在該旋轉鼓之旋轉位置位於 濺鍍位置時，對保持於旋轉鼓之基板進行濺鍍處理之濺鍍 -5- (2) 200533773 手段；以及當旋轉鼓之旋轉位置位於反應位置時’對基板 照射反應氣體之照射手段。 在此舉裝置中，在對基板照射反應氣體之照射手段中 使用離子鎗與DC電漿。 [專利文獻1]專利1 6940 84號公報 [專利文獻2]專利2 1 1 63 22號公報 [專利文獻3]專利26955 1 4號公報 【發明內容】 [發明擬解決之問題] 可是將上述濺鍍手段與照射手段緊鄰設置之裝置中， 若反氣體之流量多，則由照射手段所照射之反應區域側之 反應氣體容易超越隔板轉入薄膜形成區域，與濺鍍手段之 整體表面反應而降低薄膜形成速度。另方面，若反應氣體 之流速慢，則基板上之薄膜與反應氣體之反應速度變慢， φ 仍然在實用上不易確保充分之薄膜形成速度。 另外，在上述真空槽內設置有旋轉鼓，濺鍍手段與照 射手段之裝置雖然可以確保濺鍍手段與照射手段之物理距 離’但是爲提局反應氣體之分壓，必須裝設用於隔開機鍍 手段之薄膜形成區域與照射手段之反應區域之電導構件（ conductance)或添加排氣系統等，積極實施氣氛分離。 此外，在該等裝置中，用於對基板照射反應氣體之照 射手段中是使用離子鎗與D C電漿，但是該等有構造複雜 而維修性不良’而且要擴大照射面積不易，而且容易產生 -6 - (3) (3)200533773 電極材料之污染或異常放電之問題。 再者’要以此_裝置有效反應基板上之薄膜，必須提 高放電之電漿密度，惟若爲提高電漿密度而提高放電壓力 ，則反應氣體即擴散到薄膜形成區域而與整體（bulk )表 面反應而形成化合物，而有薄膜形成速度顯著降低之問題 〇 因此，本發明爲鑑及此種問題而完成，其目的在提供 一種薄膜處理裝置，其可以更快速之薄膜形成速度形成具 有良好特性之金屬化合物薄膜且以簡單地以低成本構成； 以及一種薄膜處理方法，以該薄膜處理裝置更快速之薄膜 形成速度形成具有良好特性之金屬化合物薄膜。 [解決問題之手段] 爲解決上述課題，申請專利範圍第1項所記載之發明具 備：真空腔室；設置於真空腔室內並將基板保持於外周而 旋轉之圓筒狀旋轉鼓；設成面對旋轉鼓之外周面以對相面對 之基板形成薄膜之薄膜形成手段；以及設成面對旋轉鼓之外 周面，並對相面對位置之基板電漿化反應氣體並照射之電 漿照射手段；電漿照射手段具有產生電漿之區域之真空腔室 內面被電介質所覆蓋之構造。 又，申請專利範圍第2項所記載之發明之特徵爲除了上 述構造，電漿照射手段是利用微波電漿化反應氣體。 申請專利範圍第3項所記載之發明之特徵爲：電漿照射 手段具備：真空腔室外之微波產生源，以及設置於真空腔 -7- (4) (4)200533773 室之喇叭型輻射體（horn )與天線之一；並透過喇叭型輻射 體與天線之一將微波產生源所產生之微波導入真空腔室內 ，且利用該微波電漿化反應氣體。 申請專利範圍第4項所記載之發明之特徵爲：電漿照射 手段具備：真空腔室外之微波產生源，以及設置於真空腔 室之電介質真空窗，並透過真空窗將微波產生源所產生之 微波導入真空腔室內，且利用該微波電漿化反應氣體。 申請專利範圍第5項所記載之發明之特徵爲：具備在電 漿照射手段產生電漿之區域形成磁場之磁場形成手段，該 磁場形成手段將強度87.5 mT之磁場形成薄片狀或尖狀（ cusp )之一，並利用該磁場產生電子回旋加速器共振電漿 〇 申請專利範圍第6項所記載之發明之薄膜形成手段具有 濺鍍手段，蒸著手段與化學蒸著手段之任一手段，或該等 手段所組合之構成。 另外，本發明之薄膜形成方法之中，申請專利範圍第7 項所記載之發明具備：薄膜形成工程，在真空腔室內使保 持基板之旋轉鼓旋轉，俾在所保持基板面向薄膜形成手段 之位置形成薄膜；以及反應工程，在真空腔室內面被電介 質覆蓋之電漿照射區域與基板相面對之位置，照射被電漿 化之反應氣體使基板上之薄膜反應，並具有重複進行薄膜 形成工程與反應工程之構造。 另外，申請專利範圍第8項所記載之發明之特徵除了上 述構造外，反應工程包含在利用電漿照射手段電漿化反應 -8- (5) (5)200533773 氣體之區域，將強度87.5mT之磁場形成薄片狀與尖狀之一 ，並利用該磁場產生電子回旋加速器共振電漿之工程。 申請專利範圍第9項所記載之發明之特徵爲：在真空腔 室設有電介質之真空窗，反應工程包含由真空窗導入微波 以發生表面波電漿之工程。 申請專利範圍第1 0項所記載之發明之特徵爲：電漿照 射手段將反應氣體電漿化俾產生離子或自由基之一或雙方 〇 申請專利範圍第1 1項所記載之發明之薄膜形成手段具有 濺鍍手段，蒸著手段與化學蒸著手段之一的構造。 [發明之效果] 利用本發明之薄膜形成裝置由於面對電漿照射手段將 反應氣體電漿化之區域的真空腔室內面被電介質所覆蓋， 所以具有電漿化之反應氣體之鈍化（Deactivation )大幅降 低，以及擴散之電漿與真空腔室內面之電性之相互作用也 降低之效果。 因此，相較於真空腔室內面未經過任何處理之情形， 可以保持低壓力下之穩定放電，而且可以分開利用濺鍍手 段之薄膜形成區域以及利用照射手段之反應區域之氣氛。 如此一來，可以簡單地以低成本構築裝置，並可以更 快速之薄膜形成速度形成具有良好特性之金屬化合物薄膜。 此外，電漿照射手段若設成以微波電漿化反應氣體， 則相較於先前利用離子鎗或DC電漿之裝置，可以在低壓下 -9- 200533773 (6) 產生高密度之電漿。因此，可以分離利用濺鍍手段之薄膜 形成區域與利用照射之反應區域之氣氛，不但可以簡單地 以低成本構築裝置，而且可以更快速之薄膜形成速度形成 具有良好特性之金屬化合物薄膜。 此時，電漿照射手段也可以具備真空腔室外之微波產 生源與設置於真空腔室之喇叭型輻射體（horn)或天線，且 透過喇叭型輻射體或天線將微波產生源所產生之微波導入真 φ 空腔室內，並藉由該微波電漿化反應反應氣體。 另外，也可以在電漿照射手段將反應氣體電漿化之區 域設置形成磁場之磁場形成手段，該磁場形成手段將強度 8 7.5 mT之磁場形成薄片狀或尖狀，並藉由該磁場產生電子 回旋加速器共振電漿。 再者，電漿照射手段也可以具備真空槽外之微波產生 器與設置於真空槽之電介質真空窗，且透過真空窗將微波 產生源所產生之微波導入真空腔室內，並藉由該微波電漿 φ 化反應氣體。 又本發明之薄膜形成方法是在基板上形成薄膜後，並 利用微波將反應氣體電漿化而活化後，將大幅降低該活性 種之鈍化之電漿照射使與基板上之薄膜反應，因此有可以 更快速之薄膜形成速度形成具有良好特性之例如金屬化合 物薄膜之效果。 【實施方式】 本發明之薄膜形成裝置具備：真空腔室；設置於真空 -10 - 200533773 (7) 腔室內’並將基板保持於外周旋轉之圓筒狀之旋轉鼓；配 置成面對上述旋轉鼓之外周面，並在對面位置之上述基板 上形成薄膜之薄膜形成手段；以及設置成面對旋轉鼓之外 周面並對相對面位置之基板將反應氣體電漿化而照射之照 射手段；而且電漿照射手段之產生電漿之區域的上述真空 腔室內面是被電介質所覆蓋。 薄膜形成手段可以適用於利用物理蒸著法與化學蒸著 法者。物理蒸著法可以使用真空蒸著，濺鍍以及離子電漿 法(Ion plating ) 〇 電漿照射手段以照射微波，尤其是由ECR所產生之電 漿爲理想。 以下以濺射裝置爲例，依據圖示之實施形態說明本發 明。 參照圖1(a) ， ( b )，其中1表示本發明之凱塞爾式 (Carcel )濺鍍薄膜形成裝置。 該濺鍍薄膜形成裝置1具有真空腔室2，而在真空腔室 2內之大致中央部分設有在外周保持有基板3之狀態下，以 旋轉軸4爲中心旋轉之圓筒狀之旋轉鼓5。 在真空腔室】之內周面’兩個濺鍍陰極（sPutter c a t h 〇 d e ) ( i賤鍍手段）6分別設置於旋轉軸4之相對位置 ，該等潑鍍陰極6連接到未圖不之外界交流電源。另外， 在濺鍍陰極6上面固定著濺鍍靶（sPuttering target ) 7。 在真空腔室1內周面設有職鍍陰極6之部分附近’設有 延伸到旋轉鼓5外周附近之防接板8。真空腔室1內之空間 -11 - 200533773 (8) 被該防接板8所分離而構成濺鍍手段之薄膜形成區域9。 該薄膜形成區域9經由貫穿真空腔室1而設置之濺鍍氣 導入管1 〇與真空腔室1外連通，而經由該濺鍍氣導入管1 〇 由外界未圖示之濺鍍氣源對薄膜區域9供應濺鍍氣。在該 濺鍍氣導入管1 0與氣體源之間設有可調節氣體流量之電導 閥（Conductancevalve)。 在設有兩個濺鍍陰極6之處的中間位置設有真空腔室1 B 之壁面突出外側而構成之長方體形狀之反應區域11。 在圍繞該反應區域1 1之真空腔室1設有微波天線（電 漿照射手段）1 2，該微波天線1 2藉由真空腔室1外之導入 窗1 3與導波管1 4連接到未圖示之微波產生源。 - 藉此，在微波產生源所產生之微波經由導入窗1 3由導 波管14傳播，並藉由微波天線12導入反應區域1 1內。圍繞 該反應區域11之真空腔室1內面是以電介質板15所覆蓋。 另外，圍繞反應區域1 1之真空腔室1之外圍面附設有 φ 用於產生電子回旋加速器共振（以下簡稱ECR )電漿之磁 電路（磁場形成手段）1 6，利用該磁電路1 6產生微波放電 用之靜磁場。具體地說，磁電路1 6可將強度8 7.5 m T之磁場 調節成由磁電路16表面產生高30mm之平面狀，而形成與 基板平行之磁場。 此外，上述微波天線〗2是設置於圖1 ( a )中，不受被 左右磁電路1 6所包夾之區域干擾之位置。 再者，該反應區域1 1係經由貫穿真空腔室1而設置之 反應氣導入管1 7與真空腔室1外連通，並透過該反應氣導 -12- 200533773 Ο) 入管1 7由外界未圖示之反應氣源對反應區域1 1供應反應氣 體。在該反應氣導入管1 7與氣體源之間設有可以調節氣體 流量之電導閥。 在包夾真空腔室1之旋轉軸4而與反應區域11相面對之 位置設有與未圖示之真空排氣系相連接之真空排氣口 18。 