200905010 九、發明說明： 【發明所屬之技術領域】 本發明關於一種電漿化學氣相沈積裝置及一種薄膜沈 積方法。 【先前技術】 一種化學氣相沈積裝置係藉由化學氣相沈積（CVD， Chemical vapor deposition)沈積薄膜在基板上，其可供應基 質氣體及反應氣體做爲來源氣體進入反應爐，並藉由利用 該排氣速率平衡該氣體供應以保持在反應爐中的壓力。在 產生電漿的電漿化學氣相沈積裝置中，該氣體溫度局部地 變得較高，造成反應爐中的氣體擾流。 理想上包含反應氣體之氣體必須緩慢及均勻地流向該 基板的上表面，而藉由氣體的反應而成長的薄膜將被沈積 在該處。已知若氣體流動太快，即造成不規則的沈積，且 如果該反應氣體的行進方向之向量並未導引朝向該基板， 該薄膜成長速率變得較慢。 習用的電漿化學氣相沈積裝置係要克服不規則沈積， 並保持成長速率，例如在日本專利編號2 6 2 8 4 0 4、未審查日 本專利申請早期公開編號H1-94615,及YoshiyukiAbe等人 在 Acta Astronautica(Great Britain)期干中"DIAMOND SYNTHESIS BY HIGH GRAVITY D.C. PLASMA CVD (HGCVD) WITH ACTIVE CONTROL OF THE SUBSTRATE TEMPERATURE"，2001 年 48 卷 2-3 期，121-127 頁。 在日本專利編號2628404中所揭示的電漿化學氣相沈 200905010 積裝置由平行或傾斜於該基板上表面之方向供應反應氣 體，自大致垂直於該基板上表面之方向供應基質氣體，並 擠壓反應氣體與基質氣體來改變反應氣體之流動方向，以 噴灑該反應氣體到該基板上表面之上。 但是，此電漿化學氣相沈積裝置爲熱電漿化學氣相沈 積裝置，其利用加熱器加熱晶座以產生熱電漿，且不需要 考慮電極的配置。如果是DC電漿化學氣相沈積裝置，其 中例如電極放置在面對該基板的位置處，電極成爲瓶頸， 使其很難在垂直於該基板的方向上形成氣體的均勻流動。 在未審查日本專利申請早期公開編號H 1 -946 1 5所述的 電漿化學氣相沈積裝置由在面對基板的陰極處提供的噴嘴 直接噴射氣體。此可允許該反應氣體由陰極流到基板。 但是利用此結構，此時產生電漿，產生活性物種之反 應氣體在變熱的陰極之噴嘴部分處呈現出高密度。因此， 沈積物逐漸地形成在陰極上並儲存在該噴嘴中，藉此千擾 氣體噴射。如果該沈積物由靠近該噴嘴處成長，並成爲凸 出物，電場集中在該凸出物上，所以電漿有可能轉變成電 弧放電或火星。再者，溫度被室溫或膨脹降低的氣體朝向 電漿噴灑，所以正極柱可部分收縮，其可能造成不規則的 薄膜沈積。 在論文"DIAMOND SYNTHESIS BY HIGH GRAVITY D.C. PLASMA CVD (HGCVD) WITH ACTIVE CONTROL OF THE SUBSTRATE TEMPERATURE"中所述及的電漿化學氣相沈 積裝置在反應爐的上部提供氣體入口，在其下部提供氣體 200905010 出口’藉以由陰極朝向陽極產生氣體流動，並通過1 第37A圖及第37B圖爲用於解釋電漿化學氣相 置之反應爐中氣體的流動圖。第3 7 A圖爲該反應 態’而第37B圖爲在1G之氣體流動之流動速率及方 箭頭所示。 在電槳化學氣相沈積裝置中，如第37A圖所示 入口 GI的位置與氣體出口 GO的位置彼此相對，而 的中心軸位在其間。因此，當移動朝向陽極的氣體 陰極的下方部分附近最多，於在氣體入口 GI處對流 與在氣體出口 GO處對流的氣體之間有溫度差，如 圖所示。再者，氣體的局部壓力會不同。 在DC電漿化學氣相沈積裝置中，在要做爲薄膜 料的活性物種中每個成分的部分壓力狀態根據電漿 體溫度而變化，且當溫度變高時，具有高化學勢的 種之部分壓力値將會高於具有相對較低的化學勢之 種之部分壓力値。在反應爐中的溫度差造成電漿中 則溫度’所以每個活性物種之部分壓力根據其位置 不規則，其會造成不均勻的薄膜沈積。 【發明内容】 如上所述’在日本專利編號2628404中揭示的 學氣相沈積裝置爲一種熱電漿化學氣相沈積裝置， 加熱器加熱該晶座以產生熱電漿，且不像是DC電 氣相沈積裝置’其很難在當該等電極放置在面對該 位置處時相對於該基板形成均勻的氣體流動。 漿。 沈積裝 爐的組 向，由 ，氣體 反應爐 在靠近 的氣體 第 37B 沈積材 中的氣 活性物 活性物 的不規 而變爲 電漿化 其利用 漿化學 基板之 200905010 在未審查日本專利申請早期公開編號H1-94615中揭示 的電漿化學氣相沈積裝置在技術上並不滿足，因爲其在當 薄膜沈積時會造成問題，且有可能造成不規則的薄膜沈積。 在論文"DIAMOND SYNTHESIS BY HIGH GRAVITY D.C. PLASMA CVD (HGCVD) WITH ACTIVE CONTROL OF THE SUBSTRATE TEMPERATURE"中揭示的電漿CVD裝置會造 成對基板無法有完全均勻的氣體供應。 因此，本發明的目的在於提供一種電漿化學氣相沈積 裝置及一種薄膜沈積方法，其可均勻地供應反應氣體到基 丰反的上表面，且即使當電極放置在面對該基板的位置處時 可確保穩定的薄膜沈積。 爲此目的，根據本發明第一態樣，其中提供一種電漿 化學氣相沈積裝置，其包含： 第〜電極，係置於反應爐中，且於該第一電極上安裝 基板； 第二電極，係置於該第一電極之上方並與該第一電極 相對’並與該第一電極產生電漿；及 第〜氣體供應噴嘴，係置於在該反應爐中該第一電極 的1%度與該第二電極的高度之間的高度處，並具有複數噴 出纟阜’該些噴出埠係以環繞該第一電極與該第二電極間之 I生電槳的區域之方式予以形成及排列。 與電漿形成活性物種之來源氣體可藉由第一氣體供應 噴嘴引進。 與電漿形成活性物種之來源氣體與基質氣體可藉由第 200905010 一氣體供應噴嘴引進。 較佳地是該第一氣體供應噴嘴應自複數噴出埠朝向第 一電極的中心軸側向地噴出氣體。 較佳地是該第一氣體供應噴嘴應以環繞該第一電極之 方式配置。 較佳地是該第一氣體供應噴嘴的複數噴出埠應排列成 相等間距。 較佳地是第一氣體供應噴嘴的複數噴出埠應具有與第 一電極的中心軸相等的距離。 較佳地是應將具有該第一氣體供應噴嘴之複數噴出埠 中之兩個的每個噴出埠組之噴出埠，予以排列成以該第一 電極的中心軸作爲中心而彼此面對。 較佳地是該第一氣體供應噴嘴之複數噴出埠的高度應 設定成高於產生該電漿的正極柱之區域的最高點。 該第一氣體供應噴嘴可具有環形，或可爲沿著反應爐 中第二電極側邊彼此面對的管路。 該電漿化學氣相沈積裝置可另包含第二氣體供應噴 嘴，其自該第二電極上方噴出基質氣體朝向由該第一氣體 供應噴嘴噴出的氣體。 較佳地是該電漿化學氣相沈積裝置應另包含配置該第 一電極之下的複數排氣導管，而由該反應爐排放氣體。 特佳地是該複數排氣導管應配置成環繞第一電極。 該第二電極可包含複數電極，且可將該第二電極與第 一電極的電極間的電壓或電流個別地設定爲任意値。 200905010 在此例中，複數電極可包括面對該第一電極中央部分 的中央電極，及面對該第一電極的周緣部分的周緣電極， 且中央電極與第一電極間的電壓或電流値在上升期間可以 設定成高於周緣電極與第一電極之間電壓或電流値。 該等複數電極可包括面對該第一電極之中央部分的中 央電極，及面對該第一電極之周緣部分的周緣電極，且在 於該中央電極及第一電極之間形成正極柱之後，中央電極 及第一電極之間的電壓或電流値可設定成小於周緣電極及 第一電極間的電壓或電流値。 較佳地是應將絕緣體配置於該等複數電極之間。 根據本發明第二態樣，其提供電漿化學氣相沈積裝 置，其包含： 電極，係具有由石墨形成的表面，且其上安裝要進行 處理的基板；及 電漿產生單元，係在該電極上產生電漿以在該基板上 實施預定製程。 根據本發明第三態樣，其提供薄膜沈積方法，其包含： 施加電壓在其上安裝基板的第一電極與第二電極之 間；及 自複數噴出埠噴出反應氣體，該等噴出埠係以環繞產 生電漿的區域之方式予以排列。 【實施方式】 以下將參照附屬圖面說明本發明之較佳具體實施例。 [第一具體實施例] -10- 200905010 第1圖爲根據本發明第一具體實施例之DC電漿化學氣 相沈積裝置的組態圖。 DC電漿化學氣相沈積裝置在要處理之基板1的上表面 之上形成薄膜，並具有處理室10做爲反應爐。處理室10 將基板1隔離外界空氣。 柱狀鋼質平臺1 1置於處理室1 0中。由具有高導熱性 及高熔點之材料製成的碟狀陽極1 1 a，例如鉬或石墨，即安 裝在平臺1 1上。陽極1 1 a具有例如80mm的直徑及20mm 的厚度。爲長方形的基板1固定在陽極11a之上安裝面上。 平臺11之設定使得平臺11可與陽極11a共同繞著軸11χ 旋轉。 在陽極11a之下的平臺11具有封閉的空間lib，其中 置有冷卻構件1 2。冷卻構件1 2係用於視需要冷卻基板1， 並建構成可以藉由移動機構（未示出）而如箭頭所示般地上 下移動。冷卻構件1 2由具有高導熱性的金屬形成，例如 銅。一種冷卻劑，例如冷卻水或氯化鈣的冷卻溶液，其由 導管12a進入冷卻構件12中的流動通道12b，並由導管12c 排出而在冷卻構件1 2中循環，以冷卻整個冷卻構件1 2。 當冷卻構件1 2向上移動時，冷卻構件1 2的上方側緊 靠到平臺1 1的底側，其可冷卻覆蓋的陽極1 1 a，其因此將 熱量自基板1帶走。自導管12c排出的冷卻劑由冷卻單元 (未示出）所冷卻，並再次排出到導管1 2a來藉以循環。冷卻 構件1 2之上方側較佳地是應大於基板1，以在平面方向上 均句地冷卻基板1。 -11 - 200905010 提供在陽極1 1 a之下的空間Π b被平臺1 1區隔’所以 空間lib的內部充滿氣體或開放至空氣中。 碟形的陰極13置於陽極11a之上。陰極13支撐在陰 極支撐1 4上，並面對陽極1 1 a。陰極l· 3由鉬、石墨或類似 者所形成，其具有高熔點’且直徑例如爲80mm ’厚度爲 20mm。陰極支撐14由隔熱氧化物製成，例如石英玻璃或 鋁，隔熱氮化物，例如氮化鋁或氮化矽，或隔熱碳化物’ 例如碳化砂。例如陰極1 3與陽極1 1 a之間的距離爲5 0 m m。 冷卻劑流經的通道可在陰極1 3中形成。冷卻劑的流動 可抑制陰極1 3的過熱。較佳的冷卻劑爲水、氯化鈣溶液及 類似者，其由處理室1 0之外供應。 用於抑制電弧發生的絕緣單元1 5置於靠近陽極1 1 a的 外側表面。絕緣單元1 5包含隔熱氧化物，例如石英玻璃或 鋁，隔熱氮化物，例如氮化鋁或氮化矽，或隔熱碳化物， 例如碳化矽等當中其中至少一項。 形狀爲環形的絕緣單元1 5以與陽極1 1 a相同的高度來 支撐，其由在處理室10之底部及環繞陽極11a之內側處直 立提供的支撐1 6所支撐。絕緣單元1 5之外徑設定成等於 或大於陰極1 3的最大外徑之1 .2倍。 因爲絕緣單元1 5用於抑制陰極1 3與陽極1丨a之間的 異常排放電（電弧放電、火花）之發生，絕緣單元1 5沿著陽 極11a之外側表面並相對於陰極13來放置。絕緣單元15 可配置成隱藏陽極1 1 a之側面。 在處理室1 0的側面上形成觀視窗1 7，以允許觀察處理 -12- 200905010 室1 0的內部。隔熱玻璃安裝在觀視窗1 7中，以確保 室1 0內的氣密性。輻射溫度計1 8經由例如觀視窗1 7 基板1之溫度，並置於處理室10之外部。 DC電漿化學氣相沈積裝置具有來源系統（未示出） 經由充氣管19供應含有反應氣體之來源氣體，排氣系| 示出），其經由排氣導管20自處理室10內部排出氣體 及電壓設定單元21。 充氣管1 9經由在處理室1 0中提供的孔洞插入到 室10中，且在反應爐中充氣管19之至少一部分由絕 形成，例如氟化樹脂或矽膠。密合劑密封在處理室1 0 洞與充氣管1 9之外側表面之間，以確保處理室1 〇內 氣密度。在處理室10中，充氣管19連接至環狀噴嘴 其爲氣體供應噴嘴。當環狀噴嘴22較佳地是具有全匱 其形狀可爲規則多邊形。 第2圖爲環狀噴嘴22及排氣導管20之示意圖。 環狀噴嘴22大致具有環狀，且爲中空，所以該來 體在其中流動。具有相等孔洞的複數噴出埠2 2 a係配 環狀噴嘴22之環狀內側表面上。噴出埠22a係提供成 1 1 X或陽極1 1 a之中心軸爲相等距離，且個別的噴出±1 係提供成相對於做爲中心的軸Π X爲點對稱方式而位 對位置處。如下所述，噴出埠22a的形成方式係環繞 電漿的區域，且該來源氣體由噴出埠22a朝向軸llx 地噴出。 環狀噴嘴2 2由附著於陰極支撐1 4之絕緣體噴嘴 處理 測量 ，其 充（未 ，以 處理 緣體 之孔 部的 22， 形， 源氣 置在 與軸 "2a 在相 產生 均勻 支撐 -13- 200905010 23所支撐。環狀噴嘴22之噴出埠22a設定成高於陽極lla 之高度，其位置在低於陰極支撐1 4的最低位置（經由陰極 支撐1 4暴露的陰極1 3之側面的最上方部分）’以及位置在 高於陽極1 1 a與陰極1 3之間形成的正極柱P C之最高點。 因爲環狀噴嘴22被支撐在此範圍中’該來源氣體輕易地進 入陰極13與陽極lla之間’並可防止在正極柱PC中的氣 體溫度由來源氣體之噴射而局部冷卻。 環狀噴嘴2 2的內徑大於陰極1 3的外徑與陽極1 1 a之 外徑。環狀噴嘴2 2的中心位在陽極1 1 a之軸1 1 X上。由陽 極1 1 a的中心朝向個別噴出埠22a之角度大致相等。 四個排氣導管20個別以相等間距穿透處理室1 〇之底 側中形成的四個孔，以圍著軸1 1 x環繞平臺1 Γ或陽極11 a。 密封劑密封於每個孔及相關排氣導管20之外側表面之間。 電壓設定單元21爲一種控制裝置，其設定陽極lla與 陰極1 3之間的電壓或電流之數値，並具有可變的電源 21b。電壓設定單元21藉由導線連接至陽極lla與陰極13。 導線通過在處理室1 0中提供的孔洞而連接到陰極1 3與陽 極1 1 a。在有導線通過的處理室1 0中的孔洞由密封劑所密 封。 電壓設定單元2 1具有控制單元2 1 a，其藉由導線連接 至輻射溫度計1 8，及由導線連接至可變電源2 1 b。當啓動 時，控制單元2 1 a代表由輻射溫度計1 8測量的基板1之溫 度，並調整陽極1 1 a與陰極1 3之間的電壓或電流値，所以 基板1的溫度成爲預定値。 -14- 200905010 接著將說明沈積製程，其使用第1圖中的DC電漿化 學氣相沈積裝置在基板1上形成薄膜。 在沈積製程中，將包含奈米碳壁的電子放電膜沈積於 基板1的上表面上。 奈米碳壁之結構爲複數花瓣式（扇形）薄碳片形成，其 具有直立的曲面’並在隨機的方向上鏈結在一起。每個薄 碳片由數個或數十個單層石墨片所形成，其每一片具有晶 格間距爲0.3 4 n m。 在該沈積製程中，首先例如鎳板切割成基板1，且大 致上利用乙醇或丙酮進行去油脂/超音波洗淨。接著，如果 基板1之上表面由金屬形成，基板1的上表面以具有高熔 點及小直徑的多個絕緣粒子來非常薄地覆蓋，例如鑽石粒 子或氧化鋁粒子。此係因爲當基板1的上表面由金屬形成 時’由來源氣體的一部分所產生的活性物種在基板1中擴 散’所以以活性物種爲導向的沈積即很難沈積在基板1的 上表面上。但是，利用多種絕緣粒子在基板1之上表面上 的薄覆蓋層可允許由基板1的上表面所沈積的沈積層，而 幾乎不會遮蔽陽極11a與陰極13之間的電場。 此基板1係放置在陽極1 1 a上。 當完成安裝基板1時，接下來處理室1 〇使用排氣系統 洩壓’且氫氣、反應氣體及在成份中含有碳的反應氣體之 化合物（含碳化合物），例如甲烷，即由充氣管1 9供應到處 理室10中。來源氣體由環狀噴嘴22之噴出埠22a噴出。 所需要的是在成份中含碳的化合物之反應氣體其整個 -15- 200905010 組成中的範圍在3 v 01 %到3 〇v 01 %之間。例如’曱院的流速 設定爲50 seem’ 氫氣的流速設定爲500 seem ’整個壓力設 定爲0.05到1.5 atm，較佳地是0.07到0· 1 atm。陽極1 la 繞著軸1 1X以1 r p m對基板1旋轉’以設定基板1上的溫 度變化在5%之內’並施加DC電壓在陽極11a與陰極13之 間，以產生電漿，並控制該電漿狀態及基板1之溫度。 在沈積奈米碳壁時，薄膜沈積在溫度900°c到1100°C 之間進行，其設定爲基板1之形成奈米碳壁之該部分的溫 度。此溫度由輻射溫度計1 8測量。此時’冷卻構件1 2大 致與陽極1 1 a區隔，以避免對於陽極1 1 a之溫度的影響。 輻射溫度計1 8之設定使得降低DC電漿化學氣相沈積裝置 之電漿輻射，並僅由在基板1之上方表面處的熱輻射來取 得溫度。 當含有多個鑽石粒子之鑽石層積層在奈米碳壁上，而 在奈米碳壁沈積製程期間改變電子放電膜之薄膜特性，例 如冷卻構件1 2向上移動而緊靠陽極1 1 a。因此，基板1之 溫度可顯著地降低而造成鑽石層的積層。當鑽石層成長 時，棒形的sp2鍵結碳，其爲奈米碳壁的修正部分，且不像 是奈米碳管，其具有塡充的核心而成長。此棒狀的碳延伸 到自鑽石層的上方表面突出，而爲結構上可能集中電場之 部分且釋放電子。 在薄膜沈積的末端平臺處，陽極11a與陰極13之間的 施加電壓即停止，然後來源氣體之供應即停止，並供應氮 氣到處理室1 0中做爲清洗氣體，以在處理室1 〇中提供氮 -16- 200905010 氣環境’然後基板1在將溫度恢復到正常溫度時移除。 根據本具體實施例之DC電漿化學氣相沈積裝置具有 以下的優點（1)到（6)。 . (1)環狀噴嘴22置於處理室1〇中，來源氣體由噴出埠 2 2 a朝向軸1 1 x側向噴出，或在側向向內的方向上，並由四 個排氣導管20排出。因爲噴出埠22a以相等間隔配置在環 狀噴嘴22中’且排氣導管20以相等間隔配置環繞平臺1 1， 來源氣體的流動相對於處理室1 〇中軸丨1 x成爲對稱性地均 勻。因爲陰極13與陰極支撐14不會干擾來源氣體的流動， 來源氣體有效率地流動到陰極1 3之中心正下方，其爲軸 Π X所在之處，所以來源氣體自基板丨之末端到中心來均勻 地分布，且由正極柱PC中來源氣體之一部分所產生的活性 物種的密度成爲均句。此可確保均勻的薄膜沈積在基板1 之上方表面上。 現在將說明檢查在實驗中來源氣體之流動中的差異造 成之影響的結果。 第3A圖及第3B圖爲解釋在比較性實驗中使用之DC 電槳化學氣相沈積裝置之組態圖。 第4A圖爲在第3A圖及第3B圖中所示之DC電漿化學 氣相沈積裝置中發生在陰極上輝光狀態圖；第4B圖爲根據 第一具體實施例之DC電漿化學氣相沈積裝置中發生在陰 極上輝光狀態圖。 在該實驗中，第1圖中DC電漿化學氣相沈積裝置之 一部分的改變方式爲來源氣體之流動不會成爲相對於軸 -17- 200905010 llx對稱，且陰極13置於陽極lla與噴嘴之間而成爲 的干擾。如第3 B圖所示，例如環狀噴嘴2 2及噴嘴支; 自處理室10內部移除，充氣管19連接至處理室1〇中 陰極支撐14之上方的氣體噴淋噴嘴25’所以氣體由氣 淋噴嘴25向下噴射，像是淋浴一般’且僅有複數排氣 20之一留下，而將停止器24插入其他排氣導管20中 防止自其中安裝有停止器24之排氣導管20排出。其 組態相同於第1圖中的DC電漿化學氣相沈積裝置。爲 示由來源氣體之入口及出口的位置相對於來源氣體做 體的移動造成的影響，在比較性實驗中，DC電漿化學 沈積裝置，類似本具體實施例之DC電漿CVD裝置， 有絕緣單元1 5。 其將可觀察到發生在第3B圖所示之修正的DC電 學氣相沈積裝置中及第1圖之DC電漿化學氣相沈積裝 陰極1 3之下的輝光狀態。請注意到來源氣體爲氫氣， 爲5 00 seem，氣壓爲30 torr，且有2A的電流通過陰極 在如第3B圖所示修正的DC電漿化學氣相沈積 中，將自氣體噴淋噴嘴25噴出的來源氣體導引到不具 止器24之一個排氣導管20,所以來源氣體不會輻射狀 動，不像是第3A圖中箭頭所示，且氣體在陰極13之 處不會相對於軸Π X對稱地流動，且來源氣體之流動 不具有停止器24之排氣導管2〇集中，如第3B圖中 串鏈線所示。因爲陰極1 3成爲對於來源氣體之流動 干擾，來源氣體變得很難環繞陰極丨3，以到達陽極 空間 掌23 位在 體噴 導管 ，以 他的 了顯 爲流 氣相 即具 漿化 置中 流速 13 ° 裝置 有停 地流 下游 朝向 點的 空間 1 1 a之 -18- 200905010 中心處的軸1 1 χ，藉此造成於基板1之上表面處到達之活性 物種之密度中平面間的變化。這種變化在當基板1變大而 使得陰極1 3與陽極1 1 a更大時更加明顯。 在如第3 B圖所示修正的DC電漿化學氣相沈積裝置 中，如第4 A圖所示。在陰極1 3處陰極輝光的形狀之傾斜 代表溫度分布亦具有傾斜’所以在基板1上的薄膜沈積有 可能改變。在如第1圖所示修正的D C電漿化學氣相沈積裝 置中，利用對比，在陰極1 3處發生的輝光不會傾斜。因此 可以確保在基板1上均勻的薄膜沈積。 (2) 因爲充氣管19由絕緣體形成’且環狀噴嘴22支撐 在絕緣體噴嘴支撐2 3上’以將環狀噴嘴2 2絕緣於電源或 接地，來自陰極1 3或陽極1 1 a之浪費的電弧放電或類似者 即不會發生。 (3) 因爲環狀的環狀噴嘴22之內徑大於陰極13與陽極 11a之外徑，環狀噴嘴22不會重疊正極柱PC，其具有陰極 1 3與陽極1 1 a之間高密度活性物種’所以在噴出埠22a之 部分處不會有以電漿爲主的溫度上升’藉以抑制在噴出埠 22a處發生沈積。 (4) 因爲環狀噴嘴22之噴出埠22a之高度高於正極柱 PC之最大點，在正極柱PC處的氣體溫度不會被自噴出埠 22a噴出的低溫氣體由側面局部地冷卻’所以不會干擾正極 柱PC之形狀的對稱性。 (5) 絕緣單元15防止電弧放電的發生，其會干擾自陰極 1 3朝向陽極1 1 a之外側表面的均勻薄膜沈積。 -19- 200905010 (6)環狀噴嘴22置於與陰極π之電極表面相同的位置 處，或是低於該電極表面的位置處，而自環狀噴嘴2 2側向 排出的來源氣體即被導引朝向下方的排氣導管2〇。此可防 止在正極柱PC中產生的高度反應性活性物種被擴散成接 觸到陰極丨3。因此其有可能防止活性物種沈積在陰極} 3 上，其造成電弧放電或火星。 [第二具體實施例] 第5A圖及第5B圖爲根據本發明第二具體實施例之dc 電漿化學氣相沈積裝置之組態圖。對於與第丨圖之組件共 用之第5A圖及第5B圖中的那些組件皆給與共用的參照編 號。 此DC電漿化學氣相沈積裝置爲第1圖中DC電漿化學 氣相沈積裝置’其陰極13改變成陰極27，且其電壓設定單 元21改變成電壓設定單元28。 陰極27具有碟形的中央電極27a，其面對陽極1 U之 中央部分’周緣電極27b，其形狀爲環（參見第5B圖），環 繞中央電極27a，其與中央電極27a同圓心，並面對陽極 1 1 a之周緣部分，及陶瓷或類似者製成的絕緣部分27c完全 塡滿在中央電極27a與周緣電極27b之間。 當沒有絕緣部分27c插入中央電極27a與周緣電極27b 之間，彼此面對之中央電極27a之側壁上及周緣電極27b 之側壁上以及在基板1上的電場強度皆會變弱，產生一部 分不會有陰極輝光覆蓋，除非中央電極27 a與周緣電極27 b 之間的距離是充份地長。因爲此部分具有較少的離子轟 -20- 200905010 擊，沈積物有可能沈積在此處。這種沈積物造成電弧放電 或火花。在此方面，絕緣部分27c被插入，以防止薄膜沈 積在彼此面對之中央電極27a之側壁上與周緣電極27b的 側壁上。 電壓設定單元28具有控制單元28a，及可變電源28b、 28c = 控制單元28a由導線連接至輻射溫度計1 8。控制單元 2 8 a具有能力來控制可變電源2 8 b、2 8 c，並個別地設定陽 極11a與中央電極27a之間的電壓或電流，及陽極11a與 中央電極27a之間的電壓或電流。其他的組態相同於第1 圖中的DC電漿化學氣相沈積裝置。 如果使用第5A圖及第5B圖中的DC電漿化學氣相沈 積裝置形成薄膜在基板1上時，基板1於電漿上升時以1 rpm的速率旋轉，平臺11與中央電極27a之間的電勢差在 電壓設定單元28之控制之下將會大於平臺Π與周緣電極 27b之間的電勢差，以設定陰極27與陽極Π a之間的電壓。 這種電壓施加在陽極1 la與中央電極27a之間產生小的正 極柱PC。此可防止電弧放電的發生，其經常發生於開始時 產生大的正極柱的時候。 在該穩定正極柱PC由施加這樣的電壓或電流而形成 在基板1之中央部分的上部後，控制單元2 8 a施加該電壓 或電流使得陽極1 1 a與中央電極27a之間的電壓或電流値 成爲小於陽極1 1 a與周緣電極2 7 b之間的電壓或電流値’ 以將陽極11a與中央電極27a之間的溫度近似於陽極11a -21 - 200905010 與周緣電極2 7 b之間的溫度’或使得那些溫度於在基板1 上進行薄膜沈積之前大致相等。 在本具體實施例中’如上所述，陰極27包含中央電極 27 a與周緣電極27 b，及陽極Ua與中央電極27 a·之間的電 壓或電流値，陽極1 1 a與周緣電極27b之間的電壓或電流 値可獨立地設定。在電漿上升時，陽極1 la與中央電極27a 之間的電壓被設定高於陽極11a與周緣電極27b之間的電 壓。因此，正極柱PC可利用將陽極1 1 a與陰極27之間的 距離變得較短來形成。要施加於陽極11a與陰極27的電壓 可以較低，藉此抑制電弧放電或火花之經常發生。 再者，流過周緣電極27b之電流會變成小於流過中央 電極27a之電流，以產生集中在基板1之中央處的正極柱 PC，然後施加到周緣電極27b之電力即增加，以增加流過 周緣電極27b之電流。此使其有可能防止發生在薄膜沈積 之初始階段之局部電弧放電，然後正極柱P C可成長到需要 的尺寸。 [第三具體實施例] 第6圖爲根據本發明第三具體實施例之DC電漿化學 氣相沈積裝置的組態例。對於第6圖中的那些組件與第1 圖中的組件共同時即給與共用的參照編號。 DC電漿CVD裝置具有處理室30做爲反應爐。處理室 3〇將基板1隔離外界空氣。 柱狀鋼質平臺11置於處理室30中。由具有高導熱性 及筒熔點之材料製成的碟狀陽極1 1 a，例如鉬或石墨，即安 -22- 200905010 裝在平臺11上。爲長方形的基板1固定在陽極lla之上方 安裝面上。平臺11之設定使得平臺11可與陽極11a共同 繞著軸11X旋轉。 在陽極lla之下的平臺11具有封閉的空間lib，其中 置有冷卻構件1 2。冷卻構件1 2係用於視需要冷卻基板1， 並建構成可以藉由移動機構（未示出）而如箭頭所示般地上 下移動。冷卻構件1 2由具有高導熱性的金屬形成，例如 銅。一種冷卻劑，例如冷卻水或氯化鈣的冷卻溶液，其由 導管12a進入冷卻構件12中的流動通道12b，並由導管12c 排出而在冷卻構件1 2中循環，以冷卻整個冷卻構件1 2。 當冷卻構件1 2向上移動時，冷卻構件1 2的上方側鄰 接到平臺1 1的底側，其冷卻位在上面的陽極1 1 a，其因此 將熱量自基板1帶走。自導管1 2c排出的冷卻劑由冷卻單 元（未示出）所冷卻，並再次排出到導管12a來藉以循環。 碟形的陰極13置於陽極lla之上方。陰極13支撐在 陰極支撐14上，並面對陽極lla。陰極13由鉬、石墨或具 有高熔點之類似材料所形成。陰極支撐1 4由隔熱氧化物， 例如石英玻璃或鋁，隔熱氮化物，例如氮化鋁或氮化矽， 或隔熱碳化物，例如碳化矽等製成。 冷卻劑流過的通道可形成在陰極1 3中。冷卻劑的流動 可抑制陰極1 3的過熱。 用於抑制電弧發生的絕緣單元1 5置於靠近陽極1 1 a的 外側表面。絕緣單元1 5包含隔熱氧化物，例如石英玻璃或 鋁’隔熱氮化物，例如氮化鋁或氮化矽，或隔熱碳化物， -23- 200905010 例如碳化矽等當中至少一項。 形狀爲環形的絕緣單元1 5以與陽極1 1 a相同的高度 支撐，其由在處理室30之底部及環繞陽極lla之內側處 立提供的支撐1 6所支撐。絕緣單元1 5之外徑設定成等 或大於陰極13的最大外徑之1.2倍。 因爲絕緣單元1 5用於抑制陰極1 3與陽極1 1 a之間 異常排放電（電弧放電、火花）之發生，絕緣單元1 5沿著 極1 1 a之外側表面並相對於陰極1 3來放置，並配置成隱 陽極1 1 a之側面。 在處理室3 0的側面上形成觀視窗1 7，以允許觀察處 室30的內部。隔熱玻璃安裝在觀視窗1 7中，以確保處 室3 0內的氣密性。輻射溫度計1 8可經由例如觀視窗1 7 量基板1之溫度，並置於處理室30之外部。 DC電漿化學氣相沈積裝置具有來源系統（未示出）， 透過充氣管31供應反應氣體做爲活性物種的來源，來源 統（未示出）’其透過充氣管32供應基質氣體（載具氣體） 排氣系統（未示出），其自處理室3 0內部經由排氣導管 排出氣體，及電壓設定單元21。 充氣管31’其由絕緣體製成，其通過在處理室30中 供的孔洞。密封劑密封在該孔洞與充氣管31之外側表面 間，以確保處理室3 0之內的氣密性。在處理室3 〇中， 氣管31連接至環狀噴嘴33。 環狀噴嘴3 3類似於第2圖所示的環狀噴嘴2 2。具有 等孔洞之複數噴出埠3 3 a以環狀的方式配置在環狀噴嘴 來 直 於 的 陽 藏 理 理 測 其 系 > 20 提 之 充 相 -24- 33 200905010 之內側表面，並以與軸1 1 X或陽極1 1 a之中心軸等距離的 方式提供。個別的噴出埠3 3 a以相對於作爲中心的軸1 ! x 之點對稱方式提供在相對位置處，而自噴出埠3 3 a朝向軸 llx均勻地噴出該來源氣體。 環狀噴嘴33由附著於陰極支撐14之絕緣體噴嘴支撐 23所支撐。環狀噴嘴33之噴出埠33a設定成其位置在低於 陰極支撐1 4的最低部分的位置處（經由陰極支撐1 4暴露的 陰極13之側面的最上方部分），以及位置在高於陽極1 1 a 與陰極1 3之間形成的正極柱PC之最高點。因爲將環狀噴 嘴3 3支撐在此範圍中，該反應氣體輕易地進入陰極1 3與 陽極11a之間，並可防止由於該反應氣體之噴出的局部冷 卻造成對於正極柱PC之對稱性的擾動。 環狀噴嘴33的內徑大於陰極13的外徑與陽極11a之 外徑。環狀噴嘴3 3的中心位在陽極1 1 a之軸1 1 X上。由陽 極1 1 a的中心朝向個別噴出埠3 3 a之角度大致相等。 四個排氣導管20個別以相等間距穿透處理室30之底 側中形成的四個孔，以圍著軸1 1 X環繞平臺1 1。密封劑密 封於每個孔及相關排氣導管20之外側表面之間。 電壓設定單元21爲一種控制裝置，其設定陽極lla與 陰極1 3之間的電壓或電流之數値，並具有可變的電源 21b。電壓設定單元21藉由導線連接至陽極lla與陰極13。 導線通過在處理室30中提供的孔洞而連接到陰極13與陽 極1 1 a。在有導線通過的處理室30中的孔洞由密封劑所密 封。 -25- 200905010 電壓設定單元21具有控制單元21a，其藉由導線連接 至輻射溫度計1 8，及由導線連接至可變電源2 1 b。當啓動 時，控制單元2 U代表由輻射溫度計1 8測量的基板1之溫 度，並調整陽極1 1 a與陰極1 3之間的電壓或電流値，所以 基板1的溫度成爲預定値。 充氣管32’其由絕緣體製成，其通過在處理室30中提 供的孔洞。密封劑密封在該孔洞與充氣管3 2之外側表面之 間，以確保處理室3 0之內的氣密性。在處理室3 0中，充 氣管32連接至氣體噴淋噴嘴34。 氣體噴淋噴嘴34放置在支撐陰極13之陰極支撐14之 上方及環狀噴嘴33之上方。具有相等孔洞之複數噴出埠環 繞軸1 1 X同圓心或輻射狀形成在氣體噴淋噴嘴34之底側 中。該等個別的噴出埠相對於做爲中心之軸1 1 X爲點對稱 地提供在相對位置處來向下噴出該基質氣體，像是淋浴。 在使用本具體實施例之DC電漿化學氣相沈積裝置進 行薄膜沈積之基本作業類似於使用第一具體實施例之DC 電槳化學氣相沈積裝置的案例。其要注意到本具體實施例 之DC電漿化學氣相沈積裝置中，基質氣體及反應氣體被 獨立地引進，且反應氣體在側向向內方向上自環狀噴嘴3 3 噴出，而基質氣體自氣體噴淋噴嘴34向下噴出。基質氣體 改變側向噴出之反應氣體之流動向量，所以該反應氣體流 動朝向該斜向位在下方的基板1。 以下將解釋環狀噴嘴3 3之高度的驗證實驗。 第7圖爲驗證實驗的簡略圖。 -26- 200905010 在該驗證實驗中，薄膜沈積之進行藉由將陽極1 1 a與 陰極13之直徑設定爲160mm，其厚度設定爲15mm’陽極 11a與陰極13之間的距離設定爲60mm，環狀噴嘴33之內 徑設定爲305mm，其管路直徑設定爲〇·25吋’氣體噴淋噴 嘴3 4之噴出埠所位在的底側與陰極1 3之底側之間的距離 設定爲260mm，由氣體噴淋噴嘴34所排出的基質氣體中氫 氣的流速設定爲600sccm，在基質氣體中氬氣的流速設定爲 48sccm，在反應氣體中甲烷的流速設定爲60sccm，氣體壓 力設定爲60Torr，陰極13與陽極11a之間的電流設定爲 16A，矽基板具有正方形，其一側邊爲75mm，及其厚度0.7mm 被使用做爲基板1，且沈積時間設定爲2小時，而改變環 狀噴嘴3 3之高度。如第7圖所示，位在陰極13之底側之 下10mm的環狀噴嘴33之噴出埠33a的位置爲高位置，且 位在陽極11a之上表面之上方的噴出埠33a的位置爲低位 置。 第8圖及第9圖爲解釋該驗證實驗的結果圖。在該驗 證實驗中，奈米碳壁之成長可在位於基板1中央及軸Ux 上的觀察點A，及與端面距離l〇mm之距離L1並與相鄰於 前述端面的兩個端面距離37.5mm之距離L2的觀察點B觀 察到。 於該反應氣體由該高位置排出之情況中，以及於該反 應氣體自該低位置排出的情況中皆觀察到在基板1上奈米 碳壁之成長。 第9A圖及％ 9C圖爲斷層攝影SEM影像，所示分別爲 -27- 200905010 在觀察點A及觀察點B處奈米碳壁之成長’當電獎化學氣 相沈積利用環狀噴嘴3 3之噴出埠3 3 a在該高位置處執行兩 個小時。第9B圖及第9D圖爲斷層攝影SEM影像’所示分 別爲在觀察點A及觀察點B處奈米碳壁之成長’當電漿化 學氣相沈積利用環狀噴嘴3 3之噴出埠3 3 a在該低位置處執 行兩個小時。 如第9A圖及第9C圖所示’當反應氣體僅由該高位置 排出時，在觀察點A及觀察點B處奈米碳壁之成長的程度 並沒有太大差異。當反應氣體僅由低位置排出時’如第9 B 圖及第9D圖所示爲奈米碳壁之成長程度之間有差異；該奈 米碳壁於觀察點B處會比觀察點A處成長較大。 造成該差異的原因似乎在該低位置處，自環狀噴嘴33 噴出的反應氣體放置過低，且相較於該高位置的情況更難 到達該觀察點A，並使得在電漿中周緣部分處（位在該中央 部分之外）的溫度會低於在該中央部分處的溫度’藉以增加 電漿中在中央部分處與在周緣部分的氣體溫度之間的差 異。在靠近基板1之外側表面處部位之電漿中的氣體溫度 下降造成具有相對較低之化學勢之活性物種的密度會增 加，並造成非均勻的薄膜沈積。 在該高位置處，另一方面，該低溫反應氣體並未直接 噴灑到正極柱PC上，所以在該氣體中的溫度梯度較小，且 不會發生非均勻的薄膜沈積。 現在將說明當改變噴出埠3 3 a之直徑時觀察薄膜沈積 之狀態的實驗。 -28- 200905010 環狀噴嘴3 3之位置係設定成如第7圖所示之高位置， 及在當改變噴出埠33a之直徑到〇.5mm、1.0mm及1.5mm 時所測量的該基板之上表面處發射率之改變。在將類似奈 米碳壁之石墨結構沈積在砂基板上的情況下，該發射率大 致會在當薄膜厚度增大時即會變得較高。在單位時間之反 應氣體的流速藉由設定利用噴出埠3 3 a直徑爲〇 . 5 m m剛噴 出之後的氣體之移動速率來設定等於5 00c m/s，設定利用噴 出埠33a直徑爲1.0mm剛噴出之後的氣體之移動速率來設 定等於125 cm/s，設定利用噴出埠33a直徑爲1.5 mm剛噴出 之後的氣體之移動速率來設定等於5 5 cm/s。 第10A圖、第丨0B圖及第10C圖爲斷層攝影SEM影像， 所示分別爲在第8圖所示之觀察點A(基板中央）處薄膜沈 積的狀態，當藉由在該高位置處具有直徑設定爲〇.5mm、 1.0mm及1.5 mm的環狀噴嘴33之噴出埠33a之電漿化學氣 相沈積裝置執行電漿化學沈積兩個小時時。第11圖所示爲 利用噴出埠33a的直徑設定爲〇.5mm、1.0mm及l，5mm在基 板1處的發射率。 該斷層攝影SEM影像顯示於噴出埠33a的直徑爲 0.5mm、噴出璋33a的直徑爲1.0mm、噴出掉33a的直徑爲 1.5 mm的任何狀況下於觀察點A及B處垂直於該基板之方 向上，在奈米碳壁之成長中沒有很大的不同。但是’在當 噴出捧 33a 之直徑爲 〇.5 mm (Φ〇_5)、1.0 mm (Φ1.0)及 1.5 mm (Φ 1.5)的情況時比較在觀察點Α處的斷層攝影SEM影像 可以瞭解，於φΐ·〇及Φΐ.5時垂直於基板的方向上奈米碳壁 -29- 200905010 之成長大於在Φ0.5時垂直於基板的方向上奈米碳壁之成 長。 由第11圖可以瞭解在基板之發射率中的改變在Φ0.5與 Φ 1. 0之間幾乎未改變並於1小時3 0分鍾之後到達該高原 期，然而在Φ 1.5時在奈米碳壁成長時發射率之增加顯示將 會變得較慢的趨勢。這種發射率的增加根據構成在該基板 之上表面上的奈米碳壁之石墨成份之密度。 其已知在垂直於該基板之方向上奈米碳壁之成長在當 朝向該基板1垂直導向的活性物種的量變得較大時會變得 更快。當Φ0.5時，該發射率較快地到達該高原期，且奈米 碳壁之高度相較於Φ 1. 0及Φ 1. 5時較低，所以側向成長的速 率之比例似乎大於Φ 1. 0及Φ 1 · 5的狀況。此代表當Φ 0.5時電 漿形成的活性物種之流動的側向速率成分大於在其他兩個 情況之側向速率成分，且甲烷氣體之噴出速率太快’所以 通過該電漿的正極柱PC之氣體的流動會略受干擾。 當Φ 1.5時，當沈積時間爲2小時，垂直於該基板的方 向上奈米碳壁之高度幾乎與Φ〇·5及Φ1.0時2小時的沈積時 間垂直於該基板的方向上奈米碳壁之高度沒有差異’但到 達該高原之發射率之速率會比其他兩個情況中的速率要 慢，且在垂直於該基板的方向上奈米碳壁之成長大致等於 Φ 1.0的情況，其代表整個石墨成分之沈積速率會低於Φ 〇 . 5 及Φ 1.0的情況，且因此奈米碳壁之側向成長的速率會變得 較慢。此似乎是因爲反應氣體的噴出速率較慢’所以反應 氣體的對流不會被干擾太多’而到達該電漿中心處反應氣 -30- 200905010 體的量小於在φθ.5及Φ1.0之情況。 也就是說，當Φ0.5時形成的奈米碳壁之基板的單位面 積比當Φ1.5時形成的奈米碳壁要有較高的密度，但在垂直 於該基板的方向上之成長較慢。當Φ1.5時形成的奈米碳壁 在垂直於該基板的方向上會比當Φ0.5時形成的奈米碳壁之 成長較快，但當該基板之單位元面積其密度成爲足夠高時 會較慢。但是，當Φ 1 · 5時形成的奈米碳壁在當沈積時間到 達兩小時時成長到充份的密度。 因此在該具體實施例中，理想上在由環狀噴嘴3 3剛噴 出之後反應氣體之移動速率爲125 cm/s左右（噴嘴爲 Φ1.0)，用於奈米碳壁之均勻成長’且理想上反應氣體之移 動速率爲55cm/s左右（噴嘴爲Φ1.5)到125cm/s左右（噴嘴爲 Φ1.0)，雖然具有略微不良的均勻度時仍可取得良好電子放 電特性。 根據本具體實施例之DC電漿化學氣相沈積裝置除了 第一具體實施例之優點之外具有以下的優點（7)。 (7)其槪略可知該反應氣體相對於基質氣體之濃度會 影響薄膜品質。但是在引入氣體混合物之方法中，該氣體 混合物具有僅混合反應氣體與基質氣體爲預定濃度，並藉 由自然產生的對流供應該氣體混合物到該基板，新引入的 氣體混合物之一部分在該氣體混合物充份到達基板1上之 前自排氣導管20排出，所以在基板1之上的反應氣體之濃 度可變成低於在引入之氣體混合物的濃度。如果在氣體混 合物中反應氣體的濃度即增加以避免反應氣體導向的沈積 -31- 200905010 物有可能發生在陰極13及支撐陰極π之陰極支撐14，使 得電獎變成電弧放電或火花。本具體實施例之DC電漿化 學氣相沈積裝置獨立地引進基質氣體與反應氣體，設定反 應氣體之噴出位置相對高於基板1，並設定基質氣體之噴 出位置高於反應氣體的噴出位置，所以朝向基板丨之反應 氣體的流動可由基質氣體之向下力量所操縱，藉以降低浪 費排出的反應氣體量。此外，基質氣體的噴出位置設定於 陰極13與支撐陰極13之陰極支撐14之上，且反應氣體之 噴出位置設定在陰極1 3之底側之下，所以該向下力量於基 質氣體到達排氣導管20時被施加，抑制反應氣體朝向陰極 13對抗基質氣體之流動的反向流動，並防止反應氣體成分 黏著到陰極13及支撐陰極13的陰極支撐14上。 [第四具體實施例] 第12A圖及第12B圖所示爲根據本發明第四具體實施 例之DC電漿化學氣相沈積裝置的組態圖。對於與第6圖之 組件共用之第1 2A圖及第1 2B圖中的那些組件皆給與共用 的參照編號。 此DC電漿化學氣相沈積裝置爲第1圖中DC電漿化學 氣相沈積裝置，其陰極13改變成陰極35,且其電壓設定單 元21改變成電壓設定單元36。 陰極35具有中央電極35a，其面對陽極11a之中央部 分，周緣電極35b，其形狀爲環（參見第12B圖）’環繞中央 電極35a，其與中央電極35a同圓心’並面對陽極11a之周 緣部分，及陶瓷或類似者製成的絕緣部分3 5 c完全塡滿在 -32- 200905010 中央電極35a與周緣電極35b之間。 若不將絕緣部分35c插入在中央電極35a與周緣電極 35b之間，則由活性物種成長的薄膜不僅沈積在基板1上， 亦在彼此面對的中央電極35a之側壁與周緣電極35b之側 壁上。在此方面，絕緣部分35c被插入，以防止薄膜沈積 在彼此面對之中央電極35a之側壁上與周緣電極35b的側 壁上。 電壓設定單元36具有控制單元36a，及可變電源36b、 3 6 c ° 控制單元36a由導線連接至輻射溫度計1 8。控制單元 36a具有能力來控制可變電源36b、36c，並個別地設定陽 極1 1 a與中央電極3 5 a之間的電壓或電流，及陽極Π a與 中央電極3 5 b之間的電壓或電流。其他的組態相同於第6 圖中的DC電漿化學氣相沈積裝置。 如果使用第12A圖及第12B圖中的DC電漿化學氣相 沈積裝置形成薄膜在基板1上時，基板1於電漿上升時以 1 rpm的速率旋轉，陽極11a與中央電極35a之間的電壓在 電壓設定單元36的控制之下會大於陽極11a與周緣電極 35b之間的電壓，以設定陰極35與陽極1 1 a之間的電壓。 這樣的施加電壓在陽極1 1 a與中央電極3 5 a之間產生小的 正極柱PC，並可防止在薄膜沈積的初始階段發生電弧放 電。 在該穩定正極柱PC由施加這樣的電壓或電流而形成 在基板1之中央部分的上部時，控制單元3 6 a施加該電壓 -33- r200905010 IX. Description of the Invention: [Technical Field] The present invention relates to a plasma chemical vapor deposition apparatus and a thin film deposition method. [Prior Art] A chemical vapor deposition apparatus deposits a thin film on a substrate by chemical vapor deposition (CVD), which supplies a matrix gas and a reactive gas as a source gas into the reaction furnace, and utilizes The exhaust rate balances the gas supply to maintain the pressure in the reactor. In a plasma chemical vapor deposition apparatus that produces plasma, the temperature of the gas locally becomes higher, causing gas turbulence in the reactor. It is desirable that the gas containing the reaction gas must flow slowly and uniformly to the upper surface of the substrate, and a film grown by the reaction of the gas will be deposited there. It is known that if the gas flows too fast, causing irregular deposition, and if the vector of the traveling direction of the reactive gas is not directed toward the substrate, the film growth rate becomes slower. A conventional plasma chemical vapor deposition apparatus is intended to overcome irregular deposition and maintain a growth rate, for example, in Japanese Patent No. 2 6 2 8 4 4 4, Unexamined Japanese Patent Application Laid-Open No. H1-94615, and Yoshiyuki Abe et al. In the Acta Astronautica (Great Britain) period "DIAMOND SYNTHESIS BY HIGH GRAVITY D. C. PLASMA CVD (HGCVD) WITH ACTIVE CONTROL OF THE SUBSTRATE TEMPERATURE", 2001, Vol. 48, No. 2-3, pp. 121-127. The plasma chemical vapor deposition 200905010 device disclosed in Japanese Patent No. 2628404 supplies a reaction gas in a direction parallel or oblique to the upper surface of the substrate, supplies a matrix gas from a direction substantially perpendicular to the upper surface of the substrate, and is extruded. The reaction gas and the matrix gas change the flow direction of the reaction gas to spray the reaction gas onto the upper surface of the substrate. However, this plasma chemical vapor deposition apparatus is a pyroplasmic chemical vapor deposition apparatus which uses a heater to heat the crystal holder to generate a thermal plasma without considering the electrode configuration. In the case of a DC plasma chemical vapor deposition apparatus in which, for example, an electrode is placed at a position facing the substrate, the electrode becomes a bottleneck, making it difficult to form a uniform flow of gas in a direction perpendicular to the substrate. The plasma chemical vapor deposition apparatus described in Japanese Unexamined Patent Application Publication No. Publication No. No. No. H. This allows the reaction gas to flow from the cathode to the substrate. However, with this structure, plasma is generated at this time, and the reaction gas which produces the active species exhibits a high density at the nozzle portion of the hot cathode. Therefore, deposits are gradually formed on the cathode and stored in the nozzle, thereby disturbing gas injection. If the deposit grows close to the nozzle and becomes a projection, the electric field is concentrated on the projection, so the plasma may be converted into an arc discharge or Mars. Furthermore, the gas whose temperature is lowered by room temperature or expansion is sprayed toward the plasma, so the positive electrode column may partially shrink, which may cause irregular film deposition. In the paper "DIAMOND SYNTHESIS BY HIGH GRAVITY D. C. The plasma chemical vapor deposition apparatus described in PLASMA CVD (HGCVD) WITH ACTIVE CONTROL OF THE SUBSTRATE TEMPERATURE" provides a gas inlet in the upper part of the reaction furnace and a gas 200905010 outlet in the lower part to generate a gas flow from the cathode toward the anode. And through Fig. 37A and Fig. 37B are flow diagrams for explaining the gas in the reactor of the plasma chemical vapor phase. Figure 37A shows the reaction state' and Figure 37B