藉此，進行真空腔室1內之排氣。 在此種構造之本實施形態中，是利用濺鍍法在基板上 形成金屬薄膜，而藉由旋轉鼓之旋轉，將基板搬送至產生 電漿之反應區域，並在反應區域將反應氣體電漿化以活化 它，由於該反應氣體被電漿化之反應區域面對之真空腔室 內面是以電介質覆蓋，因此，可以大幅度降低電漿化之反 應氣體之鈍化（Deactivation)。 因此，由於將大幅降低活性種之鈍化的電漿照射到形 成於基板上之薄膜，因此，可以更快速之薄膜形成速度製 得具有良好特性之金屬化合物膜。 其次，要說明利用上述構造之本實施形態之薄膜形成 方法。 本實施形態之薄膜形成方法包括：薄膜形成工程，在 真空腔室內，旋轉保持基板之旋轉鼓以依次搬送基板，並 在基板與薄膜形成手段相面對之位置在基板上形成薄膜； 以及反應工程，在真空腔室內面爲電介質覆蓋之電漿照射 區域與基板相對向之位置照射電漿化之反應氣體俾使基板 上之薄膜反應；而且可以依序重複進行薄膜形成工程與反 應工程。 -13- (10) (10)200533773 在此’薄膜形成手段是濺鍍法，惟並不侷限於此，例 如真空蒸著與離子電鍍法等之物理蒸著手段，甚至電漿 CVD等化學蒸著手段也可以適用。 參照圖1 ( a )，要在該濺鍍射薄膜形成裝置1進行薄 膜形成處理時，首先將基板3保持於旋轉鼓5之外周上，同 時將特定之潑鍍祀（sputtering target) 7固定於縣鍍陰極 6上面。 然後，經由真空排氣口 1 8，利用真空排氣系將真空腔 室1內之氣體排出，同時分別由濺鍍氣導入管1 0導入濺鍍 氣體，由反應氣導入管17導入反應氣體至真空腔室1內部 。藉此，真空腔室1內部達到特定之壓力狀態。 接著，僅對裝置1內之兩個職鍍陰極6中之一方施加電 壓。另外，利用磁電路1 6產生磁場，同時由微波天線1 2導 入微波，並將由反應氣導入管1 7所導入之反應氣電漿化以 將反應區域1 1變成電漿氣氛。 在此狀態下旋轉旋轉鼓5時，旋轉鼓5之旋轉位置即來 到濺鍍位置，亦即，保持於旋轉鼓5之基板3存在於被施加 電源之濺鍍陰極6側之薄膜形成區域9內部之位置。 此時，藉由來自濺鍍氣導入管1 0之濺鍍氣體濺鍍濺鍍 陰極6上之濺鍍靶7，而在保持於旋轉鼓5之基板3形成薄膜 (薄膜形成工程）。 若再旋轉旋轉鼓5，則旋轉鼓5之旋轉位置即脫離濺鍍 位置而來到反應位置，即保持於旋轉鼓5之基板3存在反應 區域1 1內之位置。 -14- (11) 200533773 此時，利用來自微波天線1 2之微波電漿化之反應氣體 與薄膜形成工程中形成於基板3之薄膜反應而形成化合物 膜（反應工程）。 此時，面對反應區域1 1之真空腔室1之內面被電介質 板1 5所覆蓋，因此，電漿化之反應氣體之鈍化被大幅降低 ，另外，擴散之電漿與真空腔室1內面之電性之相互作用 也被降低。 Φ 因此，相較於真空腔室1內面沒有施加任何處理之情 形，可以維持低壓而穩定之放電，可以容易進行薄膜區域 9與反應區域11之氣氛之分離。 而藉由持續旋轉旋轉鼓5，並交互多次重複薄膜形成 工程與反應工程而製得所望之化合物薄膜。 如上所述，本實施形態之薄膜形成方法是在基板上形 成薄膜後，利用微波電漿化反應氣體以活化後，照射大幅 度降低該活性種之鈍化之電漿俾與基板上之薄膜反應，因 φ 此可以更快速之薄膜形成速度形成具有良好特性之例如金 屬化合物薄膜。 此外，在本實施形態中，是藉由微波天線]2將微波導 入真空腔室1內，惟本發明並不侷限於此。也可以例如以 喇叭輻射體化替微波天線1 2將微波導入真空腔室1內。或 者’如圖2 ( a ) ， （ b )所示，也可以在真空腔室1設置用 電介質形成，用於產生表面波電漿之真空窗20，並藉由該 真空窗2 0將未圖示之微波產生源所產生之微波導入真空腔 室內。 (S) -15- (12) (12)200533773 再者，本實施形態之濺鍍裝置可以適用於各種化合物 薄膜，例如，氧化膜或氮化膜，氟化膜等，此時，須依企 望之化合物薄膜選擇反應氣體。 另外，本發明並不侷限於上述實施形態，必要時可能 有各種變更。 [實施例1] 在圖1所示之薄膜形成裝置上，將玻璃基板3做爲基板 3固定於旋轉鼓5，並將Ta靶固定做爲濺鍍靶，而利用未圖 示之真空排氣系由真空排氣口 18進行排氣，並使真空腔室 1內之壓力達到5 X 1(T5 Pa。然後，在該狀態下，由濺鍍氣 導入管1 0以流量3 Osccm導入氬氣，同時由反應氣導入管1 7 以流量1 〇 〇 s c c m導入氧氣，並將真空腔室1內之壓力狀態設 定爲〇.3Pa。 然後，以200rpm旋轉旋轉鼓5，同時藉由微波天線12 導入1 k w之微波。 然後，對兩個濺鍍陰極6之中之一方之濺鍍陰極6，利 甩利界交流電源施加40kHz，5kW之交流電力。 在此狀態下，連續進行60分鐘之薄膜形成。經分析製 得之薄膜得知，Ta與Ο之化學計量比（Stoichiometry )爲2 ·· 5，爲無定形構造（Amorphous substonce)。另外，膜 中未檢測出雜質，經測定可視光區域之薄膜之光學特性， 製得了 折射率 2 · 1 4，消化係數（Extinction coefficient ) 爲2xl(T5之良好光學薄膜。 -16- 200533773 (13) [實施例2] 在圖2所示之薄膜形成裝置上，以與實施例1之相同條 件分析製成之薄膜之結果，製得了與實施例1相同之良好 光學薄膜。 [比較例] 圖3所示之濺鍍薄膜形成裝置3 0是由圖1所示之濺鍍薄 膜形成裝置1之構造去除電介質板1 5者。利用該濺鍍薄膜 形成裝置3 0並且以與實施例1相同之薄膜形成條件形成薄 膜。經由分析藉此製得之薄膜之結果，消化係數爲 9 X 1 (Γ5，相較於實施例1所製得之光學薄膜，其化學特性 顯然較差。 [產業上之可利用性] 本發明之薄膜形成裝置與其薄膜形成方法可以大幅降 低使產生之電漿之活性種之鈍化，因此對於產生電漿而利 用於薄膜之形成之薄膜形成裝置與其薄膜形成方法有用。 【圖式簡單說明】 圖1爲本發明之實施形態之薄膜形成裝置之（a )槪略 平面圖，與（b )槪略側面圖。 圖2爲本發明之另一實施形態之薄膜形成裝置之（a ) 槪略平面圖，與（b )槪略側面圖。 -17- 200533773 (14) 圖3爲比較例之薄膜形成裝置之（a )槪略平面圖，與 (b )槪略側面圖。200533773 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a thin film forming apparatus for forming a thin film by a physical evaporation method and a chemical evaporation method, particularly a metal compound film, and a thin film forming method using the same. [Prior art] g In the past, a method of forming a metal compound film by a sputtering method has been a reactive sputtering method in which a reactive gas (such as oxygen, nitrogen, fluorine, etc.) is introduced into a sputtering atmosphere. To use this method to form a thin metal compound film with the same composition as the bulk, the partial pressure of the reactive gas rich in the reaction must be increased, but unreacted reactive gas reacts with the target surface to form a compound And significantly reduce the speed of film formation. In order to solve this problem, a sputtering film forming apparatus (refer to Patent Document 1) has been proposed. A sputtering method is arranged adjacent to a separator to form a thin film, and an irradiation method is used to The thin film formed by the sputtering method is irradiated with a reaction gas to form a compound thin film, and the thin film formation process using the sputtering method and the reaction process using the irradiation method are repeated. In addition, there has also been proposed a sputtering thin film forming apparatus (refer to Patent Documents 2 and 3). A vacuum drum is provided with a cylindrical rotating drum that holds the substrate (the outer periphery rotates; the rotation of the rotating drum) Sputtering -5- (2) 200533773 when the position is in the sputtering position, the substrate held on the rotating drum is sputtered; and when the rotating position of the rotating drum is in the reaction position, the irradiation means for irradiating the substrate with a reaction gas In this device, an ion gun and a DC plasma are used in an irradiation means for irradiating a substrate with a reaction gas. [Patent Document 1] Patent 1 6940 84 [Patent Document 2] Patent 2 1 63 2 22 [ Patent Literature 3] Patent No. 26955 1 [Summary of the Invention] [Problems to be Solved by the Invention] However, in a device in which the above-mentioned sputtering means and irradiation means are arranged next to each other, if the flow rate of the counter gas is large, the irradiation means is irradiated by the irradiation means. The reaction gas on the side of the reaction area easily passes over the separator and is transferred to the film formation area, which reacts with the entire surface of the sputtering means to reduce the film formation speed. On the other hand, if the flow of the reaction gas If it is slow, the reaction speed between the film on the substrate and the reaction gas becomes slow, and φ is still difficult to ensure a sufficient film formation speed in practice. In addition, the above-mentioned vacuum tank is provided with a rotating drum, a sputtering device and an irradiation device. It can ensure the physical distance between the sputtering method and the irradiation method. However, in order to increase the partial pressure of the reaction gas, it is necessary to install a conductance or separate the film formation area of the machine plating method and the reaction area of the irradiation method. Exhaust systems, etc., actively implement atmospheric separation. In addition, in these devices, an ion gun and a DC plasma are used as irradiation means for irradiating a substrate with a reaction gas, but these have complicated structures and poor maintainability. It is not easy to expand the irradiation area, and it is easy to cause the problem of -6-(3) 200533773 electrode material contamination or abnormal discharge. Furthermore, 'to use this device to effectively respond to the thin film on the substrate, you must increase the discharge plasma Density, but if the discharge pressure is increased in order to increase the plasma density, the reaction gas diffuses into the film formation area and ) Compounds are formed by surface reaction, and there is a problem that the film formation speed is significantly reduced. Therefore, the present invention has been made in consideration of such problems, and an object thereof is to provide a thin film processing apparatus which can form a film at a faster speed and has a good film formation speed. And a thin film processing method for forming a metal compound film with good characteristics at a faster film forming speed of the thin film processing device. [Means for Solving the Problems] To solve the above-mentioned problems The invention described in the first patent application scope includes: a vacuum chamber; a cylindrical rotary drum provided in the vacuum chamber and rotating while holding the substrate at the outer periphery; and provided so as to face the outer peripheral surface of the rotary drum so as to face the opposite side A thin-film forming means for forming a thin film on the substrate; and a plasma-irradiating means provided to face the outer peripheral surface of the rotating drum and plasma-plasma the reactive gas and irradiate the substrate at the opposite position; The area inside the vacuum chamber is covered with a dielectric structure. In addition, the invention described in item 2 of the patent application is characterized in that in addition to the above-mentioned structure, the plasma irradiation means uses a microwave plasma to react the reaction gas. The invention described in item 3 of the scope of the patent application is characterized in that the plasma irradiation means includes a microwave generating source outside the vacuum chamber and a horn-type radiator (-7) (4) (4) 200533773 room ( horn) and one of the antennas; and the microwave generated by the microwave generation source is introduced into the vacuum chamber through one of the horn-shaped radiator and the antenna, and the reaction gas is plasmatized by using the microwave. The invention described in item 4 of the scope of the patent application is characterized in that the plasma irradiation means includes a microwave generation source outside the vacuum chamber, and a dielectric vacuum window provided in the vacuum chamber, and the microwave generation source generated by the vacuum window passes through the vacuum window. Microwaves are introduced into the vacuum chamber, and the reaction gas is plasmatized using the microwaves. The invention described in item 5 of the scope of the patent application is characterized by having a magnetic field forming means for forming a magnetic field in a region where the plasma irradiation means generates a plasma. The magnetic field forming means forms a magnetic field having a strength of 87.5 mT into a thin sheet or a sharp (cusp) ), And use the magnetic field to generate an electron cyclotron resonance plasma. The thin film forming means of the invention described in the sixth aspect of the patent application has any of sputtering means, evaporation means and chemical evaporation means, or And other means. In addition, in the thin-film forming method of the present invention, the invention described in claim 7 of the patent application scope includes a thin-film forming process in which a rotary drum holding a substrate is rotated in a vacuum chamber, and the held substrate faces the thin-film forming means. Forming a thin film; and a reaction process in which a plasma-irradiated area covered with a dielectric inside a vacuum chamber faces a substrate, irradiating a reactive gas that is plasmatized to react the thin film on the substrate, and has a repeating thin-film formation process And reaction engineering structure. In addition to the features of the invention described in item 8 of the scope of the patent application, in addition to the above-mentioned structure, the reaction process includes a plasma reaction using plasma irradiation means. 8- (5) (5) 200533773 Gases will have an intensity of 87.5mT The magnetic field forms one of a sheet shape and a pointed shape, and uses the magnetic field to generate an electron cyclotron resonance plasma. The invention described in item 9 of the scope of the patent application is characterized in that a dielectric vacuum window is provided in the vacuum chamber, and the reaction process includes a process of introducing microwaves from the vacuum window to generate a surface wave plasma. The invention described in item 10 of the scope of the patent application is characterized in that the plasma irradiation means plasmaizes the reaction gas to generate one or both of ions or free radicals. 0 The film formation of the invention described in the scope of patent application 11 The method has a structure of one of a sputtering method, a vaporization method, and a chemical vaporization method. [Effects of the Invention] Since the thin film forming apparatus of the present invention is used to cover the interior of the vacuum chamber in the region where the reaction gas is plasmatized by the plasma irradiation means, the reaction chamber has the deactivation of the plasmatized reaction gas. Significantly reduce the effect of reducing the electrical interaction between the diffused plasma and the interior of the vacuum chamber. Therefore, compared with the case where the inside of the vacuum chamber is not subjected to any treatment, a stable discharge at a low pressure can be maintained, and the atmosphere of the film forming region by the sputtering method and the reaction region by the irradiation means can be separated. In this way, the device can be simply constructed at a low cost, and a metal compound film having good characteristics can be formed at a faster film forming speed. In addition, if the plasma irradiation means is set to plasmaize the reaction gas with a microwave, it can generate a