shows the flow rate of the gas flow at 1G and the arrow. In the electric paddle chemical vapor deposition apparatus, as shown in Fig. 37A, the position of the inlet GI and the position of the gas outlet GO are opposed to each other with the central axis therebetween. Therefore, when the vicinity of the lower portion of the gas cathode moving toward the anode is the most, there is a temperature difference between the convection at the gas inlet GI and the gas convected at the gas outlet GO, as shown in the figure. Furthermore, the partial pressure of the gas will be different. In a DC plasma chemical vapor deposition apparatus, a partial pressure state of each component in an active species to be a film material varies depending on a plasma temperature, and when the temperature becomes high, a species having a high chemical potential Part of the pressure enthalpy will be higher than the partial pressure enthalpy of the species with a relatively low chemical potential. The temperature difference in the reactor causes a temperature in the plasma. Therefore, the partial pressure of each active species is irregular according to its position, which causes uneven film deposition. SUMMARY OF THE INVENTION The vapor deposition apparatus disclosed in Japanese Patent No. 2628404 is a pyrochemical chemical vapor deposition apparatus, and the heater heats the crystal holder to generate a thermal plasma, unlike DC electrical phase deposition. The device 'it is difficult to form a uniform gas flow relative to the substrate when the electrodes are placed facing this position. Pulp. The assembly direction of the deposition furnace is changed from the randomization of the gas active material in the gas reactor 37B deposition material to the plasma slurry. The use of the pulp chemical substrate 200905010 in the early days of the unexamined Japanese patent application The plasma chemical vapor deposition apparatus disclosed in the publication No. H1-94615 is not technically satisfactory because it causes problems when the film is deposited, and may cause irregular film deposition. In the paper "DIAMOND SYNTHESIS BY HIGH GRAVITY D. C. The plasma CVD apparatus disclosed in PLASMA CVD (HGCVD) WITH ACTIVE CONTROL OF THE SUBSTRATE TEMPERATURE" causes a completely uniform gas supply to the substrate. Accordingly, it is an object of the present invention to provide a plasma chemical vapor deposition apparatus and a thin film deposition method which can uniformly supply a reaction gas to an upper surface of a base, and even when an electrode is placed at a position facing the substrate Stable film deposition is ensured. To this end, according to a first aspect of the present invention, there is provided a plasma chemical vapor deposition apparatus comprising: a first electrode disposed in a reaction furnace, and a substrate mounted on the first electrode; a second electrode Is disposed above the first electrode and opposite to the first electrode and generates plasma with the first electrode; and a first gas supply nozzle is disposed at 1% of the first electrode in the reaction furnace a height between the height and the height of the second electrode, and having a plurality of ejection ports 该 formed to surround a region of the I generator paddle between the first electrode and the second electrode arrangement. The source gas that forms the active species with the plasma can be introduced by the first gas supply nozzle. The source gas and the matrix gas which form an active species with the plasma can be introduced by a gas supply nozzle of 200905010. Preferably, the first gas supply nozzle should eject gas laterally from the plurality of ejection ports toward the central axis of the first electrode. Preferably, the first gas supply nozzle should be disposed in a manner surrounding the first electrode. Preferably, the plurality of ejection orifices of the first gas supply nozzle are arranged at equal intervals. Preferably, the plurality of ejection orifices of the first gas supply nozzle should have a distance equal to the central axis of the first electrode. Preferably, the ejection ports of each of the plurality of ejection ports having the first gas supply nozzles are arranged to face each other with the central axis of the first electrode as a center. Preferably, the height of the plurality of jets of the first gas supply nozzle is set to be higher than the highest point of the region where the positive electrode of the plasma is generated. The first gas supply nozzle may have a ring shape or may be a pipe that faces each other along the side of the second electrode in the reactor. The plasma chemical vapor deposition apparatus may further include a second gas supply nozzle that ejects the matrix gas from above the second electrode toward the gas ejected by the first gas supply nozzle. Preferably, the plasma chemical vapor deposition apparatus further comprises a plurality of exhaust conduits disposed below the first electrode, and the gas is discharged from the reactor. More preferably, the plurality of exhaust conduits should be configured to surround the first electrode. The second electrode may include a plurality of electrodes, and the voltage or current between the electrodes of the second electrode and the first electrode may be individually set to any 値. 200905010 In this example, the plurality of electrodes may include a central electrode facing the central portion of the first electrode, and a peripheral electrode facing a peripheral portion of the first electrode, and a voltage or current between the central electrode and the first electrode is present The rising period can be set to be higher than the voltage or current 之间 between the peripheral electrode and the first electrode. The plurality of electrodes may include a central electrode facing a central portion of the first electrode, and a peripheral electrode facing a peripheral portion of the first electrode, and after forming a positive electrode column between the central electrode and the first electrode, the center The voltage or current 之间 between the electrode and the first electrode can be set to be smaller than the voltage or current 间 between the peripheral electrode and the first electrode. Preferably, an insulator is disposed between the plurality of electrodes. According to a second aspect of the present invention, there is provided a plasma chemical vapor deposition apparatus comprising: an electrode having a surface formed of graphite and having a substrate to be processed thereon; and a plasma generating unit A plasma is generated on the electrodes to perform a predetermined process on the substrate. According to a third aspect of the present invention, there is provided a thin film deposition method comprising: applying a voltage between a first electrode and a second electrode on which a substrate is mounted; and ejecting a reaction gas from a plurality of ejection jets, the ejection systems are Arrange the way around the area where the plasma is generated. [Embodiment] Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. [First embodiment] -10-200905010 Fig. 1 is a configuration diagram of a DC plasma chemical vapor deposition apparatus according to a first embodiment of the present invention. The DC plasma chemical vapor deposition apparatus forms a thin film on the upper surface of the substrate 1 to be processed, and has a processing chamber 10 as a reaction furnace. The processing chamber 10 isolates the substrate 1 from outside air. A columnar steel platform 11 is placed in the processing chamber 10. A disk-shaped anode 11a made of a material having high thermal conductivity and a high melting point, such as molybdenum or graphite, is mounted on the stage 11. The anode 11a has a diameter of, for example, 80 mm and a thickness of 20 mm. The rectangular substrate 1 is fixed to the mounting surface above the anode 11a. The platform 11 is set such that the platform 11 can rotate with the anode 11a about the axis 11χ. The platform 11 below the anode 11a has a closed space lib in which a cooling member 12 is placed. The cooling member 12 is used to cool the substrate 1 as needed, and is constructed to be movable up and down as indicated by an arrow by a moving mechanism (not shown). The cooling member 12 is formed of a metal having high thermal conductivity, such as copper. A coolant, such as a cooling solution of cooling water or calcium chloride, which enters the flow passage 12b in the cooling member 12 by the conduit 12a, and is discharged by the conduit 12c to circulate in the cooling member 12 to cool the entire cooling member 1 2 . When the cooling member 12 moves upward, the upper side of the cooling member 12 abuts against the bottom side of the platform 11 which cools the covered anode 11a, which thus carries heat away from the substrate 1. The coolant discharged from the duct 12c is cooled by a cooling unit (not shown) and discharged again to the duct 12a to be circulated. The upper side of the cooling member 12 is preferably larger than the substrate 1 to uniformly cool the substrate 1 in the planar direction. -11 - 200905010 The space Π b provided under the anode 1 1 a is separated by the platform 1 1 ' so the interior of the space lib is filled with gas or opened to the air. A dish-shaped cathode 13 is placed over the anode 11a. The cathode 13 is supported on the cathode support 14 and faces the anode 11a. The cathode l·3 is formed of molybdenum, graphite or the like, which has a high melting point 'and a diameter of, for example, 80 mm' and a thickness of 20 mm. The cathode support 14 is made of a heat insulating oxide such as quartz glass or aluminum, an insulating nitride such as aluminum nitride or tantalum nitride, or an insulating carbide such as carbonized sand. For example, the distance between the cathode 13 and the anode 1 1 a is 50 m. A passage through which the coolant flows may be formed in the cathode 13. The flow of the coolant suppresses overheating of the cathode 13. Preferred coolants are water, calcium chloride solutions and the like which are supplied from outside the processing chamber 10. An insulating unit 15 for suppressing the occurrence of an arc is placed near the outer surface of the anode 11a. The insulating unit 15 includes at least one of a heat insulating oxide such as quartz glass or aluminum, an insulating nitride such as aluminum nitride or tantalum nitride, or an insulating carbide such as tantalum carbide. The insulating unit 15 in the shape of a ring is supported at the same height as the anode 11a, which is supported by a support 16 provided at the bottom of the process chamber 10 and provided directly around the inside of the anode 11a. The outer diameter of the insulating unit 15 is set to be equal to or greater than 1 of the maximum outer diameter of the cathode 13. 2 times. Since the insulating unit 15 is for suppressing the occurrence of abnormal discharge electric power (arc discharge, spark) between the cathode 13 and the anode 1a, the insulating unit 15 is placed along the outer side surface of the anode 11a and with respect to the cathode 13. The insulating unit 15 may be configured to hide the side of the anode 11a. A viewing window 17 is formed on the side of the processing chamber 10 to allow observation of the inside of the chamber 10 of the processing -12-200905010. Insulating glass is installed in the viewing window 17 to ensure airtightness in the chamber 10. The radiation thermometer 18 is placed outside the processing chamber 10 via, for example, the temperature of the substrate 1 of the viewing window. The DC plasma chemical vapor deposition apparatus has a source system (not shown) that supplies a source gas containing a reaction gas via an inflation tube 19, an exhaust system | shown), which exhausts gas from the inside of the processing chamber 10 via the exhaust duct 20 and Voltage setting unit 21. The inflation tube 19 is inserted into the chamber 10 via a hole provided in the processing chamber 10, and at least a portion of the inflation tube 19 is formed in the reaction furnace, such as a fluorinated resin or silicone. The adhesive is sealed between the 10 hole of the processing chamber and the outer side surface of the gas tube 1 9 to ensure the internal gas density of the processing chamber 1 . In the process chamber 10, the inflation tube 19 is connected to an annular nozzle which is a gas supply nozzle. When the annular nozzle 22 is preferably of full shape, its shape may be a regular polygon. 2 is a schematic view of the annular nozzle 22 and the exhaust duct 20. The annular nozzle 22 has a substantially annular shape and is hollow, so that the body flows therein. A plurality of jets 具有 2 2 a having equal holes are fitted to the annular inner side surface of the annular nozzle 22. The discharge port 22a is provided at an equal distance between the center axis of the 1 1 X or the anode 1 1 a , and the individual discharges ±1 are provided in a point-symmetric manner with respect to the axis X as the center. As described below, the discharge port 22a is formed in a region surrounding the plasma, and the source gas is ejected from the discharge port 22a toward the shaft 11x. The annular nozzle 2 2 is measured by an insulator nozzle attached to the cathode support 14 and is charged (not, to treat the hole portion 22 of the edge body, and the source gas is placed in a uniform support with the shaft " 2a - Supported by 13-200905010 23. The discharge port 22a of the annular nozzle 22 is set higher than the height of the anode 11a, and its position is lower than the lowest position of the cathode support 14 (via the side of the cathode 13 exposed by the cathode support 14) The uppermost portion)' and the position are higher than the highest point of the positive electrode PC formed between the anode 11a and the cathode 13. Since the annular nozzle 22 is supported in this range, the source gas easily enters the cathode 13 and Between the anodes 11a' and preventing the temperature of the gas in the positive electrode column PC from being locally cooled by the injection of the source gas. The inner diameter of the annular nozzle 2 2 is larger than the outer diameter of the cathode 13 and the outer diameter of the anode 11 1 a. The center of the nozzle 2 2 is on the axis 1 1 X of the anode 1 1 a. The angle from the center of the anode 1 1 a toward the individual discharge ports 22a is substantially equal. The four exhaust ducts 20 individually penetrate the processing chamber at equal intervals. 1 four holes formed in the bottom side of the crucible Surrounding the shaft 1 1 x around the platform 1 阳极 or the anode 11 a. The sealant is sealed between each hole and the outer side surface of the associated exhaust duct 20. The voltage setting unit 21 is a control device that sets the anode 11a and the cathode The voltage or current between 1 and 3 is 値 and has a variable power source 21b. The voltage setting unit 21 is connected to the anode 11a and the cathode 13 by wires. The wire is connected to the cathode through a hole provided in the processing chamber 10 1 3 and the anode 1 1 a. The hole in the processing chamber 10 through which the wire passes is sealed by a sealant. The voltage setting unit 2 1 has a control unit 2 1 a connected to the radiation thermometer 18 by wires Connected to the variable power source 2 1 b by a wire. When activated, the control unit 2 1 a represents the temperature of the substrate 1 measured by the radiation thermometer 18 and adjusts the voltage or current between the anode 11 a and the cathode 13 Therefore, the temperature of the substrate 1 becomes a predetermined 値. -14- 200905010 Next, a deposition process will be described which forms a thin film on the substrate 1 using the DC plasma chemical vapor deposition apparatus of Fig. 1. In the deposition process, Electronic placement of carbon walls The film is deposited on the upper surface of the substrate 1. The structure of the nanocarbon wall is formed by a plurality of petal-like (fan-shaped) thin carbon sheets having an upright curved surface 'and chained together in a random direction. Each thin carbon sheet Formed by several or tens of single-layer graphite sheets, each of which has a lattice spacing of 0. 3 4 n m. In the deposition process, first, for example, a nickel plate is cut into the substrate 1, and degreased/ultrasonic cleaning is performed substantially using ethanol or acetone. Next, if the upper surface of the substrate 1 is formed of metal, the upper surface of the substrate 1 is very thinly covered with a plurality of insulating particles having a high melting point and a small diameter, such as diamond particles or alumina particles. This is because the active species-oriented deposition is difficult to deposit on the upper surface of the substrate 1 because the active species generated by a part of the source gas is diffused in the substrate 1 when the upper surface of the substrate 1 is formed of metal. However, the use of a plurality of insulating particles on the upper surface of the substrate 1 allows a deposited layer deposited by the upper surface of the substrate 1 to hardly shield the electric field between the anode 11a and the cathode 13. This substrate 1 is placed on the anode 11a. When the mounting substrate 1 is completed, the processing chamber 1 泄 uses the exhaust system to relieve pressure ' and hydrogen, the reaction gas, and a compound (carbon-containing compound) containing a reaction gas of carbon in the composition, such as methane, that is, by the gas tube 1 9 is supplied to the processing chamber 10. The source gas is ejected from the discharge port 22a of the annular nozzle 22. What is needed is that the reaction gas of the carbon-containing compound in the composition ranges from 3 v 01 % to 3 〇v 01 % throughout the composition of -15-200905010. For example, the flow rate of the brothel is set to 50 seem' The flow rate of hydrogen is set to 500 seem ’ The whole pressure is set to 0. 05 to 1. 5 atm, preferably 0. 07 to 0·1 atm. The anode 1 la rotates the substrate 1 around the axis 1 1X at 1 rpm to set the temperature change on the substrate 1 within 5% and applies a DC voltage between the anode 11a and the cathode 13 to generate plasma and control The state of the plasma and the temperature of the substrate 1. When the nanocarbon wall is deposited, the film deposition is carried out at a temperature of 900 ° C to 1100 ° C, which is set as the temperature at which the portion of the substrate 1 forming the nanocarbon wall. This temperature is measured by a radiation thermometer 18. At this time, the cooling member 12 is substantially separated from the anode 11a to avoid the influence on the temperature of the anode 11a. The setting of the radiation thermometer 18 is such that the plasma radiation of the DC plasma chemical vapor deposition apparatus is lowered, and the temperature is obtained only by the heat radiation at the upper surface of the substrate 1. When a diamond layer containing a plurality of diamond particles is laminated on the nanocarbon wall, the film characteristics of the electron discharge film are changed during the nanocarbon wall deposition process, for example, the cooling member 12 is moved upward to abut the anode 11a. Therefore, the temperature of the substrate 1 can be remarkably lowered to cause lamination of the diamond layer. When the diamond layer grows, the rod-shaped sp2 bonds carbon, which is a modified part of the nano-carbon wall, and unlike the carbon nanotubes, it has a core that is filled and grows. This rod-shaped carbon extends to protrude from the upper surface of the diamond layer, and is structurally possible to concentrate a part of the electric field and release electrons. At the end platform of the film deposition, the applied voltage between the anode 11a and the cathode 13 is stopped, then the supply of the source gas is stopped, and nitrogen gas is supplied to the processing chamber 10 as a cleaning gas to be in the processing chamber 1 Providing nitrogen-16-200905010 gas environment' then substrate 1 is removed when the temperature is returned to normal temperature. The DC plasma chemical vapor deposition apparatus according to this embodiment has the following advantages (1) to (6). . (1) The annular nozzle 22 is placed in the processing chamber 1 , and the source gas is ejected laterally from the ejection port 2 2 a toward the shaft 1 1 x , or in the lateral inward direction, and is composed of four exhaust ducts 20 discharge. Since the discharge ports 22a are disposed at equal intervals in the annular nozzle 22' and the exhaust ducts 20 are disposed at equal intervals around the table 1, the flow of the source gas is symmetrically uniform with respect to the axis 丨 1 x of the process chamber 1 . Since the cathode 13 and the cathode support 14 do not interfere with the flow of the source gas, the source gas flows efficiently to the center of the cathode 13 directly below where the axis X is located, so the source gas comes from the end of the substrate to the center. It is evenly distributed, and the density of the active species produced by a portion of the source gas in the positive electrode column PC becomes a uniform sentence. This ensures that a uniform film is deposited on the upper surface of the substrate 1. The results of examining the effects of differences in the flow of source gases during the experiment will now be explained. 3A and 3B are configuration diagrams for explaining a DC electric chemical vapor deposition apparatus used in a comparative experiment. 