high-density plasma at a lower pressure than previous devices using an ion gun or a DC plasma. Therefore, it is possible to separate the atmosphere of the thin film forming area by the sputtering method and the reaction area using the irradiation. Not only can the device be simply constructed at a low cost, but also a metal compound thin film having good characteristics can be formed at a faster thin film forming speed. At this time, the plasma irradiation means may also include a microwave generation source outside the vacuum chamber and a horn-type radiator (horn) or antenna provided in the vacuum chamber, and the microwave generated by the microwave generation source is transmitted through the horn-type radiator or antenna. Into a true φ cavity, the reaction gas is plasmatized by the microwave plasma. In addition, a magnetic field forming means for forming a magnetic field may be provided in a region where the reaction gas is plasmatized by the plasma irradiation means. The magnetic field forming means forms a magnetic field having a strength of 8 7.5 mT into a sheet shape or a pointed shape, and generates electrons by the magnetic field. Cyclotron resonance plasma. Furthermore, the plasma irradiation means may also include a microwave generator outside the vacuum tank and a dielectric vacuum window provided in the vacuum tank, and the microwave generated by the microwave generation source is introduced into the vacuum chamber through the vacuum window, and the microwave power The slurry φ turns the reaction gas. In the method for forming a thin film of the present invention, after a thin film is formed on a substrate, and the reaction gas is plasma-activated by using a microwave, the passivation of the reactive species is substantially reduced by plasma irradiation to react with the thin film on the substrate. The effect of forming a thin film of a metal compound having good characteristics at a faster film formation speed can be achieved. [Embodiment] The thin film forming apparatus of the present invention includes: a vacuum chamber; a cylindrical rotary drum installed in the vacuum -10-200533773 (7) chamber and holding the substrate at the outer periphery; and configured to face the above rotation A thin film forming means for forming a thin film on the above-mentioned substrate at the opposite position on the outer peripheral surface of the drum; and an irradiating means provided to face the outer peripheral surface of the rotating drum and irradiate the substrate with the opposite gas in a plasma; and The above-mentioned vacuum chamber interior of the plasma generating area of the plasma irradiation means is covered by a dielectric. The thin film formation method can be applied to those using physical vapor deposition and chemical vapor deposition. The physical evaporation method can be vacuum evaporation, sputtering, and ion plating. The plasma irradiation means is ideal for irradiating microwaves, especially the plasma generated by ECR. Hereinafter, the present invention will be described using a sputtering device as an example, with reference to the illustrated embodiment. Referring to FIGS. 1 (a) and (b), 1 represents a Carcel sputtering film forming apparatus of the present invention. The sputtering film forming apparatus 1 includes a vacuum chamber 2, and a cylindrical rotating drum that rotates around a rotating shaft 4 as a center while holding a substrate 3 on an outer periphery in a substantially central portion of the vacuum chamber 2. 5. In the vacuum chamber], two sputtering cathodes (sPutter cathode) (i-base plating means) 6 are respectively disposed at the relative positions of the rotating shaft 4, and these sputtering cathodes 6 are connected to an unillustrated one. External AC power. A sputtering target 7 is fixed on the sputtering cathode 6. An anti-contact plate 8 extending to the vicinity of the outer periphery of the rotary drum 5 is provided near the portion where the cathode 6 is provided on the inner peripheral surface of the vacuum chamber 1. Space in the vacuum chamber 1 -11-200533773 (8) The thin film forming area 9 is formed by the anti-contact plate 8 to