4A is a glow state diagram occurring on the cathode in the DC plasma chemical vapor deposition apparatus shown in FIGS. 3A and 3B; and FIG. 4B is a DC plasma chemical vapor phase according to the first embodiment. A glow state diagram on the cathode occurs in the deposition apparatus. In this experiment, a portion of the DC plasma chemical vapor deposition apparatus in Fig. 1 is changed in such a manner that the flow of the source gas does not become symmetrical with respect to the axis -17-200905010 llx, and the cathode 13 is placed at the anode 11a and the nozzle Interference becomes a disturbance. As shown in Fig. 3B, for example, the annular nozzle 22 and the nozzle branch; removed from the interior of the processing chamber 10, the gas tube 19 is connected to the gas shower nozzle 25' above the cathode support 14 in the processing chamber 1 so the gas Injected downward by the air shower nozzle 25, such as a shower, and only one of the plurality of exhaust gases 20 is left, and the stopper 24 is inserted into the other exhaust duct 20 to prevent the exhaust duct from which the stopper 24 is mounted. 20 discharge. The configuration is the same as the DC plasma chemical vapor deposition apparatus in Figure 1. In order to show the influence of the position of the inlet and outlet of the source gas relative to the movement of the source gas body, in a comparative experiment, the DC plasma chemical deposition apparatus, like the DC plasma CVD apparatus of the present embodiment, has insulation. Unit 1 5. It will be observed that the glow state occurs in the modified DC electrical vapor deposition apparatus shown in Fig. 3B and under the DC plasma chemical vapor deposition cathode 13 of Fig. 1. Please note that the source gas is hydrogen, 500 00 seem, the pressure is 30 torr, and the current of 2A passes through the cathode in the DC plasma chemical vapor deposition modified as shown in Fig. 3B, from the gas shower nozzle 25 The ejected source gas is directed to an exhaust conduit 20 that does not have a stop 24, so the source gas does not radiate, unlike the arrows in Figure 3A, and the gas does not oppose the shaft at the cathode 13. Π X flows symmetrically, and the flow of the source gas does not have the exhaust conduit 2〇 of the stopper 24 as shown by the chain line in Fig. 3B. Since the cathode 13 becomes a disturbance to the flow of the source gas, the source gas becomes difficult to surround the cathode crucible 3 to reach the anode space at the position of the 23-position in the body jet conduit, so that his apparent flow phase is the slurry flow rate 13 ° The device has a space downstream of the stop flow toward the point 1 1 a -18- 200905010 The axis 1 1 中心 at the center, thereby causing a change in the plane between the density of the active species arriving at the upper surface of the substrate 1. This change is more pronounced when the substrate 1 becomes larger so that the cathode 13 and the anode 1 1 a are larger. In the DC plasma chemical vapor deposition apparatus modified as shown in Fig. 3B, as shown in Fig. 4A. The inclination of the shape of the cathode glow at the cathode 13 represents that the temperature distribution also has an inclination' so that film deposition on the substrate 1 is likely to change. In the D C plasma chemical vapor deposition apparatus modified as shown in Fig. 1, by contrast, the glow generated at the cathode 13 is not inclined. Therefore, uniform film deposition on the substrate 1 can be ensured. (2) Since the inflation tube 19 is formed of an insulator 'and the annular nozzle 22 is supported on the insulator nozzle holder 2' to insulate the annular nozzle 2 2 from the power source or the ground, waste from the cathode 13 or the anode 1 1 a Arcing or the like does not occur. (3) Since the inner diameter of the annular annular nozzle 22 is larger than the outer diameters of the cathode 13 and the anode 11a, the annular nozzle 22 does not overlap the positive electrode PC, and has a high density activity between the cathode 13 and the anode 11a. The species 'so there is no plasma-based temperature rise at the portion where the sputum 22a is ejected', thereby suppressing deposition at the squirt 22a. (4) Since the height of the discharge port 22a of the annular nozzle 22 is higher than the maximum point of the positive electrode column PC, the gas temperature at the positive electrode column PC is not partially cooled by the side surface from the low temperature gas ejected from the discharge port 22a. It will interfere with the symmetry of the shape of the positive electrode PC. (5) The insulating unit 15 prevents the occurrence of arc discharge which may interfere with uniform film deposition from the cathode 13 toward the outer side surface of the anode 11a. -19- 200905010 (6) The annular nozzle 22 is placed at the same position as the surface of the electrode of the cathode π, or at a position lower than the surface of the electrode, and the source gas discharged from the side of the annular nozzle 22 is Guide the exhaust duct 2〇 facing downward. This prevents the highly reactive active species generated in the positive electrode column PC from being diffused into contact with the cathode crucible 3. It is therefore possible to prevent the active species from depositing on the cathode, which causes arcing or Mars. [Second Embodiment] Figs. 5A and 5B are configuration diagrams of a dc plasma chemical vapor deposition apparatus according to a second embodiment of the present invention. Common reference numerals are assigned to those components in Figures 5A and 5B that are shared with the components of the diagram. This DC plasma chemical vapor deposition apparatus is the DC plasma chemical vapor deposition apparatus of Fig. 1 whose cathode 13 is changed to the cathode 27, and its voltage setting unit 21 is changed to the voltage setting unit 28. The cathode 27 has a dish-shaped central electrode 27a facing the central portion 'the peripheral electrode 27b of the anode 1 U, which is in the shape of a ring (see Fig. 5B), surrounding the central electrode 27a, which is concentric with the central electrode 27a, and is flush The peripheral portion of the anode 11a, and the insulating portion 27c made of ceramic or the like are completely filled between the center electrode 27a and the peripheral electrode 27b. When no insulating portion 27c is inserted between the center electrode 27a and the peripheral electrode 27b, the electric field strength on the side wall of the center electrode 27a facing each other and the side wall of the peripheral electrode 27b and on the substrate 1 is weakened, and a part of the electric field is not formed. There is a cathode glow cover unless the distance between the center electrode 27a and the peripheral electrode 27b is sufficiently long. Because this part has less ion bombardment, it is possible for deposits to deposit here. This deposit causes an arc discharge or spark. In this regard, the insulating portion 27c is inserted to prevent the film from being deposited on the side walls of the center electrode 27a facing each other and the side wall of the peripheral electrode 27b. The voltage setting unit 28 has a control unit 28a, and variable power supplies 28b, 28c = control unit 28a is connected to the radiation thermometer 18 by wires. The control unit 28 8 a has the ability to control the variable power sources 2 8 b, 2 8 c and individually set the voltage or current between the anode 11a and the center electrode 27a, and the voltage or current between the anode 11a and the center electrode 27a. . The other configuration is the same as the DC plasma chemical vapor deposition apparatus in Figure 1. If a film is formed on the substrate 1 using the DC plasma chemical vapor deposition apparatus in FIGS. 5A and 5B, the substrate 1 is rotated at a rate of 1 rpm as the plasma rises, and between the stage 11 and the center electrode 27a. The potential difference will be greater than the potential difference between the land Π and the peripheral electrode 27b under the control of the voltage setting unit 28 to set the voltage between the cathode 27 and the anode Π a. This voltage is applied between the anode 1 la and the center electrode 27a to produce a small positive pole PC. This prevents arcing from occurring, which often occurs when a large positive column is produced at the beginning. After the stable positive electrode PC is formed on the upper portion of the central portion of the substrate 1 by applying such a voltage or current, the control unit 28 8 applies the voltage or current so that the voltage or current between the anode 11 a and the central electrode 27a is applied.値 becomes a voltage or current 小于′ between the anode 11 1 a and the peripheral electrode 2 7 b to approximate the temperature between the anode 11 a and the central electrode 27 a between the anode 11 a −21 − 200905010 and the peripheral electrode 2 7 b The temperature 'or such temperatures are substantially equal before the film deposition on the substrate 1. In the present embodiment, as described above, the cathode 27 includes a central electrode 27a and a peripheral electrode 27b, and a voltage or current 値 between the anode Ua and the central electrode 27a, and the anode 11a and the peripheral electrode 27b. The voltage or current 间 can be set independently. When the plasma rises, the voltage between the anode 1 la and the center electrode 27a is set higher than the voltage between the anode 11a and the peripheral electrode 27b. Therefore, the positive electrode column PC can be formed by making the distance between the anode 11 a and the cathode 27 shorter. The voltage to be applied to the anode 11a and the cathode 27 can be lower, thereby suppressing frequent occurrence of arc discharge or spark. Further, the current flowing through the peripheral electrode 27b becomes smaller than the current flowing through the center electrode 27a to generate the positive electrode PC concentrated at the center of the substrate 1, and then the electric power applied to the peripheral electrode 27b is increased to increase the flow. The current of the peripheral electrode 27b. This makes it possible to prevent local arc discharge occurring at the initial stage of film deposition, and then the positive electrode column P C can be grown to a desired size. [THIRD EMBODIMENT] Fig. 6 is a configuration example of a DC plasma chemical vapor deposition apparatus according to a third embodiment of the present invention. A common reference number is given when the components in Fig. 6 are shared with the components in Fig. 1. The DC plasma CVD apparatus has a processing chamber 30 as a reaction furnace. The processing chamber 3 隔离 isolates the substrate 1 from outside air. A columnar steel platform 11 is placed in the processing chamber 30. A disk-shaped anode 11a made of a material having high thermal conductivity and a melting point of the cylinder, such as molybdenum or graphite, is mounted on the platform 11 as an -22-200905010. The rectangular substrate 1 is fixed to the mounting surface above the anode 11a. The platform 11 is set such that the platform 11 can rotate with the anode 11a about the axis 11X. The platform 11 below the anode 11a has a closed space lib in which a cooling member 12 is placed. The cooling member 12 is used to cool the substrate 1 as needed, and is constructed to be movable up and down as indicated by an arrow by a moving mechanism (not shown). The cooling member 12 is formed of a metal having high thermal conductivity, such as copper. A coolant, such as a cooling solution of cooling water or calcium chloride, which enters the flow passage 12b in the cooling member 12 by the conduit 12a, and is discharged by the conduit 12c to circulate in the cooling member 12 to cool the entire cooling member 1 2 . When the cooling member 12 moves upward, the upper side of the cooling member 12 is adjacent to the bottom side of the platform 1 1 which cools the anode 1 1 a on the upper side, which thus carries heat away from the substrate 1. The coolant discharged from the conduit 12c is cooled by a cooling unit (not shown) and discharged again to the conduit 12a for circulation. A dish-shaped cathode 13 is placed above the anode 11a. The cathode 13 is supported on the cathode support 14 and faces the anode 11a. The cathode 13 is formed of molybdenum, graphite or a similar material having a high melting point. The cathode support 14 is made of a heat insulating oxide such as quartz glass or aluminum, an insulating nitride such as aluminum nitride or tantalum nitride, or an insulating carbide such as tantalum carbide or the like. A passage through which the coolant flows may be formed in the cathode 13. The flow of the coolant suppresses overheating of the cathode 13. An insulating unit 15 for suppressing the occurrence of an arc is placed near the outer surface of the anode 11a. The insulating unit 15 includes a heat insulating oxide such as quartz glass or aluminum 'insulating nitride such as aluminum nitride or tantalum nitride, or heat insulating carbide, -23-200905010, for example, tantalum carbide or the like. The insulating unit 15 in the shape of a ring is supported at the same height as the anode 11a, which is supported by a support 16 provided at the bottom of the processing chamber 30 and around the inside of the anode 11a. The outer diameter of the insulating unit 15 is set to be equal to or greater than the maximum outer diameter of the cathode 13. 2 times. Since the insulating unit 15 is for suppressing the occurrence of abnormal discharge electric power (arc discharge, spark) between the cathode 13 and the anode 1 1 a, the insulating unit 15 is along the outer side surface of the pole 1 1 a and is opposite to the cathode 13 Place and configure the side of the hidden anode 1 1 a. A viewing window 17 is formed on the side of the processing chamber 30 to allow viewing of the interior of the chamber 30. The insulating glass is installed in the viewing window 17 to ensure airtightness in the chamber 30. The radiation thermometer 18 can measure the temperature of the substrate 1 via, for example, a viewing window 1 and is placed outside the processing chamber 30. The DC plasma chemical vapor deposition apparatus has a source system (not shown) through which a reactive gas is supplied as a source of active species, and a source system (not shown) which supplies a matrix gas through the gas-filled tube 32 (carrier) Gas) An exhaust system (not shown) that exhausts gas from the inside of the processing chamber 30 via an exhaust duct, and a voltage setting unit 21. The inflation tube 31' is made of an insulator that passes through a hole provided in the processing chamber 30. The sealant is sealed between the hole and the outer side surface of the gas tube 31 to ensure airtightness within the processing chamber 30. In the process chamber 3, the gas pipe 31 is connected to the annular nozzle 33. The annular nozzle 33 is similar to the annular nozzle 22 shown in Fig. 2. a plurality of ejected enthalpy 埠 3 3 a having an equal hole is arranged in an annular manner to the inner surface of the annular nozzle to directly measure the inner surface of the accommodating phase -24- 33 200905010, and The central axis of the shaft 1 1 X or the anode 1 1 a is provided equidistantly. The individual discharge ports 3 3 a are provided at opposite positions with respect to the point-symmetric manner of the axis 1 ! x as the center, and the source gas is uniformly ejected from the discharge port 3 3 a toward the axis 11x. The annular nozzle 33 is supported by an insulator nozzle support 23 attached to the cathode support 14. The discharge port 33a of the annular nozzle 33 is set to a position lower than the lowest portion of the cathode support 14 (the uppermost portion of the side of the cathode 13 exposed through the cathode support 14), and the position is higher than the anode 1 The highest point of the positive electrode PC formed between 1 a and the cathode 13 . Since the annular nozzle 33 is supported in this range, the reaction gas easily enters between the cathode 13 and the anode 11a, and the disturbance of the symmetry of the positive electrode column PC due to the local cooling of the ejection of the reaction gas can be prevented. . The inner diameter of the annular nozzle 33 is larger than the outer diameter of the cathode 13 and the outer diameter of the anode 11a. The center of the annular nozzle 33 is on the axis 1 1 X of the anode 1 1 a. The angle from the center of the anode 1 1 a toward the individual discharge ports 3 3 a is substantially equal. The four exhaust ducts 20 individually penetrate the four holes formed in the bottom side of the process chamber 30 at equal intervals to surround the platform 1 1 around the shaft 1 1 X. A sealant is sealed between each of the holes and the outer side surface of the associated exhaust conduit 20. The voltage setting unit 21 is a control device that sets the number of voltages or currents between the anode 11a and the cathode 13 and has a variable power source 21b. The voltage setting unit 21 is connected to the anode 11a and the cathode 13 by wires. The wires are connected to the cathode 13 and the anode 1 1 a through holes provided in the process chamber 30. The holes in the processing chamber 30 through which the wires pass are sealed by a sealant. -25- 200905010 The voltage setting unit 21 has a control unit 21a which is connected to the radiation thermometer 18 by wires and is connected to the variable power source 2 1 b by wires. When activated, the control unit 2 U represents the temperature of the substrate 1 measured by the radiation thermometer 18, and adjusts the voltage or current 之间 between the anode 11a and the cathode 13, so that the temperature of the substrate 1 becomes a predetermined enthalpy. The inflation tube 32' is made of an insulator that passes through a hole provided in the processing chamber 30. The sealant is sealed between the hole and the outer side surface of the gas tube 3 2 to ensure airtightness within the processing chamber 30. In the process chamber 30, the charge pipe 32 is connected to the gas shower nozzle 34. The gas shower nozzle 34 is placed above the cathode support 14 of the support cathode 13 and above the annular nozzle 33. A plurality of ejecting loops having equal holes are formed in the bottom side of the gas shower nozzle 34 about the axis 1 1 X. The individual ejecting weirs are provided point-symmetrically with respect to the central axis 1 1 X at opposite positions to eject the matrix gas downwardly, such as a shower. The basic operation of performing thin film deposition using the DC plasma chemical vapor deposition apparatus of the present embodiment is similar to the case of using the DC electric chemical vapor deposition apparatus of the first embodiment. It is to be noted that in the DC plasma chemical vapor deposition apparatus of the present embodiment, the matrix gas and the reaction gas are independently introduced, and the reaction gas is ejected from the annular nozzle 3 3 in the lateral inward direction, and the matrix gas is discharged. The gas spray nozzle 34 is ejected downward. The matrix gas changes the flow vector of the laterally ejected reaction gas, so that the reaction gas flows toward the substrate 1 which is obliquely below. The verification experiment of the height of the annular nozzle 33 will be explained below. Figure 7 is a simplified diagram of the verification experiment. -26- 200905010 In this verification experiment, film deposition was carried out by setting the diameter of the anode 11 a and the cathode 13 to 160 mm, and the thickness thereof was set to 15 mm. The distance between the anode 11a and the cathode 13 was set to 60 mm, and the ring was set. The inner diameter of the nozzle 33 is set to 305 mm, and the pipe diameter is set to 〇25 吋. The distance between the bottom side where the discharge nozzle of the gas spray nozzle 34 is located and the bottom side of the cathode 13 is set to 260 mm. The flow rate of hydrogen in the matrix gas discharged from the gas shower nozzle 34 was set to 600 sccm, the flow rate of argon gas in the matrix gas was set to 48 sccm, the flow rate of methane in the reaction gas was set to 60 sccm, and the gas pressure was set to 60 Torr. The current between 13 and the anode 11a is set to 16 A, and the crucible substrate has a square shape with a side of 75 mm and a thickness of 0. 7 mm was used as the substrate 1, and the deposition time was set to 2 hours, and the height of the annular nozzle 33 was changed. As shown in Fig. 7, the position of the discharge port 33a of the annular nozzle 33 located 10 mm below the bottom side of the cathode 13 is at a high position, and the position of the discharge port 33a positioned above the upper surface of the anode 11a is low. position. Fig. 8 and Fig. 9 are diagrams for explaining the results of the verification experiment. In this verification experiment, the growth of the nanocarbon wall can be at the observation point A on the center of the substrate 1 and on the axis Ux, and the distance L1 from the end face by a distance L1 and from the two end faces adjacent to the end face 37. . The observation point B of the distance L2 of 5 mm was observed. The growth of the carbon wall on the substrate 1 was observed in the case where the reaction gas was discharged from the high position and in the case where the reaction gas was discharged from the low position. Fig. 9A and %9C are tomographic SEM images, shown as -27-200905010 growth of nanocarbon wall at observation point A and observation point B. 'When electric prize chemical vapor deposition uses annular nozzle 3 3 The squirting 埠 3 3 a is performed at the high position for two hours. Fig. 9B and Fig. 9D are the tomographic SEM images 'showing the growth of the carbon wall at the observation point A and the observation point B, respectively. 