constitute a sputtering method. The thin film formation area 9 communicates with the outside of the vacuum chamber 1 through a sputtering gas introduction pipe 10 provided through the vacuum chamber 1, and is connected to the outside of the vacuum chamber 1 through a sputtering gas introduction pipe 10. The thin film region 9 is supplied with a sputtering gas. A conductance valve is provided between the sputtering gas introduction pipe 10 and the gas source to adjust the gas flow rate. A rectangular parallelepiped-shaped reaction region 11 is formed at the middle position where the two sputtering cathodes 6 are provided, and the wall surface of the vacuum chamber 1 B protrudes outward. A microwave antenna (plasma irradiation means) 12 is provided in the vacuum chamber 1 surrounding the reaction area 11. The microwave antenna 12 is connected to a waveguide 14 through an introduction window 1 3 outside the vacuum chamber 1. Unillustrated microwave generation source. -As a result, the microwave generated by the microwave generating source is transmitted by the waveguide 14 through the introduction window 13 and is introduced into the reaction area 11 through the microwave antenna 12. The inner surface of the vacuum chamber 1 surrounding the reaction area 11 is covered with a dielectric plate 15. In addition, a magnetic circuit (magnetic field forming means) 16 for generating a plasma of an electron cyclotron resonance (hereinafter referred to as ECR) plasma is attached to the outer surface of the vacuum chamber 1 surrounding the reaction area 11. The magnetic circuit 16 is used to generate The static magnetic field used for microwave discharge. Specifically, the magnetic circuit 16 can adjust a magnetic field with an intensity of 8 7.5 m T to generate a plane shape of 30 mm in height from the surface of the magnetic circuit 16 to form a magnetic field parallel to the substrate. In addition, the above-mentioned microwave antenna [2] is a position provided in FIG. 1 (a) and not affected by the area surrounded by the left and right magnetic circuits 16. In addition, the reaction area 11 is connected to the outside of the vacuum chamber 1 through a reaction gas introduction pipe 17 provided through the vacuum chamber 1, and passes through the reaction gas guide -12-200533773 〇) The inlet pipe 17 is not externally connected. The reaction gas source shown in the figure supplies reaction gas to the reaction area 11. An electric conductance valve capable of adjusting the gas flow rate is provided between the reaction gas introduction pipe 17 and the gas source. A vacuum exhaust port 18 connected to a vacuum exhaust system (not shown) is provided at a position facing the reaction area 11 around the rotary shaft 4 of the vacuum chamber 1. Thereby, the exhaust in the vacuum chamber 1 is performed. In this embodiment of this structure, a metal thin film is formed on a substrate by a sputtering method, and the substrate is transferred to a reaction area where a plasma is generated by the rotation of a rotary drum, and a reaction gas is plasma generated in the reaction area. To activate it, because the reaction gas is covered with a dielectric inside the vacuum chamber facing the reaction zone of the plasma, so the deactivation of the reaction gas can be greatly reduced. Therefore, since a thin film formed on a substrate is irradiated with a passivation plasma that substantially reduces the active species, a metal compound film having good characteristics can be produced at a faster film formation speed. Next, a method for forming a thin film of this embodiment using the above-mentioned structure will be described. The thin film forming method of this embodiment includes: a thin film forming process, rotating a rotary drum holding a substrate in a vacuum chamber to sequentially transfer the substrate, and forming a thin film on the substrate at a position where the substrate and the thin film forming means face each other; and a reaction process In the vacuum chamber, the plasma-irradiated area covered by the dielectric is irradiated with the plasma-generating reaction gas at a position opposite to the substrate to