'When the plasma chemical vapor deposition uses the annular nozzle 3 3, the ejection 埠 3 3 a is performed for two hours at this low position. As shown in Figs. 9A and 9C, when the reaction gas is discharged only from the high position, the degree of growth of the carbon wall at the observation point A and the observation point B is not greatly different. When the reaction gas is discharged only from the low position, as shown in Figures 9B and 9D, there is a difference in the degree of growth of the nanocarbon wall; the nanocarbon wall is at the observation point B than at the observation point A. Growing up. The reason for this difference seems to be that at the low position, the reaction gas ejected from the annular nozzle 33 is placed too low, and it is more difficult to reach the observation point A than in the case of the high position, and the peripheral portion in the plasma is made. The temperature at the location (outside the central portion) will be lower than the temperature at the central portion to increase the difference between the temperature at the central portion and the temperature at the peripheral portion of the plasma. A decrease in the temperature of the gas in the plasma near the outer surface of the substrate 1 causes an increase in the density of the active species having a relatively low chemical potential and causes non-uniform film deposition. At this high position, on the other hand, the low-temperature reaction gas is not directly sprayed onto the positive electrode PC, so the temperature gradient in the gas is small and non-uniform thin film deposition does not occur. An experiment for observing the state of film deposition when the diameter of the jet 埠 3 3 a is changed will now be described. -28- 200905010 The position of the annular nozzle 3 3 is set to a high position as shown in Fig. 7, and when the diameter of the discharge port 33a is changed to 〇. 5mm, 1. 0mm and 1. The change in emissivity at the surface above the substrate measured at 5 mm. In the case where a graphite structure similar to a carbon carbon wall is deposited on a sand substrate, the emissivity is substantially higher as the film thickness is increased. The flow rate of the reaction gas per unit time is set by using the discharge 埠 3 3 a diameter 〇 . The moving rate of the gas immediately after 5 m m is set to be equal to 50,000 c m/s, and the diameter of the discharge enthalpy 33a is set to 1. The moving rate of the gas immediately after the 0 mm ejection is set equal to 125 cm/s, and the diameter of the ejection port 33a is set to 1. The rate of gas movement after 5 mm has just ejected is set equal to 5 5 cm/s. 10A, 丨0B, and 10C are tomographic SEM images showing the state of film deposition at the observation point A (the center of the substrate) shown in Fig. 8, by being at the high position. Has a diameter set to 〇. 5mm, 1. 0mm and 1. The plasma chemical vapor deposition apparatus of the 5 mm annular nozzle 33 ejecting the crucible 33a performs plasma chemical deposition for two hours. Figure 11 shows the diameter of the jet raft 33a set to 〇. 5mm, 1. The emissivity of 0 mm and 1,5 mm at the substrate 1. The tomographic SEM image shows that the diameter of the ejection port 33a is 0. 5mm, the diameter of the spray port 33a is 1. 0mm, the diameter of the sprayed 33a is 1. In any case of 5 mm at the observation points A and B perpendicular to the substrate, there is no significant difference in the growth of the nanocarbon wall. But the diameter of the sprayed 33a is 〇. 5 mm (Φ〇_5), 1. 0 mm (Φ1. 0) and 1. 5 mm (Φ 1. 5) When comparing the tomographic SEM images at the observation point, you can understand that φΐ·〇 and Φΐ. At 5 o'clock, the growth of the nanocarbon wall -29-200905010 in the direction perpendicular to the substrate is greater than Φ0. At 5 o'clock, the length of the nanocarbon wall is perpendicular to the direction of the substrate. It can be seen from Fig. 11 that the change in the emissivity of the substrate is at Φ0. 5 and Φ 1. There is almost no change between 0 and reaches the plateau period after 1 hour and 30 minutes, however at Φ 1. At 5 o'clock, the increase in emissivity at the time of nanocarbon wall growth indicates a tendency to become slower. This increase in emissivity is based on the density of the graphite component of the nanocarbon wall constituting the upper surface of the substrate. It is known that the growth of the nanocarbon wall in the direction perpendicular to the substrate becomes faster when the amount of the active species vertically oriented toward the substrate 1 becomes larger. When Φ0. At 5 o'clock, the emissivity reaches the plateau at a faster rate, and the height of the carbon wall of the nanometer is compared with Φ. 0 and Φ 1. At 5 o'clock, the ratio of lateral growth rate seems to be greater than Φ 1. 0 and Φ 1 · 5 status. This represents when Φ 0. At 5 o'clock, the lateral velocity component of the flow of the active species formed by the plasma is greater than the lateral velocity component in the other two cases, and the ejection rate of the methane gas is too fast 'so the flow of gas through the positive electrode PC of the plasma will Slightly disturbed. When Φ 1. At 5 o'clock, when the deposition time is 2 hours, the height of the nanocarbon wall perpendicular to the direction of the substrate is almost equal to Φ 〇 · 5 and Φ 1. The 0 hour 2 hour deposition time is perpendicular to the height of the nanocarbon wall in the direction of the substrate. 'But the rate of emissivity reaching the plateau is slower than in the other two cases, and perpendicular to the substrate. The growth of the nanocarbon wall in the direction is roughly equal to Φ 1. In the case of 0, it represents that the deposition rate of the entire graphite component will be lower than Φ 〇 . 5 and Φ 1. In the case of 0, and therefore the rate of lateral growth of the nanocarbon wall becomes slower. This seems to be because the reaction gas is ejected at a slower rate 'so the convection of the reaction gas is not disturbed too much' and reaches the reaction gas at the center of the plasma. -30- 200905010 The amount of the body is smaller than φθ. 5 and Φ1. 0 case. That is, when Φ0. The unit area ratio of the substrate of the nanocarbon wall formed at 5 o'clock is Φ1. The carbon wall formed at 5 o'clock has a higher density but grows slower in the direction perpendicular to the substrate. When Φ1. The carbon wall formed at 5 o'clock is perpendicular to the substrate in the direction of Φ0. The carbon wall formed at 5 o'clock grows faster, but it is slower when the density per unit area of the substrate becomes sufficiently high. However, the carbon wall formed when Φ 1 · 5 grows to a sufficient density when the deposition time reaches two hours. Therefore, in this embodiment, it is desirable that the rate of movement of the reaction gas immediately after being ejected from the annular nozzle 3 3 is about 125 cm/s (the nozzle is Φ1. 0), for uniform growth of the carbon wall of the nano' and ideally the reaction rate of the reaction gas is about 55 cm/s (the nozzle is Φ1. 5) to about 125cm / s (nozzle is Φ1. 0) Good electrical discharge characteristics can be obtained even with slightly poor uniformity. The DC plasma chemical vapor deposition apparatus according to this embodiment has the following advantages (7) in addition to the advantages of the first embodiment. (7) It can be seen that the concentration of the reaction gas relative to the matrix gas affects the quality of the film. However, in the method of introducing a gas mixture, the gas mixture has a predetermined concentration of only the mixed reaction gas and the matrix gas, and supplies the gas mixture to the substrate by naturally occurring convection, and a part of the newly introduced gas mixture is in the gas mixture The gas is discharged from the exhaust conduit 20 before it reaches the substrate 1, so that the concentration of the reaction gas above the substrate 1 can become lower than the concentration of the gas mixture introduced. If the concentration of the reaction gas in the gas mixture is increased to avoid the deposition of the reaction gas-directed - 31-200905010, it is possible that the cathode 13 and the cathode support 14 supporting the cathode π cause the electric prize to become an arc discharge or a spark. The DC plasma chemical vapor deposition apparatus of the present embodiment independently introduces the matrix gas and the reaction gas, sets the discharge position of the reaction gas to be relatively higher than the substrate 1, and sets the discharge position of the matrix gas to be higher than the discharge position of the reaction gas, so The flow of the reaction gas toward the substrate 可由 can be manipulated by the downward force of the matrix gas, thereby reducing the amount of reactive gas that is wasted. Further, the discharge position of the matrix gas is set on the cathode support 14 of the cathode 13 and the support cathode 13, and the discharge position of the reaction gas is set below the bottom side of the cathode 13, so that the downward force reaches the exhaust gas of the matrix gas. The conduit 20 is applied to suppress the reverse flow of the reaction gas toward the cathode 13 against the flow of the matrix gas, and to prevent the reactive gas component from adhering to the cathode 13 and the cathode support 14 supporting the cathode 13. [Fourth embodiment] Figs. 12A and 12B are configuration diagrams of a DC plasma chemical vapor deposition apparatus according to a fourth embodiment of the present invention. The components in Figures 12A and 12B shared with the components of Figure 6 are given a common reference number. This DC plasma chemical vapor deposition apparatus is the DC plasma chemical vapor deposition apparatus of Fig. 1, in which the cathode 13 is changed to the cathode 35, and its voltage setting unit 21 is changed to the voltage setting unit 36. The cathode 35 has a central electrode 35a facing the central portion of the anode 11a, and a peripheral electrode 35b shaped like a ring (see Fig. 12B) 'around the central electrode 35a, which is concentric with the central electrode 35a' and faces the anode 11a The peripheral portion, and the insulating portion 35c made of ceramic or the like is completely filled between -32-200905010 between the center electrode 35a and the peripheral electrode 35b. If the insulating portion 35c is not inserted between the center electrode 35a and the peripheral electrode 35b, the film grown by the active species is deposited not only on the substrate 1, but also on the side walls of the center electrode 35a and the side wall of the peripheral electrode 35b facing each other. . In this regard, the insulating portion 35c is inserted to prevent the film from being deposited on the side walls of the center electrode 35a facing each other and the side walls of the peripheral electrode 35b. The voltage setting unit 36 has a control unit 36a, and a variable power source 36b, 3 6 c ° The control unit 36a is connected to the radiation thermometer 18 by a wire. The control unit 36a has the ability to control the variable power supplies 36b, 36c and individually set the voltage or current between the anode 11a and the center electrode 35a, and the voltage between the anode Πa and the center electrode 35b or Current. The other configuration is the same as the DC plasma chemical vapor deposition apparatus in Figure 6. If a film is formed on the substrate 1 using the DC plasma chemical vapor deposition apparatus in FIGS. 12A and 12B, the substrate 1 is rotated at a rate of 1 rpm as the plasma rises, and between the anode 11a and the center electrode 35a. The voltage is greater than the voltage between the anode 11a and the peripheral electrode 35b under the control of the voltage setting unit 36 to set the voltage between the cathode 35 and the anode 11a. Such an applied voltage generates a small positive electrode PC between the anode 11a and the center electrode 35a, and can prevent arc discharge from occurring in the initial stage of film deposition. When the stable positive electrode PC is formed on the upper portion of the central portion of the substrate 1 by applying such a voltage or current, the control unit 36 a applies the voltage -33-r
200905010 或電流使得陽極1 1 a與中央電極3 5 a之間的電壓或電 成爲小於陽極1 1 a與周緣電極35b之間的電壓或電流 以將陽極1 1 a與中央電極3 5 a之間的溫度近似於陽 與周緣電極3 5 b之間的溫度，或使得那些溫度於在 上進行薄膜沈積之前大致相等。 在本具體實施例中，如上所述，陰極35包含中央 35a與周緣電極35b，及陽極11a與中央電極35a之| 壓或電流値，陽極1 1 a與周緣電極3 5 b之間的電壓： 値可獨立地設定。在電漿上升時，陽極11a與中央電 之間的電壓被設定高於陽極lla與周緣電極35b之 壓。因此’正極柱PC可利用將陽極lla與陰極35. 距離變得較短來形成。要施加於陽極1 i a與陰極3 5 可以較低’藉此抑制電弧放電或火花之經常發生。 再者’流過周緣電極35b之電流會變成小於流 電極35a之電流，以產生在基板1之中央處集中的 P C ’然後施加到周緣電極3 5 b之功率即增加，以增 周緣電極35b之電流。此使其有可能防止發生在薄 之初始階段之局部電弧放電，然後正極柱PC可成長 的尺寸。 [第五具體實施例] 第13圖爲根據本發明第五具體實施例之DC電 氣相沈積裝置的組態圖。 第14圖爲上述第13圖之DC電漿化學氣相沈積 陰極、來源氣體噴嘴及排氣導管之示意圖。 流値 値， lla 板1 電極 的電 電流 5 35a 的電 間的 電壓 中央 極柱 流過 沈積 需要 化學 置的 -34- 200905010 第15圖爲由側向之第13圖的DC電漿化學氣相沈積裝 置之剖視圖。 DC電漿化學氣相沈積裝置在要處理之基板1的上表面 之上形成薄膜，並具有處理室50做爲反應爐。處理室50 將基板1隔離外界空氣。 長方形平行六面體鋼質平臺51置於處理室50中。由 高導熱性及高熔點之材料製成的長方形板狀陽極5 1 a，例如 銷或石墨’即安裝在平臺51上。基板1固定在陽極51a之 上方安裝面上。基板1可具有長方形狀，或複數正方基板 1可放置在陽極51a上。 在陽極51a之下的平臺51具有封閉的空間51b，其中 置有冷卻構件5 2。冷卻構件5 2係用於視需要冷卻基板1， 並建構成可以藉由移動機構（未示出）而如箭頭所示般地上 下移動。冷卻構件5 2由具有高導熱性的金屬形成，例如 銅。一種冷卻劑，例如冷卻水或氯化鈣的冷卻溶液，其由 導管52a進入冷卻構件52中的流動通道52b，並由導管52c 排出而在冷卻構件52中循環，以冷卻整個冷卻構件52。 當冷卻構件5 2向上移動時，冷卻構件5 2的上方側緊 靠在平臺51的底側，其冷卻位在上面的陽極51a，藉此將 熱量由基板1帶離。冷卻構件52的上方側爲長方形，並在 長度方向上冷卻整個平臺51。 由導管52c排出的冷卻劑由冷卻單元（未示出）冷卻，並 再次傳送到導管52a來重新循環。 提供在陽極5 1 a之下的空間5 1 b被平臺5 1區隔，所以 -35- 200905010 空間5 1 b的內部充滿氣體或開放至空氣中。 長方形板狀的陰極53置於陽極51a之上。陰極53 撐在陰極支撐14上，並面對陽極51a。陰極53由鉬、石 或具有高熔點之類似材料所形成。 陰極支撐54由隔熱氧化物，例如石英玻璃或鋁，隔 氮化物’例如氮化鋁或氮化矽，或隔熱碳化物，例如碳 矽等製成。 冷卻劑流經的通道可在陰極53中形成。冷卻劑的流 可抑制陰極5 3的過熱。較佳的冷卻劑爲水、氯化鈣溶液 類似者，其由處理室50外部供應。 用於抑制電弧發生的絕緣單元55置於靠近陽極51a 外側表面。絕緣單元5 5包含隔熱氧化物，例如石英玻璃 鋁，隔熱氮化物，例如氮化鋁或氮化矽，及隔熱碳化物 例如碳化矽等當中至少一項。 形狀爲環形的絕緣單元5 5以與陽極5 1 a相同的高度 支撐，其由在處理室50之底部及環繞陽極51a之內側處 立提供的支撐16所支撐。 因爲絕緣單元5 5用於抑制陰極5 3與陽極5 1 a之間 異常排放電（電弧放電、火花）之發生，絕緣單元5 5沿著 極51a之外側表面並相對於陰極53來放置。絕緣單元 可配置成隱藏陽極5 1 a之側面。 在處理室5 0的側面上形成觀視窗5 7，以允許觀察處 室5 0的內部。隔熱玻璃安裝在觀視窗5 7中，以確保處 室5 0內的氣密性。輻射溫度計5 8可經由例如觀視窗5 7 支 墨 熱 化 動 及 的 或 來 直 的 陽 55 理 理 測 -36- 200905010 量基板1之溫度，並置於處理室50之外部。 DC電漿化學氣相沈積裝置具有來源系統（未示出），其 可經由充氣管59供應含有反應氣體之來源氣體，排氣系統 (未示出）’其經由排氣導管60自處理室50內部排出氣體， 以及電壓設定單元61。 充氣管59經由在處理室50中提供的孔洞插入到處理 室50中，且在反應爐中充氣管59之至少一部分由絕緣體 形成’例如氟化樹脂或矽膠。密合劑密封在處理室50之孔 涧與充氣管5 9之外側表面之間，以確保處理室5 0內部的 氣密度。在處理室50中，充氣管59連接至噴嘴62 ,其爲 氣體供應噴嘴。 噴嘴62具有一部分62A，其平行於每一個陽極51a與 陰極53之長邊，及一部分62B平行於每一個陽極51a與陰 極53之另一長邊。噴嘴62可爲整個環形，或其部分62A、 62 B可由與充氣管59的連接點分支出去。噴嘴62爲中空 以傳送來源氣體。複數噴出ί阜6 2 a相對於軸5 3 X或沿著陰 極5 3之長邊側的長度方向之中心軸爲線性對稱以等間距 形成在噴嘴62的部分62A、62B中，所以來源氣體由噴出 埠6 2 a朝向基板1側向地噴出，即在側向向內方向上。 噴嘴62由附著於陰極支撐54之絕緣噴嘴支撐63所支 撐。噴嘴62之支撐高度設定的方式爲噴出埠62a低於陰極 支撐5 4的最低位置之下（陰極5 3之暴露側面的最上方部 分）’以及位置在高於陽極5 1 a與陰極5 3之間形成的正極 柱PC之最高點。因爲噴嘴62支撐在此範圍中，該來源氣 -37- 200905010 體輕易地進入陰極53與陽極51a之間，並可防止在正極柱 PC中的氣體溫度由來源氣體之噴射而局部冷卻。 噴嘴62之部分62A、62B之間的間隔大於陰極53的寬 度（短邊方向），而噴嘴62的部分62A、62B放置在長邊方 向上陰極53之兩個側面之更外側。部分62a、62B在長邊 方向上與陽極5 1 a之中心線大致爲相等距離。 排氣導管60分別穿透在處理室50之底側中形成的複 數孔洞而以相等間距環繞平臺5 1。密封劑密封於相關排氣 導管60之每個孔與外側表面之間。 電壓設定單元61爲一種控制裝置，其設定陽極51a與 陰極5 3之間的電壓或電流之數値，並具有控制單元6 1 a及 可變電源61b。電壓設定單元61藉由導線連接至陽極51a 與陰極5 3。該等導線通過在處理室5 0中提供的孔洞。在導 線通過的處理室5 0中的孔洞由密封劑所密封。 電壓設定單元6 1的控制單元6 1 a藉由導線連接至輻射 溫度計5 8，及由導線連接至可變電源6 1 b。當啓動時，控 制單元6 1 a代表由輻射溫度計5 8測量的基板1之溫度，並 調整陽極5 1 a與陰極5 3之間的電壓或電流値，所以基板1 的溫度成爲預定値。 接著將說明沈積製程，其使用第13圖中的DC電漿化 學氣相沈積裝置在基板1上形成薄膜。 在沈積製程中，將包含奈米碳壁的電子放電膜沈積於 基板1的上表面上。 在該沈積製程中，首先例如鎳板切割成基板1，且大 -38- 200905010 致上利用乙醇或丙酮進行去油脂/超音波洗淨。 此基板1係放置在陽極51a上。 完成安裝基板1時，接下來處理室50使用排氣系統洩 壓，且氫氣、反應氣體及在成份中含有碳的反應氣體之化 合物（含碳化合物），例如甲烷，即由充氣管59供應到處理 室50中。來源氣體由噴嘴62之噴出埠62a噴出。 在沈積奈米碳壁時，薄膜沈積在溫度900°C到1100°C 之間進行，其設定爲基板1之形成奈米碳壁的該部分的溫 度。此溫度由輻射溫度計5 8測量。此時，冷卻構件5 2大 致與陽極51a區隔，以避免對於陽極51a之溫度的影響。 輻射溫度計5 8之設定使得降低DC電漿化學氣相沈積裝置 之電漿輻射，並僅由在基板1之上方表面處的熱輻射來取 得溫度。 當含有多個鑽石粒子之鑽石層疊層在奈米碳壁上，而 在奈米碳壁沈積製程期間改變電子放電膜之薄膜特性，例 如冷卻構件52向上移動而緊靠陽極51a。因此，基板1之 溫度可顯著地降低而造成鑽石層的積層。當鑽石層成長 時’棒形的sp2鍵結碳，其爲奈米碳壁的修正部分，且不像 是奈米碳管’其具有塡充的核心而成長。此棒狀的碳延伸 到自鑽石層的上方表面突出，而爲結構上可能集中電場的 部分且釋放電子。 在薄膜沈積的末端平臺處，陽極5 1 a與陰極5 3之間的 施加電壓即停止，然後來源氣體之供應即停止，並供應氮 氣到處理室50中做爲清洗氣體，以在處理室50中提供氮 -39- 200905010 氣環境，然後基板1在將溫度恢復到正常溫度時移除。 根據本具體實施例之DC電漿化學氣相沈積裝置除了 第一具體實施例的優點（1)到（6)之外具有以下的優點（8)及 (9)。 (8) 爲了在具有大面積的基板1上進行薄膜沈積，其需 要增加第一具體實施例之DC電漿化學氣相沈積裝置中平 臺11與陰極13的面積（外徑）。但是增加平臺11與陰極13 之面積（外徑）可能造成不足的反應氣體被供應到平臺1 1的 中心，或可，造成周緣側及中央部分之間不可忽略的溫度 差。此有可能造成薄膜沈積的變異。 在第五具體實施例的DC電漿化學氣相沈積裝置中， 藉由對比可看出，平臺51與陰極53具有長方形，而噴嘴 62的部分62A、62B平行於長邊方向而放置。此可確保來 源氣體的供應在長邊方向上不會改變，藉此使其有可能抑 制在長邊方向上薄膜沈積的變異。適當地設定陽極51a與 陰極53在短邊方向上的長度可以確保在具有大面積之基 板1上抑制變異的薄膜沈積。 (9) 因爲平臺51與陰極53具有長方形狀，複數正方基 板1可以放置在陽極51a與陰極53之長邊方向上，所以可 在複數基板1上一次進行同時的薄膜沈積。此適合於大量 生產。在此種情況中，在相同處理槽中對複數基板1進行 薄膜沈積，所以如果在需要數目的基板上進行薄膜沈積， 即不需要考慮處理槽之間的變異。 [第六具體實施例] -40- 200905010 第16A圖爲根據本發明第六具體實施例的DC電漿化 學氣相沈積裝置的組態圖，而第1 6B圖爲由下方觀視的陰 極之平面圖。 第17圖爲上述第16A圖之DC電漿化學氣相沈積裝置 的陰極、來源氣體噴嘴及排氣導管。 第18圖爲由側向之第16A圖的DC電槳化學氣相沈積 裝置之剖視圖。 此DC電漿化學氣相沈積裝置爲第13圖所示之第五具 體實施例的D C電漿化學氣相沈積裝置，其陰極5 3改變成 陰極65，且其電壓設定單元61改變成電壓設定單元66。 陰極65具有中央電極65a，其面向陽極51a之中央部 分，周緣電極65b，其形狀爲環形環（參見第16B圖），環繞 中央電極65a，其面對陽極51a之周緣部分，及陶瓷或類似 者製成的絕緣部分6 5 c ’其完全塡滿在中央電極6 5 a與周緣 電極6 5 b之間。 若不將絕緣部分65c插入在中央電極65a與周緣電極 6 5 b之間，由活性物種成長的薄膜不僅沈積在基板1上，亦 在彼此面對的中央電極6 5 a之側壁與周緣電極6 5 b之側壁 上。在此方面，絕緣部分65c被插入，以防止碳膜沈積在 彼此面對之中央電極6 5 a之側壁上與周緣電極6 5 b的側壁 上。 電壓設定單元66具有控制單元66a，及可變電源66b、 6 6 c ° 控制單元6 6 a由導線連接至輻射溫度計1 8。控制單兀 -41 - 200905010 66a具有能力來控制可變電源66b、66c，並個別地設定陽 極51a與中央電極65a之間的電壓或電流，及陽極51a與 中央電極6 5 a之間的電壓或電流。其他的組態相同於第1 3 圖中的DC電漿化學氣相沈積裝置。 如果使用第16A圖及第16B圖中的DC電漿化學氣相 沈積裝置形成薄膜在基板1上時’基板1於電漿上升時以 1 rp m的速率旋轉，平臺5 1與中央電極6 5 a之間的電壓差 在電壓設定單元66的控制之下會大於平臺51與周緣電極 65b之間的電壓差，以設定陰極65與陽極51a之間的電壓。 這樣的施加電壓在陽極51a與中央電極65a之間產生小的 正極柱PC，並可防止在薄膜沈積的初始階段發生電弧放 電。 在該穩定正極柱PC由施加這樣的電壓或電流而形成 在基板1之中央部分的上部時，控制單元66a施加該電壓 或電流使得陽極5 1 a與中央電極65a之間的電壓或電流値 成爲小於陽極5 1 a與周緣電極65b之間的電壓或電流値， 以將陽極5 1 a與中央電極65 a之間的溫度近似於陽極5 1 a 與周緣電極65b之間的溫度，或使得那些溫度於在基板1 上進行薄膜沈積之前大致相等。 在本具體實施例中，如上所述，陰極65包含中央電極 65a與周緣電極65b，及陽極51a與中央電極65a之間的電 壓或電流値，陽極5 1 a與周緣電極65b之間的電壓或電流 値可獨立地設定。在電漿上升時，陽極51a與中央電極65 a 之間的電壓被設定高於陽極51a與周緣電極65b之間的電 -42- 200905010 壓。因此’正極柱PC可利用將陽極51 a與陰極65之間的 距離變得較短來形成。要施加於陽極51a與陰極65的電壓 可以較低，藉此抑制電弧放電或火花之經常發生。 再者’流過周緣電極6 5 b之電流會變成小於流過中央 電極65a之電流，以產生在基板1之長邊中央處集中的正 極柱PC ’然後施加到周緣電極65b之電力即增加，以增加 流過周緣電極65b之電流。此使其有可能防止發生在薄膜 沈積之初始階段之局部電弧放電，然後正極柱PC可成長到 需要的尺寸。 [第七具體實施例] 第19圖爲根據本發明第七具體實施例之Dc電漿化學 氣相沈積裝置的組態圖，在第1 9圖中與第1 3圖中的組件 共用之那些組件即給與共用的參照編號。 第20圖爲上述第19圖之DC電漿化學氣相沈積裝置的陰 極、反應氣體噴嘴、基質氣體噴淋噴嘴及排氣導管的示意圖。 第2 1圖爲由側向之第1 9圖的DC電漿化學氣相沈積裝 置之剖視圖。 DC電漿化學氣相沈積裝置在要處理之基板1的上表面 之上形成薄膜’並具有處理室70做爲反應爐。處理室70 將基板1隔離外界空氣。 長方形平行六面體鋼質平臺51置於處理室70中。由 具有高導熱性及高熔點之材料製成的長方形板狀陽極 51a，例如鉬或石墨，即安裝在平臺51上。基板1固定在 陽極51a之上方安裝面上。基板1可具有長方形狀，或複 -43- 200905010 數正方基板1可放置在陽極5U上。 在陽極5 1 a之下的平臺5 1具有封閉的空間5 1 b，其中 置有冷卻構件52。冷卻構件52係用於視需要冷卻基板1， 並建構成可以藉由移動機構（未示出）而如箭頭所示般地上 下移動。冷卻構件5 2由具有高導熱性的金屬形成，例如 銅。一種冷卻劑，例如冷卻水或氯化鈣的冷卻溶液，其由 導管52a進入冷卻構件52中的流動通道52b，並由導管52c 排出而在冷卻構件5 2中循環，以冷卻整個冷卻構件5 2。 當冷卻構件5 2向上移動時，冷卻構件5 2的上方側緊 靠在平臺5 1的底側，其冷卻位在上面的陽極5 1 a，藉此將 熱量由基板1帶離。冷卻構件5 2的上方側爲長方形，並在 長度方向上冷卻整個平臺51。 由導管5 2c排出的冷卻劑由冷卻單元（未示出）冷卻，並 再次傳送到導管52a來重新循環。 提供在陽極51a之下的空間51b被平臺51區隔，所以 空間5 1 b的內部充滿氣體或開放至空氣中。 長方形板狀的陰極53置於陽極51a之上。陰極53支 撐在陰極支撐14上，並面對陽極51a。陰極53由鉬、石墨 或具有高熔點之類似材料所形成。 陰極支撐5 4由隔熱氧化物，例如石英玻璃或鋁，隔熱 氮化物，例如氮化鋁或氮化矽，或隔熱碳化物，例如碳化 矽等製成。 冷卻劑流經的通道可在陰極5 3中形成。冷卻劑的流動 可抑制陰極5 3的過熱。較佳的冷卻劑爲水、氯化鈣溶液及 -44- 200905010 類似者，其由處理室7 0之外部供應。 用於抑制電弧發生的絕緣單元5 5置於靠近陽極5 1 a的 外側表面。絕緣單元5 5包含隔熱氧化物，例如石英玻璃或 銘，隔熱氮化物，例如氮化銘或氮化砍，或隔熱碳化物， 例如碳化矽等當中至少一項。 形狀爲環形的絕緣單元55以與陽極51a相同的高度來 支撐，其由在處理室70之底部及環繞陽極51a之內側處直 立提供的支撐1 6所支撐。 因爲絕緣單元5 5用於抑制陰極5 3與陽極5 1 a之間的 異常放電（電弧放電、火花）之發生，絕緣單元55沿著陽極 5 1 a之外側表面並相對於陰極5 3來放置。絕緣單元5 5可配 置成隱藏陽極5 1 a之側面。 在處理室70的側面中形成觀視窗57，以允許觀察處理 室7 0的內部。隔熱玻璃安裝在觀視窗5 7中，以確保處理 室7 0內的氣密性。輻射溫度計5 8經由例如觀視窗5 7測量 基板1之溫度，並置於處理室7 0之外部。 DC電漿化學氣相沈積裝置具有反應氣體系統（未示 出），其透過充氣管71供應反應氣體，來源系統（未示出）， 其透過充氣管72供應基質氣體，排氣系統（未示出），其自 處理室70內部經由排,氣導管60排出氣體，及電壓設定單 元6 1。 充氣管7 1經由在處理室7 0中提供的孔洞插入到處理 室70中，且在反應爐中充氣管71之至少一部分由絕緣體 形成，例如氟化樹脂或矽膠。密合劑密封在處理室7〇之孔 -45- 200905010 洞與充氣管7 1之外側表面之間，以確保處理室70 氣密度。在處理室70中，充氣管71連接至噴嘴73 反應氣體供應噴嘴。 噴嘴73具有一部分73A，其平行於每一個陽極 陰極53之長邊，及一部分73B平行於每一個陽極5 極53之另一長邊。噴嘴73可爲整個環形，或部分 73B可由與充氣管71的連接點分支出去。噴嘴73 以傳送反應氣體。複數噴出埠7 3 a以線性對稱方式 間距形成在噴嘴73的部分73A、73B中，所以來源 噴出埠7 3 a朝向基板1側向地噴出，即在側向向內文 噴嘴73由附著於陰極支撐54之絕緣噴嘴支撐 撐。噴嘴73之支撐高度設定的方式爲噴出埠73a低 支撐54的最低位置之下（陰極53之暴露側面的最 分），以及位置在高於陽極5 1 a與陰極5 3之間形成 柱PC之最高點。因爲噴嘴73支撐在此範圍中，該 體輕易地進入陰極5 3與陽極5 1 a之間，並可防止在 PC中的氣體溫度由來源氣體之噴射而局部冷卻。 噴嘴73之部分73A、73B之間的間隔大於陰極 度（短邊方向），而噴嘴73的部分73A、73B放置在 向上陰極5 3之兩個側面之更外側。部分7 3 A、7 3 B 方向上與陽極5 1 a之中心線大致爲相等距離。 排氣導管60分別穿透在處理室70之底側中形 數孔洞而以相等間距環繞平臺5 1。密封劑密封於相 導管60之每個孔與外側表面之間。 內部的 ，其爲 5 la與 la與陰 73A、 爲中空 以相等 氣體由 Ϊ向上。 63所支 於陰極 上方部 的正極 來源氣 正極柱 53的寬 長邊方 在長邊 成的複 關排氣 -46 - 200905010 電壓設定單元61爲一種控制裝置’其設定陽極51a與 陰極5 3之間的電壓或電流之數値，並具有控制單元6 1 a及 可變電源61b。電壓設定單元61藉由導線連接至陽極51a 與陰極53。該等導線通過在處理室70中提供的孔洞。在導 線通過的處理室7 0中的孔洞由密封劑所密封。 電壓設定單元61的控制單元61a藉由導線連接至輻射 溫度計58，及由導線連接至可變電源61b。當啓動時，控 制單元6 1 a代表由輻射溫度計5 8測量的基板1之溫度，並 調整陽極51a與陰極53之間的電壓或電流値’所以基板1 的溫度成爲預定値。 充氣管72,其由絕緣體製成，其通過在處理室70中提 供的孔洞。密封劑密封在該孔洞與充氣管72之外側表面之 間，以確保處理室7 0之內的氣密性。在處理室7 〇中’充 氣管72連接至氣體噴淋噴嘴74用於基質氣體。 氣體噴淋噴嘴74,其與陰極53具有大致相同的長度’ 其位於支撐陰極53之陰極支撐14之上及噴嘴73之上’並 放置成平行及相對於軸5 3 X爲線性對稱，其做爲沿著陰極 53之長邊方向的中心軸，以向下噴出基質氣體’像是淋浴 頭。 在使用本具體實施例之DC電漿化學氣相沈積裝置進 行薄膜沈積之基本作業類似於使用第五具體實施例2 DC 電漿化學氣相沈積裝置的情況。其要注意到本具體實施例 之DC電槳化學氣相沈積裝置中，基質氣體及反應氣體被 獨立地引進，且反應氣體在側向向內方向上自噴嘴73噴 -47- 200905010 出，而基質氣體自氣體噴淋噴嘴74向下噴出。基質氣體改 變側向噴出之反應氣體之流動向量’所以該反應氣體流動 朝向該斜向位在下方的基板1。 根據本具體實施例之DC電漿化學氣相沈積裝置除了 第五具體實施例之優點之外具有以下的優點（1 0)。 (10)其槪略可知該反應氣體相對於基質氣體之濃度會 影響薄膜品質。但是’在引進具有反應氣體與基質氣體之 氣體混合物的方法中’其僅混合到預定濃度，並由自然產 生的對流供應該氣體混合物到該基板’新的氣體混合物足 以影響基板1上的薄膜沈積，而將新引進的氣體混合物由 排氣導管60排出，其係在氣體混合物充份到達基板1之 上，所以該反應氣體可能會很浪費地消耗掉。如果在氣體 混合物中反應氣體的濃度即增加以避免反應氣體導向的沈 積物有可能發生在陰極53及支撐陰極53之絕緣陰極支撐 54，使得電漿變成電弧放電或火花。本具體實施例之DC 電漿化學氣相沈積裝置獨立地引進基質氣體與反應氣體， 設定反應氣體之噴出位置相對高於基板1，並設定基質氣 體之噴出位置高於反應氣體的噴出位置，所以朝向基板1 之反應氣體的流動可由基質氣體之向下力量所操縱’藉以 降低浪費排出的反應氣體量。此外，基質氣體的噴出位置 設定於陰極53與支撐陰極53之陰極支撐54之上’且反應 氣體之噴出位置設定在陰極5 3之底側之下’所以該向下力 量於基質氣體到達排氣導管60時被施加，抑制反應氣體朝 向陰極53對抗基質氣體之流動的反向流動，並防止反應氣 -48- 200905010 體成分黏著到陰極5 3及支撐陰極5 3的絕緣陰極支撐5 4上。 [第八具體實施例] 第22A圖及第22B圖所示爲根據本發明第八具體實施 例之D C電漿化學氣相沈積裝置的組態圖。對於與第1 9圖 之組件共用之第2 2 A圖及第2 2 B圖中的那些組件皆給與共 用的參照編號。 第23圖爲上述第22A圖之DC電漿化學氣相沈積裝置 的陰極、反應氣體噴嘴、基質氣體噴嘴及排氣導管圖。 第2 1圖爲由側向之第2 2 A圖的D C電漿化學氣相沈積 裝置之剖視圖。 此DC電漿化學氣相沈積裝置爲第19圖所示之第七具 體實施例的DC電漿化學氣相沈積裝置，其陰極53改變成 陰極75，且其電壓設定單元61改變成電壓設定單元76。 