react the thin film on the substrate; and the film formation process and the reaction process can be repeated sequentially. -13- (10) (10) 200533773 Here, the thin film formation method is sputtering, but it is not limited to this. For example, physical evaporation methods such as vacuum evaporation and ion plating, and even chemical evaporation such as plasma CVD. This means can also be applied. Referring to FIG. 1 (a), when the sputtering thin film forming apparatus 1 performs a thin film forming process, firstly, the substrate 3 is held on the outer periphery of the rotating drum 5, and a specific sputtering target 7 is fixed to County plated cathode 6 above. Then, through the vacuum exhaust port 18, the gas in the vacuum chamber 1 is exhausted by the vacuum exhaust system, and at the same time, the sputtering gas is introduced from the sputtering gas introduction pipe 10, and the reaction gas is introduced from the reaction gas introduction pipe 17 to Inside the vacuum chamber 1. Thereby, the inside of the vacuum chamber 1 reaches a specific pressure state. Next, a voltage is applied to only one of the two plated cathodes 6 in the device 1. In addition, the magnetic circuit 16 is used to generate a magnetic field, while the microwave antenna 12 is used to guide the microwave, and the reaction gas introduced by the reaction gas introduction pipe 17 is plasmatized to change the reaction area 11 to a plasma atmosphere. When the rotary drum 5 is rotated in this state, the rotary position of the rotary drum 5 comes to the sputtering position, that is, the substrate 3 held on the rotary drum 5 exists in the thin film formation area 9 on the side of the sputtering cathode 6 to which power is applied. Internal location. At this time, a thin film is formed on the substrate 3 held on the rotary drum 5 by a sputtering target 7 on the cathode 6 by a sputtering gas from the sputtering gas introduction pipe 10 (thin film forming process). If the rotary drum 5 is rotated again, the rotary position of the rotary drum 5 is separated from the sputtering position and moved to the reaction position, that is, held at a position where the substrate 3 of the rotary drum 5 exists in the reaction area 11. -14- (11) 200533773 At this time, the reaction gas from the microwave plasma from the microwave antenna 12 is used to react with the thin film formed on the substrate 3 in the thin film formation process to form a compound film (reaction process). At this time, the inner surface of the vacuum chamber 1 facing the reaction area 11 is covered by the dielectric plate 15, so the passivation of the plasmatized reaction gas is greatly reduced. In addition, the diffused plasma and the vacuum chamber 1 The internal electrical interaction is also reduced. Φ Therefore, compared with the case where no treatment is applied to the inner surface of the vacuum chamber 1, a low-voltage and stable discharge can be maintained, and the atmosphere of the thin film region 9 and the reaction region 11 can be easily separated. And by continuously rotating the rotating drum 5 and repeating the film formation process and the reaction process several times alternately, a desired compound film is obtained. As described above, the method for forming a thin film in this embodiment is to form a thin film on a substrate, and then use a microwave plasma to react the reaction gas for activation, and then irradiate the reactive plasma that substantially reduces the passivation of the active species with the thin film on the substrate. Therefore, it is possible to form a thin film of a metal compound having good characteristics at a faster film formation speed. In addition, in this embodiment, microwaves are introduced into the vacuum chamber 1 through a microwave antenna], but the present invention is not limited to this. It is also possible to introduce microwaves into the vacuum chamber 1 by replacing the microwave antenna 12 with a horn radiator, for example. Alternatively, as shown in FIGS. 2 (a) and (b), a vacuum window 20 may be provided in the vacuum chamber 1 and formed with a dielectric for generating a surface wave plasma, and the