陰極75具有中央電極75a，其面對陽極51a之中央部 分，周緣電極75b，其形狀爲環形（參見第22B圖），環繞中 央電極75 a，其面對陽極51a之周緣部分，及陶瓷或類似者 製成的絕緣部分75c完全塡滿在中央電極75a與周緣電極 7 5 b之間。 若不將絕緣部分7 5 c插入在中央電極7 5 a與周緣電極 7 5 b之間，由活性物種成長的薄膜不僅沈積在基板1上，亦 在彼此面對的中央電極75a之側壁與周緣電極75b之側壁 上。在此方面，絕緣部分7 5 c被插入，以防止碳膜沈積在 彼此面對之中央電極75a之側壁上與周緣電極75b的側壁 上0 -49- 200905010 電壓設定單元76具有控制單元76a，及可變電源76b、 7 6 c 〇 控制單元76a由導線連接至輻射溫度計58。控制單元 76a具有能力來控制可變電源76b、76c，並個別地設定陽 極5 1 a與中央電極7 5 a之間的電壓或電流，及陽極5 U與 中央電極7 5 a之間的電壓或電流。其他的組態相同於第1 3 圖中的DC電漿化學氣相沈積裝置。 如果使用第22A圖及第22B圖中的DC電漿化學氣相 沈積裝置形成薄膜在基板1上時，於電漿上升時，陽極51a 與中央電極75a之間的電壓在電壓設定單元76的控制之下 會大於陽極51a與周緣電極75b之間的電壓，以設定陰極 7 5與陽極5 1 a之間的電壓。這樣的施加電壓在陽極5 1 a與 中央電極7 5 a之間產生小的正極柱PC，並可防止在薄膜沈 積的初始階段發生電弧放電。 這種電壓或電流的施加可允許該穩定正極柱PC形成 在基板1之中央部分的上部。然後，控制單元76a施加該 電壓或電流的方式使得陽極5 1 a與中央電極7 5 a之間的電 壓或電流値成爲小於陽極5 1 a與周緣電極7 5 b之間的電壓 或電流値，以將陽極5 1 a與中央電極7 5 a之間的溫度近似 於陽極5 1 a與周緣電極7 5 b之間的溫度，或使得那些溫度 於在基板1上進行薄膜沈積之前大致相等。 在本具體實施例中，如上所述，陰極75包含中央電極 75a與周緣電極75b，及陽極51a與中央電極75a之間的電 壓或電流値，陽極51a與周緣電極75b之間的電壓或電流 -50- 200905010 値可獨立地設定。在電發上升時，陽極51a與中央電極75a 之間的電壓被設定高於陽極51a與周緣電極75b之間的電 壓。因此，正極柱PC可利用將陽極51a與陰極75之間的 距離變得較短來形成。要施加於陽極5 1 a與陰極7 5的電壓 可以較低，藉此抑制電弧放電或火花之經常發生。 再者’流過周緣電極7 5 b之電流會變成小於流過中央 電極75a之電流，以產生集中在基板1之中央處的正極柱 P C，然後施加到周緣電極7 5 b之電力即增加，以增加流過 周緣電極75b之電流。此使其有可能防止發生在薄膜沈積 之初始階段之局部電弧放電，然後正極柱PC可成長到需要 的尺寸。 本發明並不限於上述的具體實施例，並可修改成多種 其他型式。以下爲一些可能的修改。 (a) 包含複數電極的陰極2 7、3 5之結構可根據要處理 之基板1的尺寸及陽極1 1 a來適當地改變。例如，在第25 圖中的陰極90包含中央電極90a與複數周緣電極9 0b。在 此情況中，陽極11a與陰極可對每一個周緣電極90b個別 地設定電壓或電流。陶瓷的絕緣部分90c塡充在中央電極 90a與周緣電極90b之間。如第26圖及第27圖所示的每一 個陰極91、92具有複數圓形周緣電極91b、92b，其設計成 與中央電極91a、92a具有相同的大小。在每一個陰極91、 92中，陶瓷的絕緣部分91c、9 2c塡充在周緣電極91b、9 2b 與中央電極91a、92a之間。 (b) 雖然將陰極27、35建構成具有同圓心配置的中央 -51 - 200905010 電極27a、3 5a與周緣電極27b、35b，類似於第28 之陰極9 3，該陰極可建構成具有三個同圓心的中央 即環狀中央電極93a，環繞中央電極93a及與其隔離 環狀周緣電極93b，及第二環狀周緣電極93c，其環 一環狀周緣電極93b並與其隔離。 (c )冷卻構件1 2亦可修改。 第29A圖所示爲DC電漿化學氣相沈積裝置之 件12的另一個修改之上視圖，及第29B圖爲第29A 著線A-A的冷卻構件12之示意剖視圖。第30A圖爲 圖與第29B圖中冷卻構件12的上視圖，及第30B 30A圖中沿著線B-B的冷卻構件12之冷卻運作的示 圖。在第29A圖與第29B圖中所示的電漿化學氣相 置中，冷卻構件12具有導管12a、12b及12c，其中 冷卻單元9 9所供應的冷卻劑。在冷卻構件1 2的上方 上，即形成自排氣孔1 2x延伸到冷卻構件1 2之側面 溝槽12y。因此如第30B圖所示，即使當冷卻構件] 方側12w緊靠在平臺11上時，冷卻氣體通過及移動 1 2y與平臺1 1之間的縫隙中形成的通道，如由箭頭 以進行有效率的排氣與冷卻。氦氣’其排氣流速由 制器95調整，由氦氣塡充單元94傳送到三向閥98。 其排氣流速由流量控制器97調整，由氮氣塡充單元 送到三向閥9 8。當三向閥9 8打開時，冷卻的氦氣及 氮氣經由排氣孔12x噴灑到平臺11的緊靠表面上， 基板1。 圖所示 電極， 的第一 繞該第 冷卻構 圖中沿 第29A 圖爲第 意剖視 沈積裝 流過由 側1 2 w 12z之 ί 2的上 在溝槽 所示’ 流量控 氮氣’ i 96傳 冷卻的 以冷卻 -52- 200905010 [第九具體實施例] 第31圖爲根據本發明第九具體實施例之DC電漿化學 氣相沈積裝置的組態例。 DC電漿化學氣相沈積裝置在要處理之基板101的上表 面之上形成薄膜，並具有處理室110做爲反應爐。處理室 110將基板101隔離外界空氣。 柱狀鋼質平臺111放置在處理室110中，及碟狀陽極 112安裝在平臺111之上方部分處電極安裝面111a上。基 板101例如爲長方形，其放置在陽極112之上方基板安裝 面112a上。陽極112由石墨形成，且其表面之粗糙度平均 値Ra爲5 μιη左右。 在陽極 1 1 2之下的平臺1 1 1具有封閉的柱狀空間 111b，且平臺111的電極安裝面111a爲平板狀。 柱狀冷卻構件1 1 3放置在平臺1 1 1的空間1 1 1 b中。冷 卻構件1 1 3視需要用於冷卻基板1 0 1，並由具有高導熱性之 金屬所形成，例如銅。將冷卻構件1 1 3建構成可由移動機 構（未示出）上下移動，如箭頭所示。 冷卻構件1 1 3的上方端面爲面對相對於平臺1丨1之電 極安裝面111a之面111c之相對面113a(以下稱之爲“底 面”），並具有大的外徑。當冷卻構件1 1 3向上移動時，相 對面113a面對平臺111的底面111c’其方式爲接近或緊靠 成面對底面1 1 1 c。 流動通道1 1 3 b，其中流過冷卻劑，例如冷卻水或氯化 鈣溶液，其形成在冷卻構件1 1 3中。流動通道u 3b自冷卻 -53- 200905010 構件Π 3的側面穿過，通過靠近相對面1 1 3 a，並再次到達 冷卻構件1 13的側面。流動通道1 13b經由導管1 13c、1 13d 連接至冷卻單元1 1 3，所以冷卻劑由冷卻單元1 1 5冷卻，並 在流動通道1 1 3b與冷卻單元1 1 5之間循環。 排氣孔113e形成在冷卻構件113之相對面113a之中 央。排氣孔1 1 3e穿過冷卻構件1 1 3的下方側面。在冷卻構 件1 1 3的下方側面處，排氣孔1 1 3 e連接至導管1 1 6。導管 116經由閥117與流量控制器118連接至圓筒119。圓筒119 塡充有氦氣、氮氣或類似者做爲冷卻氣體。冷卻氣體塡充 在空間111b中，但並未塡充在陽極112之基板安裝面112a 側上。 顯然，冷卻構件1 1 3具有利用冷卻劑來冷卻平臺1 1 1 之機構，以及藉由從排氣孔1 1 3e噴灑冷卻氣體到平臺1 1 1 之上來冷卻平臺111的機構。因此在冷卻陽極112與基板 101時，可選擇一種使得相對面113a部分或整個緊靠在平 臺1 1 1的底面1 1 1 c上的方法，一種利用將相對面11 3a移 動更靠近底面111c而噴灑冷卻氣體到平臺111上之方法， 或兩種方法。 陰極120被支撐爲面對陽極112之基板安裝面112a。 可施加電壓來產生電漿的電源121連接至陰極120與陽極 1 1 2之間。 於處理室110中高於陰極120的位置處提供氣體供應 管路1 22，用於供應來源氣體，其由來源氣體系統（未示出） 供應到處理室1 1 0中。用於排出該來源氣體之氣體排出管 -54- 200905010 路123提供在處理室110的底部處。 氣體供應管路122與氣體排出管路123個別通過在處 理室1 1 0中提供的孔洞，及密封劑密封在每個孔洞與每個 氣體供應管路1 22與氣體排出管路1 23之外側表面之間’ 以確保處理室1 1 0內部的氣密性。連接至氣體排出管路1 23 爲排氣系統（未示出），其由氣體排出管路123排出該來源氣 體，以調整處理室110中的大氣壓力。 在處理室1 1 0的側面上形成觀視窗1 25，以允許觀察處 理室1 1 0的內部。在此例中，隔熱玻璃安裝在觀視窗1 2 5 中，以確保處理室1 1 0內部的氣密性。光譜輻射計1 2 6經 由例如觀視窗125的隔熱玻璃測量基板101之溫度，並置 於處理室1 1 0之外部。 在使用DC電漿化學氣相沈積裝置進行基板1〇1上的薄 膜沈積時，首先，基板101置於陽極112的基板安裝面112a 上。當完成基板101的安裝時，接下來，處理室110的內 部使用排氣系統洩壓，接著由氣體供應管路1 22供應來源 氣體到處理室110中。來源氣體爲要用於薄膜沈積之材料 的反應氣體（如甲烷）及基質氣體（載具氣體）（如氫氣）的混 合物，其不會成爲由預定比例的薄膜沈積材料。在碳基板 1 0 1上沈積石墨、鑽石粒子或類似者的碳膜時，該反應氣體 成爲含碳化合物的氣體。 r p m 在處理室110內的壓力即設定爲預定値，或其方式爲 藉由調整該來源氣體的供應量及排出量而使得其與該預定 値的變異落在可允許範圍內。平臺1 1 1可以例如以1 0 -55- 200905010 旋轉，以旋轉基板101及陽極1 12。在此狀況下’施加DV 電壓在陽極112與陰極120之間來產生電漿。當產生電漿 時，該電漿由反應氣體產生活性物種，藉此在基板1 〇 1上 開始薄膜沈積。旋轉基板1 0 1與陽極1 1 2降低根據基板1 〇 1 位置之溫度變化，藉此防止在基板1 0 1上薄膜沈積的變異。 爲了藉由抑制在基板1 0 1之溫度因爲沈積造成的上升 而確保所要的薄膜厚度，或藉由在薄膜沈積期間改變基板 1 0 1的溫度而改變薄膜品質，在冷卻構件1 1 3處提供的冷卻 機構要適當地選擇及使用。也就是說，相對面U3a可使其 緊靠在底面1 1 1 c上，而使得由冷卻單元1 1 5冷卻的冷卻劑 在冷卻構件1 1 3的流動通道1 1 3b中流動，或該冷卻氣體可 噴灑到底面1 1 1 c上，而允許相對面1 1 3 a接近到底面111 c， 或該冷卻氣體可被噴灑到底面1 1 1 c，而允許相對面1 1 3 a的 一部分緊靠到底面111c。 因爲基板1 0 1的表面溫度可由光譜輻射溫度計1 26測 量’基板101之冷卻時間及要施加在陽極1 1 2與陰極120 之間的電壓可根據由於電漿造成的基板101之表面溫度的 變化來控制。 當自從開始薄膜沈積而經過預定時間時，薄膜沈積即 進行到結束階段，在陽極1 1 2與陰極1 2 0之間的施加電壓 即停止，然後停止供應來源氣體，且供應氮氣到處理室1 1 〇 中做爲清洗氣體，以設定其中的壓力爲正常壓力，然後移 除基板1 0 1。 接下來將說明DC電漿化學氣相沈積裝置的優點。 -56- 200905010 ;極 電 .傳 112 因 .保 :稱 丨稱 :來 :基 1 10 a ° ;電 丨面 ;動 '電 度λ 111 約 J溫 當進行在基板101上的薄膜沈積時，基板101、 112與陰極120即暴露於陽極112與陰極120之間產生的 漿而被加熱。當提供給基板1 0 1之一部分能量由熱輻躬 遞到處理室11 0時，能量大部分由基板1 01傳遞到陽極 與平臺111，且在經由平臺1 1 1另傳遞到冷卻構件1 1 3。 爲傳遞的熱量與擴散的熱量平衡掉，基板1 0 1的溫度Π 持恆定。200905010 or current causes the voltage or electricity between the anode 11 a and the central electrode 35 a to be less than the voltage or current between the anode 11 a and the peripheral electrode 35 b to connect the anode 11 a to the central electrode 35 a The temperature is approximately the temperature between the anode and the peripheral electrode 3 5 b or such that the temperatures are substantially equal before the film deposition is performed thereon. In the present embodiment, as described above, the cathode 35 includes a center 35a and a peripheral electrode 35b, and a voltage or current 阳极 of the anode 11a and the center electrode 35a, and a voltage between the anode 11a and the peripheral electrode 35b:値 can be set independently. When the plasma rises, the voltage between the anode 11a and the central power is set higher than the pressure of the anode 11a and the peripheral electrode 35b. Therefore, the positive electrode PC can utilize the anode 11a and the cathode 35. The distance becomes shorter to form. The application to the anode 1 i a and the cathode 3 5 can be lower' thereby inhibiting the occurrence of arcing or sparking frequently. Further, the current flowing through the peripheral electrode 35b becomes smaller than the current flowing from the current electrode 35a. The power to generate P C ' concentrated at the center of the substrate 1 and then applied to the peripheral electrode 35 5 is increased, To increase the current of the peripheral electrode 35b. This makes it possible to prevent local arcing occurring in the initial stage of thinness. Then the positive electrode PC can grow in size. [Fifth Embodiment] Fig. 13 is a configuration diagram of a DC vapor deposition apparatus according to a fifth embodiment of the present invention. Figure 14 is a DC plasma chemical vapor deposition cathode of Figure 13 above, Schematic diagram of source gas nozzle and exhaust conduit. Rogue Lla plate 1 electrode electric current 5 35a electric voltage central pole flow through deposition needs to be chemically set -34- 200905010 Fig. 15 is a cross-sectional view of the DC plasma chemical vapor deposition device from the lateral view 13 . A DC plasma chemical vapor deposition apparatus forms a thin film on the upper surface of the substrate 1 to be processed, And having a processing chamber 50 as a reaction furnace. The processing chamber 50 isolates the substrate 1 from outside air. A rectangular parallelepiped steel platform 51 is placed in the processing chamber 50. a rectangular plate-shaped anode 5 1 a made of a material having high thermal conductivity and high melting point, For example, pin or graphite is mounted on platform 51. The substrate 1 is fixed to the upper mounting surface of the anode 51a. The substrate 1 may have a rectangular shape. Or a plurality of square substrates 1 may be placed on the anode 51a. The platform 51 below the anode 51a has a closed space 51b, There is placed a cooling member 52. The cooling member 52 is used to cool the substrate 1 as needed. The construction can be moved up and down as indicated by the arrow by a moving mechanism (not shown). The cooling member 52 is formed of a metal having high thermal conductivity. For example, copper. a coolant, For example, cooling water or a cooling solution of calcium chloride, It enters the flow passage 52b in the cooling member 52 by the conduit 52a, And discharged by the duct 52c to circulate in the cooling member 52, To cool the entire cooling member 52. When the cooling member 52 moves upward, The upper side of the cooling member 52 is abutted on the bottom side of the platform 51. It is cooled at the upper anode 51a, Thereby, heat is carried away from the substrate 1. The upper side of the cooling member 52 is rectangular. And cooling the entire platform 51 in the length direction. The coolant discharged from the conduit 52c is cooled by a cooling unit (not shown). It is again transferred to the conduit 52a for recirculation. The space 5 1 b provided below the anode 5 1 a is separated by the platform 5 1 , Therefore -35- 200905010 The interior of space 5 1 b is filled with gas or open to the air. A rectangular plate-shaped cathode 53 is placed on the anode 51a. The cathode 53 is supported on the cathode support 14, And facing the anode 51a. The cathode 53 is made of molybdenum, Stone or similar material with a high melting point. The cathode support 54 is made of a heat insulating oxide, Such as quartz glass or aluminum, Nitrile nitride, such as aluminum nitride or tantalum nitride, Or insulating carbide, For example, it is made of carbon or the like. A passage through which the coolant flows may be formed in the cathode 53. The flow of the coolant suppresses overheating of the cathode 53. The preferred coolant is water, Calcium chloride solution, similar, It is supplied from the outside of the processing chamber 50. An insulating unit 55 for suppressing the occurrence of an arc is placed near the outer surface of the anode 51a. The insulating unit 55 includes a heat insulating oxide, Such as quartz glass aluminum, Insulating nitride, For example, aluminum nitride or tantalum nitride, And at least one of insulating carbide such as tantalum carbide. The insulating unit 55 having a ring shape is supported at the same height as the anode 5 1 a, It is supported by a support 16 provided at the bottom of the processing chamber 50 and around the inside of the anode 51a. Because the insulating unit 5 5 is for suppressing abnormal discharge of electricity between the cathode 53 and the anode 5 1 a (arc discharge, Sparks happen, The insulating unit 55 is placed along the outer side surface of the pole 51a and with respect to the cathode 53. The insulating unit can be configured to hide the sides of the anode 5 1 a. Forming a window 5 7 on the side of the processing chamber 50 To allow observation of the interior of the chamber 50. Insulating glass is installed in the viewing window 57, To ensure air tightness within the chamber 50. The radiation thermometer 58 can measure the temperature of the substrate 1 via, for example, a thermal viewing of the ink and/or a straightening of the solar cell. It is placed outside the processing chamber 50. The DC plasma chemical vapor deposition apparatus has a source system (not shown), It can supply a source gas containing a reactive gas via the inflation tube 59. An exhaust system (not shown) that exhausts gas from the interior of the processing chamber 50 via an exhaust conduit 60, And a voltage setting unit 61. The inflation tube 59 is inserted into the processing chamber 50 via a hole provided in the processing chamber 50, And at least a portion of the gas tube 59 in the reaction furnace is formed of an insulator such as a fluorinated resin or silicone. The adhesive is sealed between the hole 处理 of the processing chamber 50 and the outer surface of the inflation tube 590, To ensure the gas density inside the processing chamber 50. In the processing chamber 50, The inflation tube 59 is connected to the nozzle 62, It is a gas supply nozzle. The nozzle 62 has a portion 62A, It is parallel to the long sides of each of the anode 51a and the cathode 53, And a portion 62B is parallel to the other long side of each of the anode 51a and the cathode 53. The nozzle 62 can be the entire ring shape. Or part 62A, 62 B can be branched by a connection point with the inflation tube 59. The nozzle 62 is hollow to deliver the source gas. The plurality of discharges 2 6 2 a are linearly symmetrical with respect to the axis 5 3 X or the central axis along the longitudinal direction of the long side of the cathode 5 3 to be formed at equal intervals in the portion 62A of the nozzle 62, 62B, Therefore, the source gas is ejected laterally toward the substrate 1 by the ejection of 埠6 2 a. That is, in the lateral inward direction. The nozzle 62 is supported by an insulating nozzle support 63 attached to the cathode support 54. The support height of the nozzle 62 is set in such a manner that the discharge port 62a is lower than the lowest position of the cathode support 54 (the uppermost portion of the exposed side of the cathode 53) and the position is higher than the anode 5 1 a and the cathode 5 3 The highest point of the positive electrode PC formed between. Because the nozzle 62 is supported in this range, The source gas -37-200905010 is easily inserted between the cathode 53 and the anode 51a. It is also possible to prevent the temperature of the gas in the positive electrode column PC from being locally cooled by the injection of the source gas. Portion 62A of nozzle 62, The interval between 62B is larger than the width of the cathode 53 (short side direction), And the portion 62A of the nozzle 62, 62B is placed on the outer side of the two sides of the cathode 53 on the long side. Part 62a, 62B is substantially equal to the center line of the anode 5 1 a in the longitudinal direction. The exhaust ducts 60 respectively penetrate the plurality of holes formed in the bottom side of the process chamber 50 to surround the platform 51 at equal intervals. The sealant is sealed between each of the associated and exhaust surfaces of the associated exhaust conduit 60. The voltage setting unit 61 is a control device. It sets the number of voltages or currents between the anode 51a and the cathode 53, It has a control unit 6 1 a and a variable power supply 61b. The voltage setting unit 61 is connected to the anode 51a and the cathode 53 by wires. The wires pass through the holes provided in the processing chamber 50. The holes in the process chamber 50 through which the wires pass are sealed by a sealant. The control unit 6 1 a of the voltage setting unit 6 1 is connected to the radiation thermometer 5 8 by wires And connected by wires to the variable power source 6 1 b. When starting up, The control unit 6 1 a represents the temperature of the substrate 1 measured by the radiation thermometer 58. And adjusting the voltage or current 阳极 between the anode 5 1 a and the cathode 5 3 , Therefore, the temperature of the substrate 1 becomes a predetermined enthalpy. Next, the deposition process will be explained. It forms a thin film on the substrate 1 using the DC plasma chemical vapor deposition apparatus of Fig. 13. In the deposition process, An electron discharge film containing a nanocarbon wall is deposited on the upper surface of the substrate 1. In the deposition process, First, for example, a nickel plate is cut into the substrate 1, And large -38- 200905010 The use of ethanol or acetone for degreasing / ultrasonic cleaning. This substrate 1 is placed on the anode 51a. When the substrate 1 is mounted, The processing chamber 50 is then vented using the exhaust system, And hydrogen, a reaction gas and a compound (carbonaceous compound) containing a reaction gas of carbon in the composition, Such as methane, That is, it is supplied into the processing chamber 50 by the inflation tube 59. The source gas is ejected from the discharge port 62a of the nozzle 62. When depositing the carbon wall of the nanometer, Film deposition is carried out at temperatures between 900 ° C and 1100 ° C. It is set as the temperature at which the portion of the substrate 1 forming the carbon nanotube wall. This temperature is measured by a radiation thermometer 58. at this time, The cooling member 52 is substantially separated from the anode 51a, The effect on the temperature of the anode 51a is avoided. The setting of the radiation thermometer 58 is such that the plasma radiation of the DC plasma chemical vapor deposition apparatus is lowered, The temperature is taken only by the heat radiation at the upper surface of the substrate 1. When a diamond layer containing multiple diamond particles is on the carbon wall of the nanometer, And changing the film properties of the electron discharge film during the nanocarbon deposition process, For example, the cooling member 52 moves upward to abut against the anode 51a. therefore, The temperature of the substrate 1 can be significantly lowered to cause lamination of the diamond layer. When the diamond layer grows, the rod-shaped sp2 bonds carbon, It is the modified part of the nano carbon wall. It does not grow like a carbon nanotube. This rod-shaped carbon extends to protrude from the upper surface of the diamond layer. It is structurally possible to concentrate the part of the electric field and release electrons. At the end platform of the film deposition, The applied voltage between the anode 5 1 a and the cathode 5 3 is stopped. Then the supply of source gas is stopped, And supplying nitrogen gas into the processing chamber 50 as a cleaning gas, To provide a nitrogen-39-200905010 gas environment in the processing chamber 50, The substrate 1 is then removed when the temperature is returned to normal temperature. The DC plasma chemical vapor deposition apparatus according to the present embodiment has the following advantages (8) and (9) in addition to the advantages (1) to (6) of the first embodiment. (8) In order to perform film deposition on the substrate 1 having a large area, It is necessary to increase the area (outer diameter) of the stage 11 and the cathode 13 in the DC plasma chemical vapor deposition apparatus of the first embodiment. However, increasing the area (outer diameter) of the stage 11 and the cathode 13 may cause insufficient reaction gas to be supplied to the center of the stage 1 1 . Or OK, A temperature difference between the peripheral side and the central part is not negligible. This may cause variations in film deposition. In the DC plasma chemical vapor deposition apparatus of the fifth embodiment, As can be seen from the comparison, The platform 51 and the cathode 53 have a rectangular shape. And the portion 62A of the nozzle 62, 62B is placed parallel to the long side direction. This ensures that the supply of source gas does not change in the long-side direction. This makes it possible to suppress variations in film deposition in the long-side direction. Properly setting the length of the anode 51a and the cathode 53 in the short-side direction can ensure the deposition of a film which suppresses variation on the substrate 1 having a large area. (9) Since the platform 51 and the cathode 53 have a rectangular shape, The plurality of square substrates 1 may be placed in the longitudinal direction of the anode 51a and the cathode 53, Therefore, simultaneous film deposition can be performed once on the plurality of substrates 1. This is suitable for mass production. In this case, Thin film deposition of the plurality of substrates 1 in the same processing tank, So if film deposition is performed on the required number of substrates, That is, there is no need to consider the variation between the processing tanks. [Sixth embodiment] -40- 200905010 Fig. 16A is a configuration diagram of a DC plasma chemical vapor deposition apparatus according to a sixth embodiment of the present invention, Figure 16B is a plan view of the cathode viewed from below. Figure 17 is a cathode of the DC plasma chemical vapor deposition apparatus of the above 16A Source gas nozzle and exhaust duct. Figure 18 is a cross-sectional view of the DC electric chemical vapor deposition apparatus of Figure 16A in the lateral direction. The DC plasma chemical vapor deposition apparatus is the D C plasma chemical vapor deposition apparatus of the fifth embodiment shown in Fig. 13. Its cathode 5 3 is changed to a cathode 65, And its voltage setting unit 61 is changed to the voltage setting unit 66. The cathode 65 has a central electrode 65a, It faces the central portion of the anode 51a, Peripheral electrode 65b, Its shape is an annular ring (see Figure 16B), Surrounding the center electrode 65a, It faces the peripheral portion of the anode 51a, The insulating portion 6 5 c ' made of ceramic or the like is completely filled between the center electrode 65 5 a and the peripheral electrode 6 5 b. If the insulating portion 65c is not inserted between the center electrode 65a and the peripheral electrode 65b, A film grown from an active species is deposited not only on the substrate 1, Also on the side walls of the center electrode 65 5 a facing each other and the side walls of the peripheral electrode 6 5 b. In this regard, The insulating portion 65c is inserted, The carbon film is prevented from being deposited on the side walls of the center electrode 65 5 facing each other and the side walls of the peripheral electrode 6 5 b. The voltage setting unit 66 has a control unit 66a, And variable power source 66b, 6 6 c ° The control unit 6 6 a is connected by wires to the radiation thermometer 18. Control