vacuum window 20 will not be shown in the figure. The microwave generated by the illustrated microwave generation source is introduced into the vacuum chamber. (S) -15- (12) (12) 200533773 Furthermore, the sputtering device of this embodiment can be applied to various compound films, such as oxide films, nitride films, and fluorinated films. For the compound film, a reactive gas is selected. The present invention is not limited to the above-mentioned embodiments, and various changes may be made as necessary. [Example 1] On the thin film forming apparatus shown in FIG. 1, a glass substrate 3 was used as a substrate 3 and fixed to a rotating drum 5, a Ta target was used as a sputtering target, and a vacuum exhaust (not shown) was used. The gas is evacuated from the vacuum exhaust port 18 and the pressure in the vacuum chamber 1 reaches 5 × 1 (T5 Pa. Then, in this state, argon gas is introduced from the sputtering gas introduction pipe 10 at a flow rate of 3 Osccm. At the same time, oxygen is introduced from the reaction gas introduction tube 17 at a flow rate of 100 sccm, and the pressure state in the vacuum chamber 1 is set to 0.3 Pa. Then, the rotary drum 5 is rotated at 200 rpm and introduced through the microwave antenna 12 1 kw microwave. Then, to one of the two sputtered cathodes 6, a 40 kHz, 5 kW AC power was applied to the AC power source. In this state, film formation was continued for 60 minutes. The thin film obtained after analysis shows that the stoichiometry ratio of Ta to 0 is 2 · 5, which is an amorphous structure (Amorphous substonce). In addition, no impurities were detected in the film. The optical properties of the film yield a refractive index of 2 · 1 4 The digestion coefficient (Extinction coefficient) is 2xl (a good optical film of T5. -16- 200533773 (13) [Example 2] On the thin film forming apparatus shown in FIG. 2, it is made by analyzing under the same conditions as in Example 1. As a result of the thin film, the same good optical film as in Example 1 was produced. [Comparative Example] The sputtering film forming apparatus 30 shown in FIG. 3 removes the dielectric from the structure of the sputtering film forming apparatus 1 shown in FIG. Plates 15. The thin film forming apparatus 30 was used to form a thin film under the same thin film forming conditions as in Example 1. As a result of analyzing the thin film thus prepared, the digestion coefficient was 9 X 1 (Γ5, compared with The chemical properties of the optical film prepared in Example 1 are obviously poor. [Industrial Applicability] The film forming apparatus and the film forming method of the present invention can greatly reduce the passivation of the active species of the generated plasma, so It is useful for a thin-film forming device and a thin-film forming method for generating a plasma for thin-film formation. [Brief Description of the Drawings] FIG. 1 (a) outlines a thin-film forming device according to an embodiment of the present invention. Figure 2 is a schematic side view of (b). Figure 2 is a schematic plan view of (a) and (b) a side view of a thin film forming apparatus according to another embodiment of the present invention. -17- 200533773 (14) 3 is a schematic plan view (a) and a side view (b) of a thin film forming apparatus of a comparative example.
要元件符號說明】 U3 電子回旋加速器共振 U5 電子回旋加速器電漿 U5 尖狀 U6 濺鍍 U6 蒸鍍 P3 〜/ 5 整體 p3 〜fl 0 污染 1 薄膜形成裝置 2 真空腔室 3 基板 4 旋轉軸 旋轉鼓 6 濺鍍陰極 7 濺鍍靶 8 防接板 9 薄膜形成區域 10 濺鍍氣導入管 11 反應區域 12 微波天線 13 導入窗 -18- (15)200533773 14 導波管 1 5 電介質板 16 磁電路 17 反應氣導入管 18 真空排氣口 20 真空窗Key component symbols] U3 Electron cyclotron resonance U5 Electron cyclotron plasma U5 Sharp U6 Sputtering U6 Evaporation P3 ~ / 5 Overall p3 ~ fl 0 Pollution 1 Thin film forming device 2 Vacuum chamber 3 Substrate 4 Rotating shaft rotary drum 6 Sputtering cathode 7 Sputtering target 8 Anti-contact plate 9 Film formation area 10 Sputter gas introduction tube 11 Reaction area 12 Microwave antenna 13 Introductory window-18- (15) 200533773 14 Waveguide tube 1 5 Dielectric plate 16 Magnetic circuit 17 Reaction gas introduction tube 18 Vacuum exhaust port 20 Vacuum window
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