unit -41 - 200905010 66a has the ability to control the variable power supply 66b, 66c, And individually setting the voltage or current between the anode 51a and the center electrode 65a, And a voltage or current between the anode 51a and the center electrode 65a. The other configuration is the same as the DC plasma chemical vapor deposition apparatus in Figure 13. If the film is formed on the substrate 1 using the DC plasma chemical vapor deposition apparatus in Figs. 16A and 16B, the substrate 1 is rotated at a rate of 1 rp m as the plasma rises. The voltage difference between the stage 5 1 and the center electrode 65 5 a is greater than the voltage difference between the stage 51 and the peripheral electrode 65b under the control of the voltage setting unit 66. The voltage between the cathode 65 and the anode 51a is set. Such an applied voltage generates a small positive electrode PC between the anode 51a and the center electrode 65a, It also prevents arc discharge during the initial stages of film deposition. When the stable positive electrode PC is formed on the upper portion of the central portion of the substrate 1 by applying such a voltage or current, The voltage or current is applied by the control unit 66a such that the voltage or current between the anode 51a and the center electrode 65a becomes smaller than the voltage or current between the anode 51a and the peripheral electrode 65b. The temperature between the anode 5 1 a and the center electrode 65 a is approximated to the temperature between the anode 5 1 a and the peripheral electrode 65 b, Or the temperatures are substantially equal before the film deposition on the substrate 1. In this particular embodiment, As mentioned above, The cathode 65 includes a center electrode 65a and a peripheral electrode 65b. And the voltage or current between the anode 51a and the center electrode 65a, The voltage or current 之间 between the anode 5 1 a and the peripheral electrode 65b can be independently set. When the plasma rises, The voltage between the anode 51a and the center electrode 65a is set higher than the voltage between the anode 51a and the peripheral electrode 65b by -42 - 200905010. Therefore, the positive electrode column PC can be formed by making the distance between the anode 51a and the cathode 65 shorter. The voltage to be applied to the anode 51a and the cathode 65 can be low, This suppresses the occurrence of arcing or sparks frequently. Furthermore, the current flowing through the peripheral electrode 6 5 b becomes smaller than the current flowing through the central electrode 65a. The electric power generated by the positive pole PC ′ concentrated at the center of the long side of the substrate 1 and then applied to the peripheral electrode 65b is increased, To increase the current flowing through the peripheral electrode 65b. This makes it possible to prevent local arcing that occurs during the initial stages of film deposition. The positive column PC can then be grown to the desired size. [Seventh embodiment] Fig. 19 is a configuration diagram of a Dc plasma chemical vapor deposition apparatus according to a seventh embodiment of the present invention, Those components that are shared with the components in Figure 13 in Figure 19 are given a common reference number. Figure 20 is a diagram showing the cathode of the DC plasma chemical vapor deposition apparatus of the above Fig. 19. Reaction gas nozzle, Schematic diagram of a substrate gas shower nozzle and an exhaust conduit. Figure 21 is a cross-sectional view of the DC plasma chemical vapor deposition apparatus of the nineteenth aspect in the lateral direction. The DC plasma chemical vapor deposition apparatus forms a thin film ' on the upper surface of the substrate 1 to be processed and has a processing chamber 70 as a reaction furnace. The processing chamber 70 isolates the substrate 1 from outside air. A rectangular parallelepiped steel platform 51 is placed in the processing chamber 70. a rectangular plate-shaped anode 51a made of a material having high thermal conductivity and high melting point, Such as molybdenum or graphite, That is, it is installed on the platform 51. The substrate 1 is fixed to the upper mounting surface of the anode 51a. The substrate 1 may have a rectangular shape. Or -43- 200905010 The number square substrate 1 can be placed on the anode 5U. The platform 5 1 below the anode 5 1 a has a closed space 5 1 b, A cooling member 52 is disposed therein. The cooling member 52 is used to cool the substrate 1 as needed. The construction can be moved up and down as indicated by the arrow by a moving mechanism (not shown). The cooling member 52 is formed of a metal having high thermal conductivity. For example, copper. a coolant, For example, cooling water or a cooling solution of calcium chloride, It enters the flow passage 52b in the cooling member 52 by the conduit 52a, And discharged by the conduit 52c to circulate in the cooling member 52, To cool the entire cooling member 52. When the cooling member 52 moves upward, The upper side of the cooling member 52 is abutted on the bottom side of the platform 5 1 . It is cooled at the upper anode 5 1 a, Thereby, heat is carried away from the substrate 1. The upper side of the cooling member 52 is rectangular. And cooling the entire platform 51 in the length direction. The coolant discharged from the conduit 52c is cooled by a cooling unit (not shown). It is again transferred to the conduit 52a for recirculation. The space 51b provided below the anode 51a is partitioned by the platform 51, Therefore, the interior of the space 5 1 b is filled with gas or opened to the air. A rectangular plate-shaped cathode 53 is placed on the anode 51a. The cathode 53 is supported on the cathode support 14, And facing the anode 51a. The cathode 53 is made of molybdenum, Graphite or a similar material with a high melting point. The cathode support 5 4 is made of a heat insulating oxide, Such as quartz glass or aluminum, Insulating nitride, For example, aluminum nitride or tantalum nitride, Or insulating carbide, For example, it is made of tantalum carbide. A passage through which the coolant flows may be formed in the cathode 53. The flow of the coolant suppresses overheating of the cathode 53. The preferred coolant is water, Calcium chloride solution and -44- 200905010 similar, It is supplied from the outside of the processing chamber 70. An insulating unit 55 for suppressing the occurrence of an arc is placed near the outer surface of the anode 5 1 a . The insulating unit 55 includes a heat insulating oxide, Such as quartz glass or Ming, Insulating nitride, Such as nitriding or nitriding, Or insulating carbide, For example, at least one of carbonized bismuth and the like. The insulating unit 55 having a ring shape is supported at the same height as the anode 51a. It is supported by a support 16 provided at the bottom of the processing chamber 70 and vertically at the inner side of the anode 51a. Because the insulating unit 5 5 is for suppressing abnormal discharge between the cathode 53 and the anode 5 1 a (arc discharge, Sparks happen, The insulating unit 55 is placed along the outer side surface of the anode 5 1 a and with respect to the cathode 53. The insulating unit 55 can be configured to hide the side of the anode 51a. A viewing window 57 is formed in a side surface of the processing chamber 70, To allow observation of the interior of the processing chamber 70. Insulating glass is installed in the viewing window 57, To ensure airtightness in the processing chamber 70. The radiation thermometer 58 measures the temperature of the substrate 1 via, for example, a viewing window 57. It is placed outside the processing chamber 70. The DC plasma chemical vapor deposition apparatus has a reactive gas system (not shown), It supplies the reaction gas through the inflation tube 71. Source system (not shown), It supplies the matrix gas through the inflation tube 72, Exhaust system (not shown), It passes through the row inside the processing chamber 70, The gas conduit 60 exhausts gas, And voltage setting unit 6 1. The inflation tube 71 is inserted into the processing chamber 70 via a hole provided in the processing chamber 70, And at least a portion of the gas tube 71 is formed of an insulator in the reaction furnace, For example, fluorinated resin or silicone. The adhesive is sealed between the hole of the processing chamber 7-45-200905010 and the outer surface of the inflation tube 7 1 To ensure the gas density of the process chamber 70. In the processing chamber 70, The gas tube 71 is connected to the nozzle 73 to supply a reaction gas supply nozzle. The nozzle 73 has a portion 73A, It is parallel to the long side of each anode cathode 53, And a portion 73B is parallel to the other long side of each of the anode 5 poles 53. The nozzle 73 can be the entire ring shape. Or portion 73B may be branched by a connection point with the inflation tube 71. The nozzle 73 is for conveying a reaction gas. The plurality of jets 埠 7 3 a are formed in a linearly symmetric manner at a portion 73A of the nozzle 73, In 73B, Therefore, the source ejects 埠7 3 a and is ejected laterally toward the substrate 1, That is, the laterally-facing nozzles 73 are supported by insulating nozzles attached to the cathode support 54. The support height of the nozzle 73 is set to be below the lowest position of the lower support 54 of the discharge port 73a (the most minute of the exposed side of the cathode 53), And the position is higher than the highest point of the column PC formed between the anode 5 1 a and the cathode 5 3 . Because the nozzle 73 is supported in this range, The body easily enters between the cathode 53 and the anode 5 1 a. It is also possible to prevent the temperature of the gas in the PC from being locally cooled by the injection of the source gas. Portion 73A of nozzle 73, The interval between 73B is greater than the cathode degree (short side direction), And the portion 73A of the nozzle 73, 73B is placed on the outer side of the two sides of the upper cathode 53. Part 7 3 A, 7 3 The direction of B is approximately equal to the centerline of anode 5 1 a. The exhaust ducts 60 respectively penetrate the number of holes in the bottom side of the process chamber 70 to surround the platform 51 at equal intervals. The sealant is sealed between each of the holes and the outer side surface of the phase conduit 60. Internal , It is 5 la and la and yin 73A, It is hollow with equal gas from Ϊ up. 63. The wide-length side of the positive-source gas positive electrode column 53 supported on the upper portion of the cathode is formed on the long side. -46 - 200905010 The voltage setting unit 61 is a control device which sets the anode 51a and the cathode 53. The number of voltages or currents between, It has a control unit 6 1 a and a variable power supply 61b. The voltage setting unit 61 is connected to the anode 51a and the cathode 53 by wires. The wires pass through the holes provided in the processing chamber 70. The holes in the process chamber 70 through which the wires pass are sealed by a sealant. The control unit 61a of the voltage setting unit 61 is connected to the radiation thermometer 58 by a wire, And connected to the variable power source 61b by a wire. When starting up, The control unit 6 1 a represents the temperature of the substrate 1 measured by the radiation thermometer 58. The voltage or current 値 between the anode 51a and the cathode 53 is adjusted so that the temperature of the substrate 1 becomes a predetermined enthalpy. Inflatable tube 72, It is made of an insulator, It passes through the holes provided in the process chamber 70. The sealant is sealed between the hole and the outer surface of the gas tube 72, To ensure airtightness within the processing chamber 70. In the process chamber 7 充, the charge pipe 72 is connected to the gas shower nozzle 74 for the matrix gas. Gas spray nozzle 74, It has substantially the same length as the cathode 53 'which is located above the cathode support 14 of the support cathode 53 and above the nozzle 73' and is placed in parallel and linearly symmetric with respect to the axis 5 3 X, It is taken as the central axis along the long side of the cathode 53, The substrate gas is ejected downwards like a shower head. The basic operation of performing thin film deposition using the DC plasma chemical vapor deposition apparatus of the present embodiment is similar to the case of using the fifth embodiment of the DC plasma chemical vapor deposition apparatus. It is to be noted that in the DC electric chemical vapor deposition apparatus of the present embodiment, The matrix gas and the reaction gas are independently introduced. And the reaction gas is sprayed from the nozzle 73 in the lateral inward direction -47-200905010, The matrix gas is ejected downward from the gas shower nozzle 74. The matrix gas changes the flow vector of the reaction gas which is laterally ejected, so that the reaction gas flows toward the substrate 1 which is located obliquely downward. The DC plasma chemical vapor deposition apparatus according to this embodiment has the following advantages (10) in addition to the advantages of the fifth embodiment. (10) It can be seen that the concentration of the reaction gas relative to the matrix gas affects the quality of the film. However, 'in the method of introducing a gas mixture having a reaction gas and a matrix gas', it is only mixed to a predetermined concentration, And supplying the gas mixture to the substrate by a naturally occurring convection, the new gas mixture is sufficient to affect the deposition of the film on the substrate 1, The newly introduced gas mixture is discharged from the exhaust duct 60. It is sufficient for the gas mixture to reach the substrate 1, Therefore, the reaction gas may be wasted wastefully. If the concentration of the reaction gas in the gas mixture is increased, it is possible to prevent the reaction gas-directed deposit from occurring on the cathode 53 and the insulated cathode support of the support cathode 53. Make the plasma into an arc discharge or spark. The DC plasma chemical vapor deposition apparatus of the specific embodiment independently introduces a matrix gas and a reaction gas, Setting the discharge position of the reaction gas to be relatively higher than the substrate 1, And setting the discharge position of the matrix gas higher than the discharge position of the reaction gas, Therefore, the flow of the reaction gas toward the substrate 1 can be manipulated by the downward force of the matrix gas to reduce the amount of waste gas discharged. In addition, The discharge position of the matrix gas is set on the cathode 53 of the cathode 53 and the support cathode 53 and the discharge position of the reaction gas is set below the bottom side of the cathode 53. Therefore, the downward force reaches the exhaust gas conduit 60. When it is applied, Suppressing the reverse flow of the reaction gas toward the cathode 53 against the flow of the matrix gas, And the reaction gas is prevented from adhering to the cathode 53 and the insulating cathode support 5 4 supporting the cathode 53. [Eighth Embodiment] Figs. 22A and 22B are configuration diagrams of a D C plasma chemical vapor deposition apparatus according to an eighth embodiment of the present invention. Common reference numerals are assigned to those components in Figures 2 2 A and 2 2 B that are shared with the components of Figure 19. Figure 23 is a cathode of the DC plasma chemical vapor deposition apparatus of the above 22A Reaction gas nozzle, Matrix gas nozzle and exhaust conduit diagram. Figure 21 is a cross-sectional view of the D C plasma chemical vapor deposition apparatus from the lateral 2 2 A diagram. The DC plasma chemical vapor deposition apparatus is the DC plasma chemical vapor deposition apparatus of the seventh embodiment shown in Fig. 19. Its cathode 53 is changed to a cathode 75, And its voltage setting unit 61 is changed to the voltage setting unit 76. The cathode 75 has a central electrode 75a, It faces the central portion of the anode 51a, Peripheral electrode 75b, Its shape is a ring (see Figure 22B), Surrounding the center electrode 75 a, It faces the peripheral portion of the anode 51a, The insulating portion 75c made of ceramic or the like is completely filled between the center electrode 75a and the peripheral electrode 75b. If the insulating portion 7 5 c is not inserted between the center electrode 75 5 a and the peripheral electrode 7 5 b, A film grown from an active species is deposited not only on the substrate 1, It is also on the side wall of the center electrode 75a and the side wall of the peripheral electrode 75b which face each other. In this regard, The insulating portion 7 5 c is inserted, To prevent the carbon film from being deposited on the side walls of the central electrode 75a facing each other and the side wall of the peripheral electrode 75b, the voltage setting unit 76 has a control unit 76a, And variable power supply 76b, 7 6 c 〇 The control unit 76a is connected by wires to the radiation thermometer 58. Control unit 76a has the ability to control variable power supply 76b, 76c, And individually setting the voltage or current between the anode 5 1 a and the center electrode 7 5 a, And the voltage or current between the anode 5 U and the center electrode 75 5 a. The other configuration is the same as the DC plasma chemical vapor deposition apparatus in Figure 13. If a film is formed on the substrate 1 using the DC plasma chemical vapor deposition apparatus in FIGS. 22A and 22B, When the plasma rises, The voltage between the anode 51a and the center electrode 75a is greater than the voltage between the anode 51a and the peripheral electrode 75b under the control of the voltage setting unit 76, To set the voltage between the cathode 75 and the anode 5 1 a. Such an applied voltage produces a small positive electrode PC between the anode 5 1 a and the central electrode 75 5 a, It can prevent arcing from occurring at the initial stage of film deposition. The application of such a voltage or current allows the stable positive electrode PC to be formed on the upper portion of the central portion of the substrate 1. then, The voltage or current is applied by the control unit 76a such that the voltage or current 阳极 between the anode 5 1 a and the central electrode 75 a becomes less than the voltage or current 阳极 between the anode 5 1 a and the peripheral electrode 7 5 b, The temperature between the anode 5 1 a and the center electrode 75 5 a is approximated to the temperature between the anode 5 1 a and the peripheral electrode 7 5 b, Or the temperatures are substantially equal before the film deposition on the substrate 1. In this particular embodiment, As mentioned above, The cathode 75 includes a center electrode 75a and a peripheral electrode 75b. And a voltage or current between the anode 51a and the center electrode 75a, The voltage or current between the anode 51a and the peripheral electrode 75b -50-200905010 can be independently set. When the electricity is rising, The voltage between the anode 51a and the center electrode 75a is set higher than the voltage between the anode 51a and the peripheral electrode 75b. therefore, The positive electrode column PC can be formed by making the distance between the anode 51a and the cathode 75 shorter. The voltage to be applied to the anode 5 1 a and the cathode 7 5 can be lower, This suppresses the occurrence of arcing or sparks frequently. Furthermore, the current flowing through the peripheral electrode 7 5 b becomes smaller than the current flowing through the central electrode 75a. To generate a positive electrode column P C concentrated at the center of the substrate 1, Then the power applied to the peripheral electrode 7 5 b is increased, To increase the current flowing through the peripheral electrode 75b. This makes it possible to prevent local arc discharge occurring at the initial stage of film deposition. The positive column PC can then be grown to the desired size. The invention is not limited to the specific embodiments described above, Can be modified into a variety of other types. The following are some possible modifications. (a) a cathode comprising a plurality of electrodes. The structure of 3 5 can be appropriately changed depending on the size of the substrate 1 to be processed and the anode 11a. E.g, The cathode 90 in Fig. 25 includes a central electrode 90a and a plurality of peripheral electrodes 90b. In this case, The anode 11a and the cathode can individually set a voltage or current for each peripheral electrode 90b. The insulating portion 90c of the ceramic is interposed between the center electrode 90a and the peripheral electrode 90b. Each cathode 91 as shown in Figures 26 and 27, 92 has a plurality of circular peripheral electrodes 91b, 92b, It is designed to be connected to the center electrode 91a, 92a has the same size. At each cathode 91, 92, Insulating portion 91c of ceramic, 9 2c is filled in the peripheral electrode 91b, 9 2b and the central electrode 91a, Between 92a. (b) although the cathode 27, 35 is constructed to have a center with the same center configuration -51 - 200905010 Electrode 27a, 3 5a and the peripheral electrode 27b, 35b, Similar to the cathode 9 3 of the 28th, The cathode can be constructed to have a center of the same center, that is, a ring-shaped central electrode 93a. Surrounding the central electrode 93a and isolating the annular peripheral electrode 93b, And a second annular peripheral electrode 93c, It is looped and isolated from an annular peripheral electrode 93b. (c) The cooling member 12 can also be modified. Figure 29A shows a top view of another modification of the DC 12 chemical vapor deposition apparatus. And Fig. 29B is a schematic cross-sectional view of the cooling member 12 of the 29A line A-A. Figure 30A is a top view of the cooling member 12 of the Figure and Figure 29B, And a diagram of the cooling operation of the cooling member 12 along the line B-B in the 30B 30A diagram. In the plasma chemical vapor phase shown in Figures 29A and 29B, The cooling member 12 has a conduit 12a, 12b and 12c, The coolant supplied by the cooling unit 99. Above the cooling member 12, That is, the groove 12y extending from the vent hole 1 2x to the side surface of the cooling member 12 is formed. Therefore, as shown in Figure 30B, Even when the cooling member] side 12w abuts against the platform 11, The cooling gas passes through and moves the passage formed in the gap between the tunnel and the platform 1 1 , As indicated by the arrows for efficient venting and cooling. The exhaust gas flow rate is adjusted by the controller 95. It is sent to the three-way valve 98 by the helium charging unit 94. The exhaust flow rate is adjusted by the flow controller 97. It is sent to the three-way valve 9 8 by a nitrogen charging unit. When the three-way valve 9 8 is open, The cooled helium gas and nitrogen gas are sprayed onto the abutting surface of the platform 11 via the vent hole 12x, Substrate 1. Figure shows the electrode, The first winding in the first cooling pattern along the 29th A is the intentional cross-sectional deposition loading through the side of the 1 2 w 12z ί 2 of the upper channel in the 'flow-controlled nitrogen' i 96 cooling to cool -52-200905010 [Ninth embodiment] FIG. 31 is a configuration example of a DC plasma chemical vapor deposition apparatus according to a ninth embodiment of the present invention. A DC plasma chemical vapor deposition apparatus forms a thin film on the upper surface of the substrate 101 to be processed, And having the processing chamber 110 as a reaction furnace. The processing chamber 110 isolates the substrate 101 from outside air. The columnar steel platform 111 is placed in the processing chamber 110, And the dished anode 112 is mounted on the electrode mounting surface 111a at the upper portion of the stage 111. The substrate 101 is, for example, rectangular. It is placed on the substrate mounting surface 112a above the anode 112. The anode 112 is formed of graphite. The surface roughness average 値Ra is about 5 μηη. The platform 1 1 1 below the anode 1 1 2 has a closed cylindrical space 111b, Further, the electrode mounting surface 111a of the stage 111 has a flat plate shape. The columnar cooling member 1 1 3 is placed in the space 1 1 1 b of the platform 1 1 1 . Cooling member 1 1 3 is used to cool the substrate 1 0 1 as needed And formed of a metal with high thermal conductivity, For example copper. The cooling member 1 1 3 is constructed to be movable up and down by a moving mechanism (not shown). As indicated by the arrow. The upper end surface of the cooling member 1 1 3 is an opposite surface 113a (hereinafter referred to as a "bottom surface") facing the surface 111c of the electrode mounting surface 111a with respect to the stage 1? And has a large outer diameter. When the cooling member 1 1 3 moves upward, The opposite surface 113a faces the bottom surface 111c' of the platform 111 in such a manner as to approach or abut against the bottom surface 1 1 1 c. Flow channel 1 1 3 b, Where the coolant flows, For example, cooling water or calcium chloride solution, It is formed in the cooling member 113. The flow passage u 3b is self-cooling -53- 200905010 The side of the member Π 3 passes through, By approaching the opposite face 1 1 3 a, And reaching the side of the cooling member 1 13 again. Flow channel 1 13b via conduit 1 13c, 1 13d is connected to the cooling unit 1 1 3, Therefore, the coolant is cooled by the cooling unit 115. And it circulates between the flow channel 1 1 3b and the cooling unit 1 15 5 . The vent hole 113e is formed at the center of the opposite surface 113a of the cooling member 113. The vent hole 1 1 3e passes through the lower side surface of the cooling member 1 1 3 . At the lower side of the cooling member 1 1 3, The venting opening 1 1 3 e is connected to the conduit 1 16 . The conduit 116 is coupled to the barrel 119 via a valve 117 and a flow controller 118. The cylinder 119 is filled with helium, Nitrogen or the like is used as a cooling gas. The cooling gas is filled in the space 111b, However, it is not filled on the substrate mounting surface 112a side of the anode 112. Obviously, The cooling member 1 1 3 has a mechanism for cooling the platform 1 1 1 with a coolant. And a mechanism for cooling the platform 111 by spraying a cooling gas from the vent 1 1 3e onto the platform 1 1 1 . Therefore, when the anode 112 and the substrate 101 are cooled, Alternatively, a method of causing the opposing face 113a to partially or entirely abut against the bottom face 1 1 1 c of the platform 1 1 1 , A method of spraying a cooling gas onto a platform 111 by moving the opposite surface 113a closer to the bottom surface 111c, Or two methods. The cathode 120 is supported to face the substrate mounting surface 112a of the anode 112. A power source 121 to which a voltage can be applied to generate plasma is connected between the cathode 120 and the anode 1 12 . A gas supply line 1 22 is provided at a location in the processing chamber 110 that is higher than the cathode 120, Used to supply source gases, It is supplied to the process chamber 110 by a source gas system (not shown). A gas discharge pipe for discharging the source gas - 54 - 200905010 A path 123 is provided at the bottom of the process chamber 110. The gas supply line 122 and the gas discharge line 123 individually pass through the holes provided in the treatment chamber 110. And a sealant is sealed between each of the holes and each of the gas supply line 1 22 and the outer side surface of the gas discharge line 1 23 to ensure airtightness inside the processing chamber 110. Connected to the gas discharge line 1 23 as an exhaust system (not shown), It discharges the source gas from the gas discharge line 123, To adjust the atmospheric pressure in the processing chamber 110. Forming window 1 25 is formed on the side of the processing chamber 110 To allow observation of the interior of the processing chamber 110. In this case, Insulating glass is installed in the viewing window 1 2 5 To ensure the airtightness inside the processing chamber 110. The spectroradiometer 1 2 6 measures the temperature of the substrate 101 by an insulating glass such as a viewing window 125, It is placed outside the processing chamber 110. When a film deposition on the substrate 1〇1 is performed using a DC plasma chemical vapor deposition apparatus, First of all, The substrate 101 is placed on the substrate mounting surface 112a of the anode 112. When the mounting of the substrate 101 is completed, Next, The interior of the processing chamber 110 is vented using an exhaust system, The source gas is then supplied to the process chamber 110 by a gas supply line 1 22 . The source gas is a mixture of a reaction gas (e.g., methane) and a matrix gas (carrier gas) (e.g., hydrogen) of a material to be used for film deposition, It does not become a film deposition material in a predetermined ratio. Depositing graphite on the carbon substrate 110 When diamond particles or similar carbon films, This reaction gas becomes a gas of a carbon-containing compound. r p m is set to a predetermined pressure in the processing chamber 110, Or by adjusting the supply and discharge of the source gas such that the variation with the predetermined enthalpy falls within an allowable range. The platform 1 1 1 can be rotated, for example, from 1 0 -55 to 200905010. The substrate 101 and the anode 1 12 are rotated. In this case, a DV voltage is applied between the anode 112 and the cathode 120 to generate a plasma. When plasma is produced, The plasma produces active species from the reactive gas, Thereby, film deposition is started on the substrate 1 〇 1 . Rotating the substrate 1 0 1 and the anode 1 1 2 lowers the temperature change according to the position of the substrate 1 〇 1 , Thereby, variation in film deposition on the substrate 110 is prevented. In order to ensure the desired film thickness by suppressing the rise of the temperature of the substrate 110 due to deposition, Or changing the film quality by changing the temperature of the substrate 1 0 1 during film deposition, The cooling mechanism provided at the cooling member 113 is appropriately selected and used. That is, The opposite surface U3a can be placed against the bottom surface 1 1 1 c, The coolant cooled by the cooling unit 115 is caused to flow in the flow passage 1 1 3b of the cooling member 1 1 3, Or the cooling gas can be sprayed onto the bottom surface 1 1 1 c, Allowing the opposite face 1 1 3 a to approach the bottom face 111 c, Or the cooling gas can be sprayed onto the bottom surface 1 1 1 c, A portion of the opposing face 1 1 3 a is allowed to abut against the bottom face 111c. Since the surface temperature of the substrate 110 can be measured by the spectral radiation thermometer 126, the cooling time of the substrate 101 and the voltage to be applied between the anode 112 and the cathode 120 can be varied according to the surface temperature of the substrate 101 due to the plasma. To control. When a predetermined time has elapsed since the start of film deposition, The film deposition is carried out to the end stage, The applied voltage between the anode 1 1 2 and the cathode 1 2 0 is stopped, Then stop supplying the source gas, And supplying nitrogen gas into the treatment chamber 1 1 〇 as a cleaning gas, To set the pressure among them as normal pressure, The substrate 1 0 1 is then removed. Next, the advantages of the DC plasma chemical vapor deposition apparatus will be explained. -56- 200905010 ; Extreme electricity . Pass 112 because of . Bao: nickname: to: base 1 10 a °; electric 丨 surface; dynamic 'electricity λ 111 about J temperature When performing film deposition on the substrate 101, the substrate 101, 112 and the cathode 120 are exposed to the anode 112 The slurry generated between the cathode 120 and the cathode 120 is heated. When a portion of the energy supplied to the substrate 110 is transferred from the heat transfer to the process chamber 110, most of the energy is transferred from the substrate 101 to the anode and the stage 111, and is further transferred to the cooling member 1 via the platform 1 1 1 3. The temperature of the substrate 1 0 1 is kept constant for the heat transferred and the heat of diffusion to be balanced.
薄膜沈積可同時在陽極112由石墨形成（以下此電棰 之爲“石墨電極”）以及陽極1 1 2由鉬形成（以下此電棰 之爲“鉬電極”）之情況下進行，並比較其結果。 在石墨電極與鉬電極的例子中，沈積條件爲使得誃 源氣體將在反應氣體中甲烷的流速設定爲50 seem，而右 質氣體中氫的流速設定爲500 seem，其被供應到處理室 中，且一般壓力藉由調整排出速度而保持在79 9 9.3 2 P 此外，藉由施加電力產生電漿的方式爲陰極· 120與石i 極及鉬電極之間的電流密度成爲0 . 1 5 A / c m2 (電流/電梗 積）。 鉬電極的表面之粗糙度平均値Ra爲1.5 μιη，大量穆 的導熱度λ爲132 W· m1· Κ·1。要做爲陽極112之石墨 極的表面之粗糙度平均値Ra爲5 μιη，大量移動的導熱 爲 120 W . m·1 · Κ—1。 厚度爲0.5 mm之矽用於基板101，且第31圖中平臺 之相對面11 3a與底面1 1 lc之間的距離X設定爲60mm， 爲自薄膜沈積開始之後2個小時，藉以改變基板1 0 1白< -57- 200905010 度。在此期間中，使用石墨電極在電漿化學氣相沈積裝置 中於基板上形成奈米碳壁成爲複數平行六面體（扇形） 薄碳片，其具有直立的曲面，並在隨機方向上鏈結在一起。 每個薄碳片由數個或數十個單層石墨片所形成，其每一片 具有晶格間距爲〇.34nm。 然後，距離x接近於〇 · 5 m m。接 著，做爲冷卻氣體之氦氣以5 0 0 s c c m經由排氣孔1 1 3 e供應 到平臺1 1 1之下方空間1 1 1 b中，以降低基板1 〇 1之溫度。 在此期間內，於使用石墨電極的電漿化學氣相沈積裝置 中，含有微晶鑽石粒子之微晶鑽石膜，其晶粒大小爲奈米 等級（小於丨μπι)，其沈積在基板101上的奈米碳壁上’奈 米碳壁的一部分主要隨著微晶鑽石粒子的成長而成長’並 穿過在微晶鑽石膜中的縫隙，藉此形成針狀的碳棒’其由 微晶鑽石膜之表面突出。此碳棒在其中形成有碳’且不像 是圓筒結構，例如奈米碳管，其爲具有中空內部的薄碳層’ 其爲堅硬，並具有高的機械強度，因爲其自奈米碳壁成長。 光譜輻射計1 26用於測量基板1 〇1的溫度’並執行來 自基板1 0 1之紅外線輻射的強度光譜儀’且基板1 0 1的溫 度與其發射率藉由使用灰體近似（gray body approximation) 來評估。 第3 2圖所示爲對於不同陽極11 2測量的基板1 〇 1之溫 度。 如第3 2圖所示，對於任一電極’基板1 〇 1的溫度在開 始薄膜沈積之後的3 0分鐘之內到達尖峰點，然後基板1 〇 1 的溫度即會下降而電流密度爲恆定。基板1 〇1的溫度具有 -58- 200905010 下降趨勢的理由爲做爲大量石墨片的奈米碳壁沈積在基板 101上，基板101的上方表面之發射率即上升，藉此增加來 自基板101的上方表面在處理室中輻射的傳遞熱量。再者， 於基板101的發射率因爲奈米碳壁沈積在基板101上而到 達恆定値之後，基板101的溫度即可穩定。這種現象顯示 當化學氣相沈積於基板101的溫度高於900°C時，周遭發 射率會大幅影響基板1 01的溫度。 比較對於不同電極而變化的基板1 0 1之溫度顯示在初 始沈積區域中，基板1 0 1的溫度將大幅變化，在石墨電極 上基板1 0 1的溫度要低於在鉬電極上基板1 0 1之溫度1 00°C 或更多。在後續狀態中，溫度變爲穩定，即使距離X爲 0.5 mm，在利用石墨電極時基板101的溫度比利用鉬電極時 基板101的溫度要低40°C。 第33圖所示爲在第32圖中反應爐中施加於電漿的電 力改變，而施加的電流爲恆定。 在薄膜沈積時，於陽極1 1 2與陰極1 20之間流動的電 流密度被控制成固定於0.15 A/cm2，而所施加的電壓自動 地根據氣體狀態來改變。實際上，電極之間的氣體密度愈 低，施加的電壓即會愈低。如果使用鉬電極，其使得基板 1 0 1的溫度變高，周遭氣體溫度由基板1 0 1及電極而增加， 並因此降低其密度，所以允許具有相同密度的電流來流動 的電壓對於石墨電極即變低，其使得基板1 0 1的溫度較低。 當在使用鉬電極時施加的電力永遠會低於使用石墨電極 時，因此在電力上的改變量即等於或小於施加電力的1.5%。 -59- 200905010 即使所施加功率幾乎未改變時，在鉬電極與石墨電極 之間基板101的溫度中永遠會有1 〇 〇。C的差異的原因是石 墨電極比鉬電極在溫度區域中較容易讓熱量逸出。似乎比 鉬電極要具有較低導熱性及較粗糙表面的石墨電極較容易 逸出熱量，因爲熱輻射會比接觸式在導熱性之分布要提供 導熱性上更大的分布。由於較大的接觸熱阻抗，如果電極 材料本身的導熱性並不明顯，由於表面反射，鉬的發射率 爲0.3左右，相較於石墨的發射率0.9或更高，所以其可輕 易地解釋成石墨電極使得基板1 01的溫度較低。 當基板1 0 1的溫度變高時，鉬電極與石墨電極之間的 溫度差趨勢上要更大時，其對應於事實上接觸式導熱性的 傳遞熱量會正比於溫度差異而改變，然而輻射熱式的導熱 性的傳遞熱量正比於絕對溫度的四次方而改變，所以基板 101的溫度愈高，快速排出的傳遞熱量即愈高，使其很難增 加溫度。那些因素亦指出熱輻射率亦大於薄膜沈積中的熱 傳導。 爲了估計熱傳導系統的傳遞熱量，使我們考慮將鏡面 拋光的基板放置在具有粗糙度平均値Ra的陽極上。假設表 面y爲基板的底側，表面z爲陽極之上表面，且基板的底 側y爲鏡面，該表面可製作成大致爲平面，而相較於陽極 的粗糙度平均値Ra。因此，該接觸式熱傳遞可視爲經由陽 極投射長度Ra來造成。在此例中，假設基板1 0 1的溫度爲 L，且陽極的溫度爲T2，由於接觸而由該基板流到該陽極 之單位面積的熱傳遞量…㈠可由下式表示。 -60- 200905010 公式 W n = λThe thin film deposition can be carried out simultaneously with the anode 112 being formed of graphite (hereinafter referred to as "graphite electrode") and the anode 11 2 being formed of molybdenum (hereinafter referred to as "molybdenum electrode"), and comparing result. In the examples of the graphite electrode and the molybdenum electrode, the deposition conditions are such that the source gas has a flow rate of methane in the reaction gas set to 50 seem, and the flow rate of hydrogen in the right gas is set to 500 seem, which is supplied to the processing chamber. And the general pressure is maintained at 79 9 9.3 2 P by adjusting the discharge speed. Further, the plasma is generated by applying electric power to the current density between the cathode 120 and the stone electrode and the molybdenum electrode becomes 0.15 A. / c m2 (current/electrical infarction). The surface roughness of the molybdenum electrode has an average 値Ra of 1.5 μηη, and the thermal conductivity λ of a large amount of MU is 132 W·m1·Κ·1. The roughness of the surface of the graphite electrode to be the anode 112 is 値Ra of 5 μηη, and the heat transfer of a large amount of movement is 120 W·m·1 · Κ-1. The crucible having a thickness of 0.5 mm is used for the substrate 101, and the distance X between the opposite surface 11 3a of the stage and the bottom surface 1 1 lc in Fig. 31 is set to 60 mm, which is 2 hours after the start of film deposition, thereby changing the substrate 1 0 1 white < -57- 200905010 degrees. During this period, a graphite electrode is used to form a nanocarbon wall on the substrate in a plasma chemical vapor deposition apparatus to form a plurality of parallelepiped (fan-shaped) thin carbon sheets having an upright curved surface and chained in a random direction. Put it together. Each of the thin carbon sheets is formed of several or tens of single-layer graphite sheets each having a lattice spacing of 〇.34 nm. Then, the distance x is close to 〇 · 5 m m. Next, helium gas as a cooling gas is supplied to the lower space 1 1 1 b of the stage 1 1 1 via the vent hole 1 1 3 e at a temperature of 500 s c c m to lower the temperature of the substrate 1 〇 1 . During this period, in a plasma chemical vapor deposition apparatus using a graphite electrode, a microcrystalline diamond film containing microcrystalline diamond particles having a grain size of nanometer order (less than 丨μπι) is deposited on the substrate 101. On the carbon wall of the nanocarbon, a part of the nanocarbon wall grows mainly with the growth of the microcrystalline diamond particles and passes through the gap in the microcrystalline diamond film, thereby forming a needle-shaped carbon rod. The surface of the diamond film is prominent. This carbon rod is formed with carbon ' therein and is not like a cylindrical structure, such as a carbon nanotube, which is a thin carbon layer having a hollow interior' which is hard and has high mechanical strength because it is derived from nanocarbon Wall growth. A spectroradiometer 1 26 is used to measure the temperature of the substrate 1 〇 1 and perform an intensity spectrometer of infrared radiation from the substrate 101 and the temperature of the substrate 110 and its emissivity are approximated by the use of gray body approximation. To evaluate. Figure 3 2 shows the temperature of substrate 1 〇 1 measured for different anodes 11 2 . As shown in Fig. 3, for any electrode 'the temperature of the substrate 1 〇 1 reaches the peak point within 30 minutes after the start of film deposition, the temperature of the substrate 1 〇 1 is lowered and the current density is constant. The reason why the temperature of the substrate 1 具有1 has a downward trend of -58 to 200905010 is that the nanocarbon wall as a large amount of graphite sheets is deposited on the substrate 101, and the emissivity of the upper surface of the substrate 101 rises, thereby increasing the substrate 101 from the substrate 101. The heat transferred by the upper surface radiating in the processing chamber. Furthermore, the temperature of the substrate 101 can be stabilized after the emissivity of the substrate 101 reaches a constant enthalpy due to deposition of the nanocarbon wall on the substrate 101. This phenomenon shows that when the temperature of the chemical vapor deposition on the substrate 101 is higher than 900 ° C, the peripheral emission rate greatly affects the temperature of the substrate 101. Comparing the temperature of the substrate 110 changed for different electrodes is shown in the initial deposition region, the temperature of the substrate 110 will vary greatly, and the temperature of the substrate 1 0 1 on the graphite electrode is lower than that on the substrate 10 on the molybdenum electrode. 1 temperature is 1 00 ° C or more. In the subsequent state, the temperature became stable, and even if the distance X was 0.5 mm, the temperature of the substrate 101 when using the graphite electrode was 40 ° C lower than the temperature of the substrate 101 when the molybdenum electrode was used. Fig. 33 is a view showing the change in the electric force applied to the plasma in the reaction furnace in Fig. 32, and the applied current is constant. At the time of film deposition, the current density flowing between the anode 11 2 and the cathode 1 20 was controlled to be fixed at 0.15 A/cm 2 , and the applied voltage was automatically changed in accordance with the gas state. In fact, the lower the gas density between the electrodes, the lower the applied voltage will be. If a molybdenum electrode is used, which causes the temperature of the substrate 110 to become high, the ambient gas temperature is increased by the substrate 101 and the electrode, and thus the density thereof is lowered, so that a voltage having a current of the same density is allowed to flow for the graphite electrode It goes low, which makes the temperature of the substrate 110 lower. When the molybdenum electrode is used, the electric power applied is always lower than when the graphite electrode is used, and thus the amount of change in electric power is equal to or less than 1.5% of the applied electric power. -59- 200905010 Even if the applied power is hardly changed, there will always be 1 〇 温度 in the temperature of the substrate 101 between the molybdenum electrode and the graphite electrode. The reason for the difference in C is that the graphite electrode is easier to allow heat to escape than the molybdenum electrode in the temperature region. It seems that a graphite electrode having a lower thermal conductivity and a rougher surface than a molybdenum electrode is more likely to escape heat because the thermal radiation provides a greater distribution of thermal conductivity than the contact type in the distribution of thermal conductivity. Due to the large contact thermal impedance, if the thermal conductivity of the electrode material itself is not obvious, the emissivity of molybdenum is about 0.3 due to surface reflection, which is easily interpreted as compared with the emissivity of graphite of 0.9 or higher. The graphite electrode makes the temperature of the substrate 101 lower. When the temperature of the substrate 110 becomes high, when the temperature difference between the molybdenum electrode and the graphite electrode tends to be larger, the heat transfer corresponding to the contact thermal conductivity is changed in proportion to the temperature difference, but the radiant heat The heat transfer of the thermal conductivity is changed in proportion to the fourth power of the absolute temperature, so the higher the temperature of the substrate 101, the higher the heat transfer quickly discharged, making it difficult to increase the temperature. Those factors also indicate that the thermal emissivity is also greater than the heat transfer in film deposition. In order to estimate the heat transfer of the heat transfer system, we have considered placing the mirror-polished substrate on an anode having a roughness average 値Ra. Assuming that the surface y is the bottom side of the substrate, the surface z is the upper surface of the anode, and the bottom side y of the substrate is a mirror surface, the surface can be made substantially planar, and the roughness 値 Ra is compared with the roughness of the anode. Therefore, the contact heat transfer can be regarded as being caused by the anode projection length Ra. In this example, assuming that the temperature of the substrate 110 is L and the temperature of the anode is T2, the amount of heat transfer from the substrate to the unit area of the anode due to the contact... (1) can be expressed by the following formula. -60- 200905010 Formula W n = λ
Ra (T, - T2 ) 其中λ爲陽極材料的導熱性，r爲基板101與陽極112 之間的外觀接觸面積與基板101與陽極Π2之間的真實接 觸面積的比例，而Ra爲該表面的粗糙度平均値。雖然在更 爲準確的公式中對於基板1 〇 1與陽極1 1 2之間的間距引入 修正項，在此處對於粗略計算即將其省略。 除了在固體之間接觸造成的熱傳遞之外，在基板1 〇 1 與陽極1 1 2之間的縫隙中有經由氣體傳遞的熱傳導。如果 熱傳遞簡化成藉由位在具有不同溫度之兩個平行板之間的 靜態層的熱傳遞，在〇. 1或更低的壓力之環境中，其對於 電漿化學氣相沈積在取得如第3 2圖所示之資料時很正 常，該平均自由路徑可視爲充份大於該基板底側的表面粗 糙度。因此，傳遞熱量可視爲自由分子熱傳導。此時，傳 遞熱量Wgl可表示成下式。 公式 2Ra (T, - T2 ) where λ is the thermal conductivity of the anode material, r is the ratio of the apparent contact area between the substrate 101 and the anode 112 to the true contact area between the substrate 101 and the anode Π 2, and Ra is the surface The average roughness is 値. Although a correction term is introduced for the spacing between the substrate 1 〇 1 and the anode 1 1 2 in a more accurate formula, it will be omitted here for rough calculation. In addition to the heat transfer caused by the contact between the solids, there is heat transfer through the gas in the gap between the substrate 1 〇 1 and the anode 11 2 . If heat transfer is simplified to heat transfer by a static layer between two parallel plates having different temperatures, in a pressure of 0.1 or lower, it is obtained for plasma chemical vapor deposition. The data shown in Fig. 3 is normal, and the mean free path can be regarded as being sufficiently larger than the surface roughness of the bottom side of the substrate. Therefore, heat transfer can be regarded as free molecular heat conduction. At this time, the transfer heat Wgl can be expressed as follows. Formula 2
Wgx =(1-γ)χ«·Λ·/7·(Γ1 -Τ2)Wgx = (1-γ)χ«·Λ·/7·(Γ1 -Τ2)
τ = τ,+τ2 2 fr + ιλτ = τ, +τ2 2 fr + ιλ
k 2πηιΤ 其中Λ爲自由分子熱導性，〇t爲可適化係數，ρ爲壓力， -61 - 200905010 γ爲比熱率，k爲波茲曼（Bolzmann)常數，且m爲氣體分子 的質量。爲了簡化粗略計算，該計算利用將可適化係數設 定爲最大値1來進行，且比熱率爲7/5及氣體分子的質量 爲3.3 X 1〇·27 Kg，其爲電漿主要氣體之氫分子的値。 最後，讓我們考慮輻射式傳遞熱的量。將該陽極視爲 無限平行板，由於熱輻射從平面y傳遞到平面z之熱傳遞 量Wm可表示成下式。 公式 3 HOxcrh4-：^4)·丁」. —I---1 ε2 其中^與^分別爲平面y與平面ζ的發射率，σ爲史特 凡-波兹曼（Stefan-Bolzmann)常數（5.67 X 1CT8 WnT2K'4)。 對於那三種熱傳遞機制，熱傳遞量的計算係在以下狀 況中計算：要做爲基板之矽的發射率爲0.6，鉬的發射率爲 〇 . 3，石墨的發射率爲〇. 9，基板1 0 1與陽極1 1 2之間的外 觀接觸面積與基板101與陽極112之間的真實接觸面積的 比例爲1/1000000，基板溫度爲920°C，陽極基板爲860°C， 且基板面積爲對於鉬電極，對基板101之接觸熱 導性成爲約5 W，鉬電極與基板1 0 1之間的自由分子導向的 熱導性成爲約10W，而熱輻射熱成爲約5W，然而對於石墨 電極，對基板1 0 1之接觸熱導性成爲約1 W，石墨電極與基 板1 〇 1之間的自由分子導向的熱導性成爲約1 0W，而熱輻 射熱成爲約1 1 W。當未施加應力到該介面且r成爲非常小 的値時，不隨著r變動之熱輻射及自由分子熱導性之傳遞 -62- 200905010 熱的比例會成爲較高。 我們考慮到當由電漿熱傳遞到基板爲固定的小r的情 況。即使基板與陽極之間的外觀接觸面積與基板及陽極之 間的真實接觸面積的比例r由於布局改變而變化時，r的絕 對値很小，所以由該基板傳遞熱量到該陽極之改變幾乎不 會根據輻射式的傳遞熱量，並僅改變正比於r改變的接觸 式傳遞熱量。此時，因爲輻射式傳遞熱量的貢獻成爲較大， 在接觸式傳遞熱量中大部分的改變即正比於（T,4 T24)，並 可由相對於溫度變化爲大的輻射式傳遞熱量改變來補償， 藉此使其有可能相對地降低1的改變量。顯示有大的分布 到輻射式傳遞熱的石墨電極可抑制相對於在具有小發射率 之電極中的改變在基板溫度中的變化，藉此穩定該等薄膜 沈積條件。 對於陽極1 1 2使用石墨電極可防止不想要的沈積物被 沈積在陽極1 1 2上，如下所述。 第34Α圖及第34Β圖所示分別爲薄膜沈積之後鉬電極 與石墨電極之狀態的照片。 將陽極1 1 2做爲鉬電極，如第34Α圖所示，於薄膜沈 積之後碳膜形成在並未安裝基板101的部分上。因此，當 新的基板放置在具有形成碳膜的鉬電極上時，在形成有碳 膜的部分處的表面粗糙度進一步改變，所以接觸式傳遞熱 使得溫度控制更加困難。 對於石墨電極，如第34B圖所示，幾乎沒有沈積物， 所以在表面粗糙度沒有變化的更爲穩定的溫度控制即成爲 -63- 200905010 可能。 雖然鉬電極的碳膜與鉬電極之底側之間的阻抗爲3ΜΩ 或更高，且在陽極與陰極本身之間施加電壓發生變化時， 石墨電極之上表面（無關於基板放置的部分或未放置基板 的部分）與該底部之間的阻抗與薄膜沈積之前並無變化’且 在陽極上表面與陰極之間施加的電壓可在平面上爲均勻。 因爲對陽極112使用石墨電極’成爲絕緣體之碳膜幾 乎不會沈積在陽極112上，所以陽極Π2之大體形狀於薄 膜沈積期間並不改變。此可防止電漿形狀的改變’其中可 預期薄膜沈積可穩定化。 本發明並不限於上述的具體實施例’並可修正成多種 其他型式。 如第35圖所示，在容納基板的凹處可形成在基板 安裝面1 1 2 a中，以加寬陽極1 1 2的熱輻射表面’以增加熱 輻射。 在此例中，較佳地是陽極1 1 2之底側爲突出，其突出 來匹配陽極1 1 2的凹處之深度，以使陽極1 1 2的均勻度均 勻，而使得陽極112之溫度均勻’且其較佳地是凹處形成 在平臺111之電極安裝面Ilia中，以匹配於陽極112之突 出且平臺111之底側爲突出，其突出來匹配電極安裝面 1 1 1 a之凹處的深度’以使平臺1 1 1的均句度均勻，而使得 平臺1 1 1的溫度均勻。然後較佳地是在相對面1 1 3 a中形成 的凹處而安裝在平臺111之底側中。 如第3 6圖所示’即使基板1 0 1的底側並非平滑，凹處 -64 - 200905010 可形成爲匹配基板1 ο 1的形狀，所以基板1 ο 1可安裝在該 凹處中。 在此例中，較佳地是陽極1 1 2之底側爲突出，其突出 來匹配陽極112的凹處之深度，以使陽極112的均句度均 句，而使得陽極1 1 2之溫度均勻，且其較佳地是凹處形成 在平臺111之電極安裝面111a中，以匹配於陽極112之突 出且平臺111之底側爲突出，其突出來匹配電極安裝面 1 1 1 a之凹處的深度，以使平臺1 1 1的均勻度均句，而使得 平臺1 1 1的溫度均句。然後較佳地是在相對面1 1 3 a中形成 的凹處而安裝在平臺111之底側中。 可以另使用在電源121施加在陽極112與陰極120之 間的D V電壓並未受到限制的結構，及施加高頻率之電漿 化學氣相沈積裝置。在此例中，對於電極使用石墨來冷卻 基板1 0 1即可冷卻具有熱輻射之基板，並可穩定薄膜沈積。 在不背離本發明之廣義精神與範圍之下可對其實施多 種具體實施例及改變。上述的具體實施例係要說明本發 明’而非限制本發明之範圍。本發明的範圍由所附申請專 利範圍而非具體實施例來表示。在本發明之申請專利範圍 之同等意義與申請專利範圍之內進行的多種修正可以視爲 在本發明的範圍中。 【圖式簡單說明】 第1圖爲根據本發明第一具體實施例之D C電漿化學氣 相沈積裝置的組態圖； 第2圖爲第1圖之環狀噴嘴及排氣埠之平面圖； -65- 200905010 第3A圖及第3B圖爲用於解釋在比較實驗中DC電漿 化學氣相沈積裝置之組態圖； 第4A圖爲在第3A圖及第3B圖中所示之DC電漿化學 氣相沈積裝置中發生在陰極上輝光狀態圖； 第4B圖爲根據第一具體實施例之dc電漿化學氣相沈 積裝置中發生在陰極上輝光狀態圖； 第5A圖及第5B圖爲根據本發明第二具體實施例中DC 電漿化學氣相沈積裝置之組態圖； 第6圖爲根據本發明第三具體實施例之DC電漿化學氣 相沈積裝置的組態圖； 第7圖爲驗證實驗的簡略圖； 第8圖爲用於解釋該驗證實驗之結果的圖； 第9A圖到第90圖爲用於解釋該驗證實驗之結果的影k 2πηιΤ where Λ is the thermal conductivity of the free molecule, 〇t is the adaptability coefficient, ρ is the pressure, -61 - 200905010 γ is the specific heat rate, k is the Boltzmann constant, and m is the mass of the gas molecule. In order to simplify the rough calculation, the calculation is performed by setting the adaptability coefficient to a maximum 値1, and the specific heat rate is 7/5 and the mass of the gas molecule is 3.3 X 1 〇·27 Kg, which is the hydrogen of the plasma main gas. The sputum of the molecule. Finally, let us consider the amount of radiant heat transfer. The anode is regarded as an infinite parallel plate, and the heat transfer amount Wm transmitted from the plane y to the plane z due to heat radiation can be expressed as follows. Equation 3 HOxcrh4-:^4)·丁”. —I---1 ε2 where ^ and ^ are the emissivity of plane y and plane 分别, respectively, and σ is the Stefan-Bolzmann constant ( 5.67 X 1CT8 WnT2K'4). For the three heat transfer mechanisms, the calculation of the heat transfer amount is calculated in the following cases: the emissivity of the substrate is 0.6, the emissivity of molybdenum is 0.3, and the emissivity of graphite is 〇 9. The ratio of the apparent contact area between 1 0 1 and the anode 1 1 2 to the true contact area between the substrate 101 and the anode 112 is 1/1000000, the substrate temperature is 920 ° C, the anode substrate is 860 ° C, and the substrate area For the molybdenum electrode, the thermal conductivity of the contact with the substrate 101 is about 5 W, the thermal conductivity of the free molecular orientation between the molybdenum electrode and the substrate 101 is about 10 W, and the heat of radiant heat is about 5 W, whereas for the graphite electrode The thermal conductivity of the contact with the substrate 110 was about 1 W, and the thermal conductivity of the free molecular orientation between the graphite electrode and the substrate 1 成为1 was about 10 W, and the heat of radiant heat was about 1 W. When no stress is applied to the interface and r becomes a very small enthalpy, the heat radiation that does not fluctuate with r and the thermal conductivity of the free molecule are transferred -62-200905010 The ratio of heat becomes higher. We consider the case when the heat is transferred from the plasma to the substrate as a fixed small r. Even if the ratio r of the apparent contact area between the substrate and the anode and the true contact area between the substrate and the anode changes due to the layout change, the absolute 値 of r is small, so the change of heat transferred from the substrate to the anode is hardly The heat is transferred according to the radiant type, and only the contact type heat transfer which is changed in proportion to r is changed. At this time, since the contribution of the radiant heat transfer becomes large, most of the change in the contact heat transfer is proportional to (T, 4 T24), and can be compensated by the radiant heat transfer change which is large with respect to the temperature change. This makes it possible to relatively reduce the amount of change of one. The graphite electrode showing a large distribution to the radiant heat transfer can suppress variations in the substrate temperature with respect to changes in the electrode having a small emissivity, thereby stabilizing the film deposition conditions. The use of a graphite electrode for the anode 1 1 2 prevents unwanted deposits from being deposited on the anode 1 1 2 as described below. Fig. 34 and Fig. 34 are photographs showing the state of the molybdenum electrode and the graphite electrode after film deposition, respectively. The anode 11 2 was used as a molybdenum electrode, and as shown in Fig. 34, a carbon film was formed on a portion where the substrate 101 was not mounted after the film was deposited. Therefore, when a new substrate is placed on the molybdenum electrode having the carbon film formed, the surface roughness at the portion where the carbon film is formed is further changed, so the contact transfer heat makes temperature control more difficult. For the graphite electrode, as shown in Fig. 34B, there is almost no deposit, so a more stable temperature control with no change in surface roughness becomes -63-200905010. Although the impedance between the carbon film of the molybdenum electrode and the bottom side of the molybdenum electrode is 3 Μ Ω or higher, and the voltage applied between the anode and the cathode itself changes, the upper surface of the graphite electrode (without the portion placed on the substrate or not) The impedance between the portion where the substrate is placed and the bottom is unchanged from that before film deposition' and the voltage applied between the upper surface of the anode and the cathode may be uniform in the plane. Since the carbon film which becomes the insulator for the anode 112 is hardly deposited on the anode 112, the general shape of the anode Π2 does not change during the deposition of the film. This prevents a change in the shape of the plasma, where it is expected that the film deposition can be stabilized. The invention is not limited to the specific embodiments described above and can be modified into a variety of other forms. As shown in Fig. 35, a recess in which the substrate is accommodated may be formed in the substrate mounting surface 1 1 2 a to widen the heat radiating surface ' of the anode 112 to increase heat radiation. In this case, it is preferred that the bottom side of the anode 112 is a protrusion that protrudes to match the depth of the recess of the anode 112 to make the uniformity of the anode 112 uniform, and the temperature of the anode 112 Uniformly' and preferably recessed in the electrode mounting surface Ilia of the platform 111 to match the protrusion of the anode 112 and the bottom side of the platform 111 is protruding, which protrudes to match the concave surface of the electrode mounting surface 1 1 1 a The depth is 'to make the uniformity of the platform 1 1 1 uniform, and the temperature of the platform 11 1 is uniform. It is then preferably mounted in the bottom side of the platform 111 in a recess formed in the opposite face 1 1 3 a. As shown in Fig. 3', even if the bottom side of the substrate 110 is not smooth, the recess -64 - 200905010 can be formed to match the shape of the substrate 1 ο 1 , so that the substrate 1 ο 1 can be mounted in the recess. In this case, it is preferred that the bottom side of the anode 112 is a protrusion that protrudes to match the depth of the recess of the anode 112 so that the average degree of the anode 112 is uniform, and the temperature of the anode 112 is made. Uniform, and preferably concavely formed in the electrode mounting surface 111a of the platform 111 to match the protrusion of the anode 112 and the bottom side of the platform 111 is protruding, which protrudes to match the concave surface of the electrode mounting surface 1 1 1 a The depth is such that the uniformity of the platform 1 1 1 is uniform, and the temperature of the platform 1 1 1 is uniform. It is then preferably mounted in the bottom side of the platform 111 in a recess formed in the opposite face 1 1 3 a. A structure in which the D V voltage applied between the anode 112 and the cathode 120 by the power source 121 is not limited, and a plasma chemical vapor deposition apparatus which applies a high frequency can be additionally used. In this case, the use of graphite to cool the substrate 110 for the electrode cools the substrate having heat radiation and stabilizes film deposition. Numerous embodiments and changes may be made without departing from the spirit and scope of the invention. The above-described embodiments are intended to illustrate the invention and not to limit the scope of the invention. The scope of the invention is indicated by the scope of the appended claims rather Various modifications made within the meaning of the scope of the invention and the scope of the claims can be construed as being within the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a configuration diagram of a DC plasma chemical vapor deposition apparatus according to a first embodiment of the present invention; FIG. 2 is a plan view of the annular nozzle and the exhaust manifold of FIG. 1; -65- 200905010 Figures 3A and 3B are diagrams for explaining the configuration of a DC plasma chemical vapor deposition apparatus in a comparative experiment; Figure 4A is a DC power shown in Figures 3A and 3B. a glow state diagram occurring on the cathode in the slurry chemical vapor deposition apparatus; FIG. 4B is a glow state diagram occurring on the cathode in the dc plasma chemical vapor deposition apparatus according to the first embodiment; FIGS. 5A and 5B a configuration diagram of a DC plasma chemical vapor deposition apparatus according to a second embodiment of the present invention; FIG. 6 is a configuration diagram of a DC plasma chemical vapor deposition apparatus according to a third embodiment of the present invention; 7 is a simplified diagram of the verification experiment; FIG. 8 is a diagram for explaining the result of the verification experiment; FIGS. 9A to 90 are diagrams for explaining the result of the verification experiment
第11圖爲實驗結果圖； 第12A圖及第12B圖爲根據本發明第四具體實施例之 DC電漿化學氣相沈積裝置之組態圖； 第13圖爲根據本發明第五具體實施例之DC電漿化學 氣相沈積裝置的組態圖； 第14圖爲上述第13圖之DC電漿化學氣相沈積裝置的 陰極、來源氣體噴嘴及排氣導管之圖； 第15圖爲由側向之第13圖的DC電漿化學氣相沈積裝 置之剖視圖， -66- 200905010 第16A圖及第16B圖爲根據本發明第六具體實施例之 DC電漿化學氣相沈積裝置之組態圖； 第17圖爲上述第16A圖之DC電漿化學氣相沈積裝置 的陰極、來源氣體噴嘴及排氣導管之圖； 第18圖爲由側向之第16A圖的DC電漿化學氣相沈積 裝置之剖視圖； 第19圖爲根據本發明第七具體實施例之DC電漿化學 氣相沈積裝置的組態圖； 第20圖爲上述第19圖之DC電漿化學氣相沈積裝置的 陰極、反應氣體噴嘴、基質氣體噴嘴及排氣導管之圖； 第21圖爲由側向之第19圖的DC電漿化學氣相沈積裝 置之剖視圖； 第22A圖及第22B圖爲根據本發明第八具體實施例之 DC電漿化學氣相沈積裝置之組態圖； 第23圖爲上述第22A圖之DC電漿化學氣相沈積裝置 的陰極、反應氣體噴嘴、基質氣體噴嘴及排氣導管之圖； 第24圖爲由側向之第22A圖的DC電漿化學氣相沈積 裝置之剖視圖； 第25圖爲該陰極的修正圖； 第26圖爲該陰極的修正圖； 第27圖爲該陰極的修正圖； 第2 8圖爲該陰極的修正圖； 第29A圖及第29B圖爲冷卻構件的修正圖； 第30A圖及第30B圖爲該冷卻構件的修正圖； -67- 200905010 第3 1圖爲根據本發明第九具體實施例之電漿化學氣相 沈積裝置的組態圖； 第3 2圖爲在薄膜沈積時石墨電極與鉬電極的溫度之間 的差異圖； 第3 3圖爲施加於電漿的功率變化圖； 第34A圖及第34B圖爲薄膜沈積之後陽極的狀態圖； 第3 5圖爲該電漿化學氣相沈積裝置之修正的簡略組態 圖； 第3 6圖爲該電漿化學氣相沈積裝置之修正的簡略組態 圖； 第37A圖爲習用電漿化學氣相沈積裝置的組態圖；及 第37B圖爲用於解釋第37A圖所示之習用電漿化學氣 相沈積裝置中反應爐中氣體的流動圖。 【主要元件符號說明】 1 基板 10 處理室 11 平臺 11a 陽極 lib 空間 llx 軸 12 冷卻構件 12a 導管 12b 流動通道 12c 導管 -68- 200905010 12w 上方側 12x 排氣孔 12y 溝槽 12z 側面 13 陰極 14 陰極支撐 15 絕緣單元 16 支撐 17 觀視窗 18 輻射溫度計 19 充氣管 20 排氣導管 21 電壓設定單元 21a 控制單元 21b 可變電源 22 環狀噴嘴 22a 噴出埠 23 絕緣體噴嘴支撐 24 停止器 25 氣體噴淋噴嘴 27 陰極 27a 中央電極 27b 周緣電極 27c 絕緣部分 28 電壓設定單元 -69 200905010 28a 控制單元 28b 可變電源 28c 可變電源 30 處理室 31 充氣管 32 充氣管 33 環狀噴嘴 33a 噴出埠 34 氣體噴淋噴嘴 35 陰極 35a 中央電極 35b 周緣電極 35c 絕緣部分 36 電壓設定單元 36a 控制單元 36b 可變電源 36c 可變電源 50 處理室 51 平臺 51a 陽極 51b 空間 52 冷卻構件 52a 導管 52b 流動通道 52c 導管 -70- 200905010 53 陰極 53x 軸 54 陰極支撐 55 絕緣單元 57 觀視窗 58 輻射溫度計 59 充氣管 60 排氣導管 61 電壓設定單元 61a 控制單元 61b 可變電源 62 噴u賀 62a 噴出埠 62A 部分 62B 部分 63 絕緣噴嘴支撐 65 陰極 65a 中央電極 65b 周緣電極 65c 絕緣部分 66 電壓設定單元 66a 控制單元 66b 可變電源 66c 可變電源 70 處理室 -71 200905010 71 充氣管 72 充氣管 73 噴嘴 73a 噴出埠 73A 部分 73B 部分 74 氣體噴淋噴嘴 75 陰極 75a 中央電極 75b 周緣電極 75c 絕緣部分 76 電壓設定單元 76a 控制單元 76b 可變電源 76c 可變電源 90 陰極 90a 中央電極 90b 周緣電極 90c 絕緣部分 91 陰極 91a 中央電極 91b 周緣電極 91c 絕緣部分 92 陰極 92a 中央電極 200905010 92b 圓形周緣電極 92c 絕緣部分 93 陰極 93a 中央電極 93b 第一環狀周緣電極 93c 第二環狀周緣電極 94 氦氣塡充單元 96 氮氣塡充單元 95 流量控制器 97 流量控制器 98 三向閥 99 冷卻單元 101 基板 110 處理室 111 平臺 112 陽極 111a 電極安裝面 111b 空間 111c 底面 112 陽極 112a 基板安裝面 113 冷卻構件 113a 相對面 113b 流動通道 113c 導管 -73 200905010 113d 導管 113e 排氣孔 115 冷卻單元 116 導管 117 閥 118 流量控制器 119 圓筒 120 陰極 121 電源 122 氣體供應管路 123 氣體排出管路 125 觀視窗 126 光譜輻射計 PC 正極柱 GI 氣體入口 GO 氣體出口 A 觀察點 B 觀察點 -74-11 is a diagram showing experimental results; FIGS. 12A and 12B are configuration diagrams of a DC plasma chemical vapor deposition apparatus according to a fourth embodiment of the present invention; and FIG. 13 is a fifth embodiment of the present invention. A configuration diagram of a DC plasma chemical vapor deposition apparatus; Fig. 14 is a diagram of a cathode, a source gas nozzle, and an exhaust conduit of the DC plasma chemical vapor deposition apparatus of the above Fig. 13; Fig. 15 is a side view A cross-sectional view of the DC plasma chemical vapor deposition apparatus of Fig. 13, -66-200905010, Figs. 16A and 16B are configuration diagrams of a DC plasma chemical vapor deposition apparatus according to a sixth embodiment of the present invention. Figure 17 is a diagram of the cathode, source gas nozzle and exhaust conduit of the DC plasma chemical vapor deposition apparatus of Figure 16A above; Figure 18 is a DC plasma chemical vapor deposition of the horizontal 16A 19 is a configuration diagram of a DC plasma chemical vapor deposition apparatus according to a seventh embodiment of the present invention; and FIG. 20 is a cathode of the DC plasma chemical vapor deposition apparatus of the above 19th embodiment; Diagram of reaction gas nozzle, substrate gas nozzle and exhaust conduit Figure 21 is a cross-sectional view of the DC plasma chemical vapor deposition apparatus of the 19th aspect; the 22A and 22B are DC plasma chemical vapor deposition apparatus according to the eighth embodiment of the present invention; FIG. 23 is a diagram of a cathode, a reaction gas nozzle, a substrate gas nozzle, and an exhaust conduit of the DC plasma chemical vapor deposition apparatus of the above-mentioned 22A; FIG. 24 is a lateral view of FIG. 22A. A cross-sectional view of the DC plasma chemical vapor deposition apparatus; Fig. 25 is a correction diagram of the cathode; Fig. 26 is a correction diagram of the cathode; Fig. 27 is a correction diagram of the cathode; and Fig. 28 is a correction of the cathode Fig. 29A and Fig. 29B are correction diagrams of the cooling member; Figs. 30A and 30B are correction diagrams of the cooling member; -67- 200905010, Fig. 3 1 is a diagram according to a ninth embodiment of the present invention A configuration diagram of a slurry chemical vapor deposition apparatus; Fig. 3 is a graph showing the difference between the temperature of the graphite electrode and the molybdenum electrode during film deposition; and Fig. 3 is a graph showing the power change applied to the plasma; And Figure 34B is a state diagram of the anode after film deposition; Figure 35 shows the A simplified configuration diagram of the correction of the plasma chemical vapor deposition apparatus; Fig. 3 is a simplified configuration diagram of the modification of the plasma chemical vapor deposition apparatus; and Fig. 37A is a conventional plasma chemical vapor deposition apparatus The configuration diagram; and Fig. 37B are diagrams for explaining the flow of gas in the reaction furnace in the conventional plasma chemical vapor deposition apparatus shown in Fig. 37A. [Main component symbol description] 1 Substrate 10 Processing chamber 11 Platform 11a Anode lib Space llx Axis 12 Cooling member 12a Conduit 12b Flow channel 12c Conduit-68- 200905010 12w Upper side 12x vent hole 12y Groove 12z Side 13 Cathode 14 Cathode support 15 Insulation unit 16 Support 17 View window 18 Radiation thermometer 19 Inflator tube 20 Exhaust duct 21 Voltage setting unit 21a Control unit 21b Variable power supply 22 Annular nozzle 22a Spray port 23 Insulator nozzle support 24 Stopper 25 Gas shower nozzle 27 Cathode 27a Central electrode 27b Peripheral electrode 27c Insulated portion 28 Voltage setting unit - 69 200905010 28a Control unit 28b Variable power supply 28c Variable power supply 30 Processing chamber 31 Inflator tube 32 Inflator tube 33 Annular nozzle 33a Discharge 埠 34 Gas shower nozzle 35 Cathode 35a central electrode 35b peripheral electrode 35c insulating portion 36 voltage setting unit 36a control unit 36b variable power supply 36c variable power supply 50 processing chamber 51 platform 51a anode 51b space 52 cooling member 52a conduit 52b flow channel 52c -70- 200905010 53 Cathode 53x Axis 54 Cathode support 55 Insulation unit 57 View window 58 Radiation thermometer 59 Inflation tube 60 Exhaust duct 61 Voltage setting unit 61a Control unit 61b Variable power supply 62 Spray uhe 62a Spray 埠 62A Part 62B Part 63 Insulated nozzle support 65 cathode 65a central electrode 65b peripheral electrode 65c insulating portion 66 voltage setting unit 66a control unit 66b variable power supply 66c variable power supply 70 processing chamber - 71 200905010 71 inflation tube 72 inflation tube 73 nozzle 73a ejection 埠 73A portion 73B portion 74 gas shower nozzle 75 cathode 75a central electrode 75b peripheral electrode 75c insulating portion 76 voltage setting unit 76a control unit 76b variable power supply 76c variable power supply 90 cathode 90a central electrode 90b peripheral electrode 90c insulating portion 91 cathode 91a central electrode 91b peripheral electrode 91c Insulation portion 92 Cathode 92a Central electrode 200905010 92b Circular peripheral electrode 92c Insulation portion 93 Cathode 93a Central electrode 93b First annular peripheral electrode 93c Second annular peripheral electrode 94 Helium filling 96 Nitrogen charging unit 95 Flow controller 97 Flow controller 98 Three-way valve 99 Cooling unit 101 Substrate 110 Processing chamber 111 Platform 112 Anode 111a Electrode mounting surface 111b Space 111c Bottom surface 112 Anode 112a Substrate mounting surface 113 Cooling member 113a Opposite surface 113b Flow channel 113c conduit-73 200905010 113d conduit 113e vent 115 cooling unit 116 conduit 117 valve 118 flow controller 119 cylinder 120 cathode 121 power supply 122 gas supply line 123 gas discharge line 125 view window 126 spectral radiometer PC positive Column GI gas inlet GO gas outlet A observation point B observation point -74-